WO2020125714A1 - 双组分水性聚氨酯涂料组合物以及由其形成的低光泽度涂层 - Google Patents

双组分水性聚氨酯涂料组合物以及由其形成的低光泽度涂层 Download PDF

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WO2020125714A1
WO2020125714A1 PCT/CN2019/126608 CN2019126608W WO2020125714A1 WO 2020125714 A1 WO2020125714 A1 WO 2020125714A1 CN 2019126608 W CN2019126608 W CN 2019126608W WO 2020125714 A1 WO2020125714 A1 WO 2020125714A1
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component
copolymer
weight
coating composition
range
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PCT/CN2019/126608
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English (en)
French (fr)
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甘延长
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 EP19898592.1A priority Critical patent/EP3901229A4/en
Priority to US17/413,005 priority patent/US20220064479A1/en
Priority to CA3122446A priority patent/CA3122446A1/en
Publication of WO2020125714A1 publication Critical patent/WO2020125714A1/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
    • 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
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents

Definitions

  • the present application relates to a two-component waterborne polyurethane coating composition.
  • the present application also relates to a low gloss coating obtained from the two-component waterborne polyurethane coating composition.
  • the two-component water-based polyurethane coating composition as an important water-based two-component coating, has high performance and
  • the advantage of multi-function is the development direction of water-based coatings. It has the advantages of low film forming temperature, strong adhesion, good wear resistance, high hardness, chemical resistance and weather resistance. VOC is significantly reduced, and the performance is better than or Equivalent to solvent-based two-component polyurethane coatings.
  • the two-component waterborne polyurethane coating composition is composed of an NCO group-containing polyisocyanate curing agent and an OH group-containing waterborne polyol, and its coating film performance is mainly determined by the composition and structure of the waterborne polyol.
  • the water-based polyol includes acrylic polyol, polyester polyol, polyurethane or alkyd polyol, and may also be a hybrid mixture of two or more of the above.
  • Acrylic polyol has the advantages of low molecular weight, high hydroxyl functionality and small particle size. It can be made with isocyanate prepolymer with light color, excellent light and color retention, chemical resistance, strong anti-pollution performance, outdoor weather resistance Good high-decorative paint can also be made into external anti-corrosion decorative paint.
  • Matte coatings also known as low gloss coatings
  • the demand for water-based matte coatings is increasing.
  • low gloss coatings are mainly obtained by adding a certain amount of matting agent to the coating composition. After the coating composition thus formed is formed into a film, the matting agent particles distributed in the paint film make the surface uneven, increase the scattering of light and reduce the reflection, thereby producing a low-gloss matte effect.
  • the matting agent material due to the limitation of the characteristics of the matting agent material, common matting agents such as micron-scale silica are difficult to disperse in the polymer emulsion, and long-term storage is extremely prone to sedimentation.
  • common matting agents such as micron-scale silica are difficult to disperse in the polymer emulsion, and long-term storage is extremely prone to sedimentation.
  • due to the poor transparency of the matting agent it is easy to cause the paint film to become white and the permeability is reduced.
  • the matting agent has a strong thickening property, the amount of addition is limited, and it is difficult to produce a lower gloss product.
  • the coating industry still needs a two-component waterborne polyurethane coating composition suitable for providing low gloss coatings.
  • the present application provides a two-component waterborne polyurethane coating composition, comprising:
  • a film-forming resin composition comprising an aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure
  • the hydroxyacrylic polymer particles having a core-shell structure include an outer shell formed by copolymer A and an inner core formed by copolymer B,
  • the glass transition temperature of the copolymer A is in the range of -20°C to 60°C
  • the glass transition temperature of the copolymer B is in the range of 20°C to 100°C
  • the hydroxy acrylic polymer having a core-shell structure The glass transition temperature of the particles is in the range of 10°C to 90°C.
  • the present application provides a low-gloss coating, characterized in that the low-gloss coating has a gloss of 75 ° or less at 60 ° , the low-gloss coating according to the present invention
  • the applied two-component waterborne polyurethane coating composition is formed.
  • the present application provides a method for preparing an aqueous dispersion of hydroxy acrylic resin polymer particles having a core-shell structure, which includes the following steps:
  • a monomer mixture for forming copolymer B use the aqueous emulsion obtained by swelling the monomer mixture for forming copolymer B, and then use the monomer mixture for forming copolymer B to perform in-situ emulsion polymerization To obtain an aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure, wherein the hydroxyacrylic polymer particles having a core-shell structure contain copolymer A as a shell and copolymer B as a core, wherein the aqueous dispersion of The solid content is controlled at 30-45% by weight.
  • the inventor of the present application pioneered to provide a two-component waterborne polyurethane coating composition
  • a film-forming resin composition containing an aqueous dispersion of hydroxyacrylic polymer particles with a specific core-shell structure, and a polyisocyanate cross Joint agent; in the absence of matting agent, the two-component waterborne polyurethane coating composition can provide a low gloss coating after curing, the low gloss coating has a gloss of 75 ° or less at 60 ° Degree, reduce or eliminate the negative effects (such as loss of coating fluidity) caused by the introduction of matting agents in the prior art to reduce the gloss of the coating.
  • the inventor of the present application was also surprised to find that the cured coating formed from this two-component waterborne polyurethane coating composition has comparable, even better hardness and chemical resistance than conventional waterborne coating compositions Sex.
  • composition is described as including or containing specific components, it is expected that optional components not mentioned in this application are not excluded from the composition, and that the composition is expected to be composed or composed of the components involved, or In cases where the method is described as including or containing specific process steps, it is expected that the method does not exclude optional process steps not covered by this application, and it is expected that the method may be constituted or composed of the process steps involved.
  • low gloss coating refers to a coating with a gloss of 0.1 to 80, preferably 1 to 75, which is measured at a reflection angle of 60° by means of a Sheen small hole gloss meter .
  • the term “matting agent-free” means that the two-component waterborne polyurethane coating composition of the present application is completely free of additional additives that can produce a matting effect.
  • Such agents include, but are not limited to, micron synthetic silica, micronized wax, stearate, talc/chlorite powder, and other agents known to those skilled in the art that can be used for matting.
  • 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 likewise any upper limit can be combined with any other upper limit to form an unspecified range.
  • each point or single value between the end points of the range is included in the range.
  • each point or single numerical value may be combined with any other point or single numerical value as its own lower limit or upper limit or with other lower or upper limits to form an unspecified range.
  • the numerical range defined by the endpoints includes all numerical values within the range, for example, the range of 1 to 5 covers the numerical values 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and so on.
  • the disclosed numerical range includes all sub-ranges within the broader range, for example, the range of 1 to 5 includes sub-ranges 1 to 4, 1.5 to 4.5, 1 to 2, and so on.
  • FIG. 1 schematically shows the film-forming resin composition of Example 1 and commercially available 2D and 3D drawings of the surface of the paint film formed by the two-component aqueous polyurethane coating composition prepared by mixing the XP 2655 curing agent with an OH/NCO molar ratio of 1/1.5.
  • FIG. 2 schematically shows the film-forming resin composition of Example 2 and commercially available 2D and 3D drawings of the surface of the paint film formed by the two-component aqueous polyurethane coating composition prepared by mixing the XP 2655 curing agent with an OH/NCO molar ratio of 1/1.5.
  • FIG. 3 schematically shows the film-forming resin composition of Example 3 and commercially available 2D and 3D drawings of the surface of the paint film formed by the two-component aqueous polyurethane coating composition prepared by mixing the XP 2655 curing agent with an OH/NCO molar ratio of 1/1.5.
  • FIG. 4 schematically shows the film-forming resin composition of Example 4 and commercially available 2D and 3D drawings of the surface of the paint film formed by the two-component aqueous polyurethane coating composition prepared by mixing the XP 2655 curing agent with an OH/NCO molar ratio of 1/1.5.
  • FIG. 5 schematically shows the film-forming resin composition of Example 5 and commercially available 2D and 3D drawings of the surface of the paint film formed by the two-component aqueous polyurethane coating composition prepared by mixing the XP 2655 curing agent with an OH/NCO molar ratio of 1/1.5.
  • Figure 6 schematically shows the commercially available models as XP 2470 waterborne hydroxyl polyacrylic acid dispersion and commercially available XP 2655 curing agent is mixed with OH/NCO molar ratio of 1/1.5 to form a 2D image of the paint film surface.
  • FIG. 7 schematically shows the core-shell structure hydroxy acrylic resin emulsion prepared according to Example 7 of CN107434842A and the commercially available XP 2655 curing agent is mixed with OH/NCO molar ratio of 1/1.5 to form a 2D image of the paint film surface.
  • Fig. 8 schematically shows the film-forming resin model MT2008 # of Guangdong Huaguoshan Environmental Protection Technology Co., Ltd. and the commercially available film-forming resin XP 2655 curing agent is mixed with OH/NCO molar ratio of 1/1.5 to form a 2D image of the paint film surface.
  • the present application provides a two-component waterborne polyurethane coating composition, comprising:
  • a film-forming resin composition comprising an aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure
  • the hydroxyacrylic polymer particles having a core-shell structure include an outer shell formed by copolymer A and an inner core formed by copolymer B,
  • the glass transition temperature of the copolymer A is in the range of -20°C to 60°C
  • the glass transition temperature of the copolymer B is in the range of 20°C to 100°C
  • the hydroxy acrylic polymer having a core-shell structure The glass transition temperature of the particles is in the range of 10°C to 90°C.
  • film-forming resin composition refers to a resin composition that constitutes the main body of a coating layer formed from the two-component aqueous polyurethane coating composition of the present application, which may include hydroxyacrylic polymer particles having a core-shell structure Aqueous dispersion, solvent and optional additional additives.
  • the film-forming resin composition comprises, relative to the total weight of the film-forming resin composition, from about 20% to about 100% by weight, preferably from about 30% to about 99% by weight, more preferably from about 60% by weight to About 90% by weight of an aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure.
  • the film-forming resin composition includes about 25% by weight, about 35% by weight, about 45% by weight, about 55% by weight, about 65% by weight, relative to the total weight of the film-forming resin composition. About 75% by weight, about 85% by weight, about 95% by weight, or about 99% by weight aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure.
  • the outer shell is soft, and its glass transition temperature (Tg) is in the range of -20°C to 60°C.
  • Tg refers herein to the glass transition temperature, which is the temperature at which a polymer changes from a glassy, brittle state to a rubber state.
  • the Tg value can be experimentally determined by using a technique such as differential scanning calorimetry (DSC) or calculated using the Fox equation. Unless otherwise stated, the Tg values and ranges given herein are based on Tg calculated using the Fox equation.
  • the Tg of the copolymer with n copolymerized comonomers passes the weight fraction W of each comonomer type and the Tg (in open terms) of the homopolymer obtained from each comonomer Degree meter) gives:
  • Tg calculated in degrees Kelvin can be easily converted to degrees Celsius (°C).
  • the inventors believe that the Tg of the outer shell greatly affects the ability of the aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure as a film-forming resin to coagulate into a film.
  • the lower the Tg of the outer shell the better the flexibility of the shell, and the polymer particles can also coagulate into a film at a lower temperature.
  • such a soft shell can withstand the shearing action during the coating process without cracking.
  • the copolymer shell is designed to have a low Tg.
  • the copolymer shell of the polymer particles has a Tg of 60°C or lower, preferably has a Tg of 50°C or lower, more preferably has a Tg of 40°C or lower, and even more preferably has a Tg of 30 Tg or lower.
  • the copolymer shell of the polymer particles has a Tg of -20°C or higher, more preferably a Tg of 0°C or higher, even more preferably a Tg of 5°C or higher.
  • the polymer particles are designed as a soft shell hard core structure.
  • the glass transition temperature of the copolymer core is at least 10°C higher than the glass transition temperature of the copolymer shell, preferably at least 15°C higher, more preferably at least 20°C higher, even more preferably at least 25°C higher or higher.
  • the aqueous dispersion of hydroxyacrylic polymer particles having a core-shell structure determined according to experiments has a Tg in the range of 0-30°C, preferably, the Tg is in the range of 10-30°C Within range.
  • the acid value of the copolymer A is in the range of 3-40 mg KOH/g
  • the acid value of the copolymer B is in the range of 0-10 mg KOH/g
  • the hydroxy acrylic acid with a core-shell structure is polymerized
  • the acid value of the particles is in the range of 3-40mg KOH/g.
  • the acid value is measured by ISO 2114 titration.
  • the hydroxy value of the copolymer A is in the range of 40-150 mg KOH/g
  • the hydroxy value of the copolymer B is in the range of 5-60 mg KOH/g
  • the hydroxy acrylic acid with a core-shell structure is polymerized
  • the hydroxyl value of the particles is in the range of 40-150 mg KOH/g, preferably the hydroxyl value of the core-shell structured hydroxy acrylic polymer particles is in the range of 42-80 mg KOH/g.
  • the hydroxyl value is measured by ISO4629 titration.
  • each of the copolymer A and the copolymer B is formed of the following monomers:
  • (meth)acrylate means acrylate, methacrylate and mixtures of both.
  • suitable C1-C20 alkyl methacrylates suitable for this application include, but are not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methyl N-butyl acrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-octyl methacrylate Ester, 2-ethylhexyl methacrylate, nonyl methacrylate, 2-methyloctyl methacrylate, 2-tert-butylheptyl methacrylate, 3-isopropylheptyl methacrylate , Decyl methacrylate, undec
  • methyl methacrylate ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate, particularly preferred are methyl methacrylate, tert-butyl methacrylate or butyl methacrylate .
  • C1-C20 alkyl acrylates suitable for this application include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tertiary acrylate Butyl ester, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, 2-methyl-octyl acrylate, acrylic acid -2-tert-butylheptyl, 3-isopropylheptyl acrylate, decyl acrylate, undecyl acrylate, 5-methyl undecyl acrylate, dodecyl acrylate, acrylic-2 -Methyl dodecyl ester, tridecyl acrylate
  • Suitable vinyl aromatic compounds b) having up to 20 carbon atoms include, but are not limited to, styrene, vinyl toluene, o-methylstyrene, p-methylstyrene, ⁇ -butylstyrene, 4 -N-butylstyrene, 4-n-decylstyrene, halogenated styrene (eg monochlorostyrene, dichlorostyrene, tribromostyrene or tetrabromostyrene). Styrene is preferred.
  • Suitable ethylenically unsaturated monomers with acid functional groups c) include, but are not limited to, phosphate functionalized or carboxylic acid functionalized monomers, preferably carboxylic acid functionalized monomers such as acrylic acid, methacrylic acid , Monoalkyl esters or anhydrides of ⁇ -carboxyethyl acrylate, crotonic acid, fumaric acid, maleic anhydride, itaconic acid or dibasic acid (for example, monoalkyl maleate). Particularly preferred is acrylic acid or methacrylic acid, and methacrylic acid is most particularly preferred.
  • Also suitable as compounds of component c) are unsaturated, free-radically polymerizable compounds having phosphate groups or phosphonate groups or sulfonic acid groups or sulfonate groups, which have been described in eg WO 00/39181 (Page 8, line 13 to page 9, line 19).
  • Suitable hydroxy C1-C20 alkyl (meth)acrylates include, but are not limited to, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate Ester or hydroxybutyl acrylate.
  • the monomers forming the copolymer A include: 45-75% by weight of the components based on the total weight of components a), b), c) and d) being 100% by weight a), 0-10% by weight of component b), 4-15% by weight of component c), and 10-45% by weight of component d).
  • the monomers forming the copolymer A include: 45-75% by weight of the components based on the total weight of components a), b), c) and d) being 100% by weight a), 0-10% by weight of component b), 4-15% by weight of component c), and 1-30% by weight of component d).
  • the monomers forming the copolymer B include: based on the total weight of components a), b), c) and d) being 100% by weight, 50-85% by weight of the component a), 0-20% by weight of component b), 0.5-5% by weight of component c), and 10-35% by weight of component d).
  • the weight ratio of the monomer forming the copolymer A to the monomer forming the copolymer B is 1:5 to 4:1, preferably 1:2 to 2:1.
  • the film-forming resin composition of the present application may also contain conventional additives that do not adversely affect the two-component aqueous polyurethane coating composition or the cured coating obtained therefrom.
  • Suitable additives include, for example, improve the processability or manufacturing performance of the composition, enhance the aesthetics of the composition, improve the specific functional properties or characteristics of the coating composition or the cured composition obtained therefrom (such as adhesion to the substrate) ) Or those that reduce costs.
  • Additives that may be included are, for example, fillers, lubricants, film-forming aids, wetting agents, plasticizers, defoamers, colorants, antioxidants, flow control agents, thixotropic agents, dispersants, adhesion promoters, UV Stabilizers, thickeners, pH adjusters, solvents, or combinations thereof.
  • the content of each optional ingredient is sufficient for its intended purpose, but preferably, such content does not adversely affect the two-component aqueous polyurethane coating composition or the cured coating obtained therefrom.
  • the film-forming resin composition of the present application may contain a thickening agent, a dispersing agent, a defoaming agent, a wetting agent, a pH adjusting agent, a filler, a film-forming aid, a mildew-proofing agent, a preservative or Any combination thereof can be used as a conventional additive.
  • the total amount of conventional additives is 0.1% to about 10% by weight relative to the total weight of the film-forming resin composition.
  • the film-forming resin composition according to the present application includes a weight relative to the film-forming resin composition
  • additional additives selected from one or more of defoamers, surfactants, wetting agents and thickeners;
  • the total amount of all components is 100% by weight.
  • alcohols such as ethylene glycol, propylene glycol, hexanediol, benzyl alcohol, etc.
  • alcohol esters such as dodecyl alcohol ester
  • alcohol ethers such as ethylene glycol butyl ether, Propylene glycol methyl ether, propylene glycol ether, propylene glycol n-propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, tripropylene glycol n-butyl ether, etc.
  • alcohol ether esters such as hexanediol butyl ether acetate Ester etc.
  • BYK 028 available from BYK Corporation can be used.
  • BYK 341 available from BYK Corporation can be used.
  • BYK 348 available from BYK Corporation can be used.
  • ACRYSOL RM TM -2020E can be used.
  • the film-forming resin composition of the present application contains an aqueous dispersion of hydroxyacrylic polymer particles having a specific core-shell structure, wherein the hydroxyacrylic polymer particles having a core-shell structure include an outer shell formed of copolymer A and a copolymer B In the inner core, the outer shell is soft and has a lower glass transition temperature, while the inner core is hard and has a higher glass transition temperature, and the core-shell ratio is appropriate.
  • This aqueous dispersion of hydroxyacrylic polymer particles with a soft-shell hard core structure provides good film-forming properties, requiring only a small amount of film-forming aids to form a film, greatly reducing the VOC content in the coating, making the coating more compliant Environmental requirements.
  • the inventor was surprised to find that the coatings formulated with such an aqueous dispersion of soft shell hard core structured hydroxyacrylic polymer particles have a large number of microporous structures, which was difficult to foresee before the present application. Without being bound to any theory, the applicant speculates that this surface microporous structure may be the main reason for the low gloss of the coating.
  • the hydroxyl groups are mainly distributed in the outer shell portion of the emulsion, thereby increasing the probability of contact with the polyisocyanate crosslinking agent and increasing the crosslinking density of the coating, thus The hardness and chemical resistance of the coating have been significantly improved, and the amount of polyisocyanate crosslinking agent required for curing has also been significantly reduced.
  • the emulsion polymerization technique for preparing an aqueous latex from ethylenically unsaturated monomers is well known in the polymer field, and any conventional emulsion polymerization process such as a single-stage polymerization process, a multi-stage polymerization process, a continuous process, etc. can be used. It is well known that the seed polymerization process can be used to prepare aqueous latex in order to control the structure and composition of the polymer particles contained in the aqueous latex.
  • the aqueous latex is prepared as follows: a) Under the action of an appropriate emulsifier and with the aid of stirring, the monomer mixture is dispersed into an emulsion in water, and then the formulated emulsion droplets are added to Polymerization is carried out in a polymerization reactor containing an initiator to form a seed emulsion as a polymer shell; b) Next, in the presence of the seed emulsion, the formed seed emulsion is swollen with another monomer mixture, and the other This monomer mixture undergoes in-situ emulsion polymerization to form polymer particles with a core-shell structure.
  • a method for preparing an aqueous dispersion of hydroxyacrylic resin polymer particles having a core-shell structure comprising the following steps: 1) providing for forming copolymer A Monomer mixture: in the presence of water, emulsifier and a part of the initiator, metering the monomer mixture for forming copolymer A with respect to the total weight of the monomer mixture 1-20% by weight, and then metering in The remaining monomer mixture for forming copolymer A and the remaining initiator are emulsion polymerized to obtain an aqueous emulsion containing copolymer A, wherein the solid content of the aqueous emulsion is controlled in the range of 20-30% by weight; and 2) Provide a monomer mixture for forming copolymer B: use the aqueous emulsion obtained by swelling the monomer mixture for forming copolymer B, and then use the monomer mixture for forming copolymer B
  • emulsifiers examples include anionic surfactants, nonionic surfactants, or combinations thereof, which are well known in the art.
  • McCutcheon s Detergents and Emulsifers (MC Publishing Co., Glen Rock, N.J.) disclose some surfactants suitable for emulsion polymerization.
  • Other types of stabilizing agents can also be used, such as protective colloids.
  • a combination of anionic surfactants and nonionic surfactants is used.
  • Nonionic surfactants include alkylphenol polyoxyethylene ethers and fatty alcohol polyoxyethylene ethers.
  • alkylphenol polyoxyethylene ethers are used.
  • Anionic surfactants include aliphatic carboxylates, aliphatic sulfonates, aliphatic sulfates, and aliphatic phosphates.
  • alkali metals such as Na, K or Li, or alkaline earth metal salts such as Ca or Ba are used.
  • an aliphatic sulfonate is used, preferably an alkali metal dodecyl sulfonate, and more preferably sodium dodecyl sulfonate (SDS).
  • any known free radical initiator can be used to initiate the polymerization reaction.
  • useful initiators include initiators that thermally decompose at the polymerization temperature to generate free radicals.
  • water-soluble and water-insoluble initiators examples include persulfates, such as ammonium persulfate or alkali metal persulfates (including potassium, sodium, or lithium); peroxides, such as cumene hydrogen peroxide, tert-butyl hydrogen peroxide, Di-tert-butyl peroxide, dioctyl peroxide, tert-butyl pervalerate, tert-butyl perisononanoate, tert-butyl peroctoate, tert-butyl peroctodecanoate, peroxy Di(2-ethylhexyl) dicarbonate, bis(isotridecyl) peroxydicarbonate; azo compounds such as azobis(isobutyronitrile
  • a chain transfer agent is optionally added, and the chain transfer agent includes, but is not limited to, n-dodecyl mercaptan, isooctyl 3-mercaptopropionate, and ⁇ -methyl
  • styrene dimers and the like are preferably n-dodecyl mercaptan.
  • the amount of emulsifier and initiator and the reaction conditions such as reaction temperature, stirring speed, etc. can be determined by those skilled in the art based on experience .
  • the pre-emulsification process of the monomer mixture is performed at a stirring speed of 2000 rpm or higher, preferably at a stirring speed of 4000 rpm or higher.
  • polyisocyanate crosslinking agent refers to a polyisocyanate compound, an isocyanate oligomer, or a combination thereof.
  • the polyisocyanate crosslinking agent contains two or more isocyanate functional groups, which can undergo chain extension and crosslinking reactions with the film-forming resin composition, thereby forming a three-dimensional network structure in the coating.
  • Suitable polyisocyanate crosslinking agents include aliphatic polyisocyanates, aromatic polyisocyanates, or any combination thereof.
  • aliphatic polyisocyanate refers to a polyisocyanate compound in which an isocyanate group is directly attached 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 poly Phenyl polyisocyanate.
  • a polyurethane-type prepolymer of any polyisocyanate compound listed above, a polyester-type prepolymer of any polyisocyanate compound listed above, or a polymer of any polyisocyanate compound listed above can be used Ether prepolymer and any combination thereof.
  • the polyurethane type prepolymer, polyester type prepolymer or polyether type prepolymer can be made by any suitable method known to those of ordinary skill in the art.
  • a polyurethane-type prepolymer can be made by reacting a polyol monomer and one or more of polyisocyanate compounds under appropriate conditions; a polyester-type prepolymer or a polyether-type prepolymer It can be produced by reacting polyester polyol or polyether polyol with one or more of polyisocyanate compounds under appropriate conditions.
  • a polyurethane-type prepolymer polyester-type prepolymer or polyether-type prepolymer, any appropriate commercial product can be used as the polyurethane-type prepolymer.
  • Preferred polyisocyanate crosslinking agents are unblocked or blocked polyisocyanates, more preferably hydrophilic group modified and/or at least partially hydrophilic group modified, unblocked polyisocyanates, even more preferred Modified by hydrophilic groups.
  • the polyisocyanate crosslinking agent is a hydrophilic group modified polyisocyanate crosslinking agent.
  • any suitable commercially available product such as Coverstro’s XP 2655 (hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI)).
  • the amounts of the polyisocyanate crosslinking agent and the film-forming resin composition are selected such that the molar ratio of hydroxyl groups (OH) to isocyanate groups (NCO) in the resulting system varies in the range of 1:1 to 1:2.5.
  • the molar ratio of hydroxyl groups (OH) to isocyanate groups (NCO) is less than 1:2.5, the handling properties of the resulting two-component polyurethane topcoat and/or the mechanical properties of the resulting coating may be reduced.
  • the molar ratio of hydroxyl groups (OH) to isocyanate groups (NCO) is greater than 1:1, the resulting coating has poor curing properties.
  • additional inert diluents that do not affect the reactivity of the above film-forming resin composition and polyisocyanate cross-linking agent can be added during the preparation of the film-forming resin composition and/or polyisocyanate cross-linking agent , For example, to reduce the viscosity of each component. Therefore, the amounts of the film-forming resin composition and the polyisocyanate curing agent are not limited to the above ranges, and can be adjusted according to actual needs.
  • the two-component aqueous polyurethane coating composition can be prepared by: before application, the film-forming resin composition and the polyisocyanate curing agent are simply mixed in a mixing device at a predetermined weight ratio.
  • the mixed two-component waterborne polyurethane coating composition can be applied using various methods familiar to those skilled in the art, including spraying (eg, air-assisted, airless or electrostatic spraying), brushing, roller coating, overflow coating, and dipping .
  • the mixed two-component aqueous polyurethane coating composition is applied by spraying.
  • Two-component waterborne polyurethane coating compositions can be applied to various wet film thicknesses.
  • the wet film thickness preferably provides a dry film thickness of about 13 to about 260 ⁇ m, and more preferably about 75 to about 150 ⁇ m.
  • the applied coating can be cured by air drying or by using various drying devices (for example, ovens) familiar to those skilled in the art to accelerate the curing.
  • a low gloss coating is provided, characterized in that the low gloss coating has a gloss of 75 ° or less at 60 ° , and the low gloss coating Formed from a two-component waterborne polyurethane coating composition according to the present application.
  • the low gloss coating has a gloss of 60 ° or less at 60 ° .
  • the surface of the low gloss coating has micropores, and the average diameter of the micropores is 1-10 microns, preferably 5-10 microns.
  • the surface of the low gloss coating has micropores, and the average depth of the micropores is 0.1-2 microns, preferably 0.3-1.5 microns.
  • average depth refers to the sum of the maximum profile peak height Zp and the maximum profile valley depth Zv of a microwell within a sampling length, and the average is measured multiple times.
  • the present application also relates to the use of the two-component aqueous polyurethane coating composition according to the present application in the preparation of a low gloss coating, wherein the low gloss coating has a gloss at 60 ° of 60 or less.
  • the viscosity of the aqueous dispersion of polymer particles is measured in seconds (s) using an NK-2 viscosity cup according to ASTM D 4212.
  • the air drying time was measured according to GB/T 1728-1979 (1989).
  • Pendulum hardness is used to measure the curing performance of the curing system. Measured according to GB/T 1730-2007.
  • This test is used to measure the hardness of cured coatings. Use ASTM D3363 to evaluate pencil hardness. The data is reported as the pencil hardness of the last successful test before the coating cracked. Thus, for example, if the coating does not break when tested with a 2H pencil, but breaks when tested with a 3H pencil, the coating is reported to have a pencil hardness of 2H.
  • Adhesion test was performed to assess whether the coating adhered to the coated substrate. This adhesion test is performed in accordance with ASTM 3359-Test Method B. Adhesion is usually divided into a grade of 0-5B, where 5B represents the optimal adhesion.
  • the surface of the sample is imaged in dark field mode by an optical microscope.
  • the microscope used is Keyence VHX-5000, with a Z1000 type lens.
  • aqueous dispersion of hydroxyacrylic resin polymer particles having a core-shell structure was prepared according to the ingredients shown in Table 3 below. The specific steps are: the mixed monomer of M1 is first emulsified with 0.3 wt% SDS emulsifier and 70 wt% DIW. Under a mixed atmosphere of nitrogen and oxygen, add a 5wt% M1 solution to a four-necked flask equipped with a SDS, APS, and DIW equipped with a thermometer, overhead stirrer, and gas inlet, then heat to 80-90°C and keep under stirring 20 minutes, and then the remaining M1 solution and APS solution were added dropwise over about 100 minutes and 120 minutes, respectively.
  • copolymer A The solid content of copolymer A is controlled in the range of 20-30% by weight.
  • the film-forming resin composition was prepared according to the ingredients in Table 5 below.
  • the film-forming aid, water, and additional additives were added to the aqueous dispersion of the hydroxyacrylic resin polymer particles having a core-shell structure of Samples 1-5 under stirring, thereby forming a film-forming resin composition.
  • a film resin composition was prepared using aqueous hydroxyacrylic acid dispersions WQ1321P, OH-7, and OH-8 from Valspar as Comparative Examples 1-3, respectively.
  • the film-forming resin composition prepared above is combined with XP2655 (hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI) from Coverstro) is mixed in a certain ratio.
  • XP2655 hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI) from Coverstro
  • the properties of the pendulum rod hardness, gloss, adhesion, chemical resistance and other properties of the cured coating were measured. The results are shown in Table 6. Prior to testing, the coating formed above was dried in air for 7 days.
  • the two-component waterborne polyurethane coating composition according to the present application after curing, obtained a coating with a significantly lower gloss compared to other acrylic waterborne latexes from Valspar,
  • the low gloss coating has a gloss of 75 ° or less at 60 ° .
  • the coating has acceptable coating properties, including adhesion, hardness, and chemical resistance.
  • the inventors compared the difference in performance, especially the glossiness, the applicant separately compared Examples 1-5 and other commercially available acrylic resins Emulsion, for example model XP 2470 waterborne hydroxyacrylic acid dispersion, Guangdong Huaguoshan Environmental Protection Technology Co., Ltd. model MT2008 # film-forming resin and the coating made of core-shell structured hydroxyacrylic resin emulsion prepared according to Example 7 of CN107434842A, the image is shown in Figure 1-8.
  • acrylic resins Emulsion for example model XP 2470 waterborne hydroxyacrylic acid dispersion, Guangdong Huaguoshan Environmental Protection Technology Co., Ltd. model MT2008 # film-forming resin and the coating made of core-shell structured hydroxyacrylic resin emulsion prepared according to Example 7 of CN107434842A, the image is shown in Figure 1-8.
  • a two-component waterborne polyurethane coating composition according to the present application has a large number of micropores formed on the surface of the coating after curing, which is significantly different from the prior art coating.

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Abstract

一种双组分水性聚氨酯涂料组合物，包含成膜树脂组合物，其包含具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体和多异氰酸酯交联剂，该具有核壳结构的羟基丙烯酸聚合物颗粒包含由共聚物A形成的外壳和共聚物B形成的内核，该共聚物A的玻璃化转变温度在-20℃至60℃范围内，该共聚物B的玻璃化转变温度在20℃至100℃范围内，该具有核壳结构的羟基丙烯酸聚合物颗粒的玻璃化转变温度在10℃至90℃范围内。该双组分聚氨酯涂料组合物可形成低光泽度涂层。

Description

双组分水性聚氨酯涂料组合物以及由其形成的低光泽度涂层
相关申请的交叉引用
本申请要求2018年12月21日提交的中国专利申请201811570831.7的权益，所述申请通过引用整体并入本文。
技术领域
本申请涉及一种双组分水性聚氨酯涂料组合物。本申请还涉及由该双组分水性聚氨酯涂料组合物得到的低光泽度涂层。
背景技术
近年来，随着人们环保意识的增强和环保法规的健全，水性涂料受到人们越来越多的关注，其中双组分水性聚氨酯涂料组合物作为一种重要水性双组分涂料，具有高性能和多功能的优点，是水性涂料的发展方向，其具有成膜温度低、附着力强、耐磨性好、硬度高以及耐化学品、耐侯性好等优越性能，VOC显著降低，性能优于或等同于溶剂型双组分聚氨酯涂料。
双组分水性聚氨酯涂料组合物是由含NCO基的多异氰酸酯固化剂和含OH基的水性多元醇组成，其涂膜性能主要由水性多元醇的组成和结构决定。水性多元醇包括丙烯酸多元醇、聚酯多元醇、聚氨酯或醇酸多元醇，也可以是上述两种或更多的杂化混合物。丙烯酸多元醇具有相对分子质量低、羟基官能度高以及粒径小等优点，与异氰酸酯预聚物可制成色泽浅、保光保色性优、耐化学腐蚀、抗污染性能强，户外耐候性好的高装饰性涂料，也可制成外用防腐蚀装饰漆。
哑光涂层(也被称为低光泽涂层)相较于高光涂层具有视觉效果典雅柔和的特点，特别适用于建筑涂装，特别是内墙建筑涂层。随着人们对高品质生活的追求，使得对水性哑光涂料的需求越来越大。目前，在涂料工业中，主要是通过向涂料组合物中加入一定量的消光剂来获得低光泽涂层。如此形 成的涂料组合物成膜后，分布于漆膜中的消光剂粒子使得表面凹凸不平，增大对光的散射和减少反射，从而产生低光泽的哑光效果。但由于消光剂材料本身特性的限制，常见的消光剂例如微米级二氧化硅在聚合物乳液中分散困难，长期存储极易产生沉降。另外由于消光剂透明度差，容易造成漆膜发白，通透性降低的现象。同时消光剂具有较强的增稠性，加入量受限，难以制得较低光泽度的产品。
因此，涂料工业中仍然需要一种适用于提供低光泽涂层的双组分水性聚氨酯涂料组合物。
发明内容
一方面，本申请提供了一种双组分水性聚氨酯涂料组合物，包含：
成膜树脂组合物，包含具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体；和
多异氰酸酯交联剂，
其中，所述具有核壳结构的羟基丙烯酸聚合物颗粒包含由共聚物A形成的外壳和由共聚物B形成的内核，
所述共聚物A的玻璃化转变温度在-20℃到60℃范围内，所述共聚物B的玻璃化转变温度在20℃到100℃范围内，所述具有核壳结构的羟基丙烯酸聚合物颗粒的玻璃化转变温度在10℃到90℃范围内。
另一方面，本申请提供了一种低光泽度涂层，其特征在于，所述低光泽度涂层在60 °下具有75 °或更小的光泽度，所述低光泽度涂层根据本申请的双组分水性聚氨酯涂料组合物形成。
另一方面，本申请提供了一种制备具有核壳结构的羟基丙烯酸树脂聚合物颗粒的水性分散体的方法，其包括如下步骤：
1)提供用于形成共聚物A的单体混合物：在水、乳化剂和一部分引发剂的存在下，计量添加相对于所述单体混合物的总重1-20重量％的用于形成共聚物A的单体混合物，然后再计量加入剩余的用于形成共聚物A的单体混合物和剩余的引发剂，乳液聚合得到含有共聚物A的水性乳液，其中所述水性乳液的固含量被控制在20-30重量％的范围内；并且
2)提供用于形成共聚物B的单体混合物：采用所述用于形成共聚物B的单体混合物溶胀所得到的水性乳液，然后使用于形成共聚物B的单体混合物进行原位乳液聚合，得到具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体，其中所述具有核壳结构的羟基丙烯酸聚合物颗粒包含共聚物A作为外壳和共聚物B作为内核，其中所述水性分散体的固含量控制为30-45重量％。
本申请的发明人开创性地提供了一种双组分水性聚氨酯涂料组合物，其包含：含有特定核壳结构的羟基丙烯酸聚合物颗粒的水性分散体的成膜树脂组合物，和多异氰酸酯交联剂；在不含消光剂的情况下，该双组分水性聚氨酯涂料组合物固化之后能够提供低光泽度涂层，所述低光泽度涂层在60 °下具有75 °或更小的光泽度，减少或消除了现有技术中通过引入消光剂来降低涂层光泽度所带来的负面影响(例如涂层流动性损失)。
本申请的发明人还惊讶地发现，由这种双组分水性聚氨酯涂料组合物形成的固化涂层，与由常规水性涂料组合物相比，具有可比较的、甚至更优的硬度和耐化学性。
本申请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，本申请其它特征、目的和优点将变得清楚。
定义
在本文中使用时，除非另有说明，“一种”、“这种”、“至少一种”和“一种或多种”以及不使用数量词的情形可互换使用。因此，例如包含“一种”添加剂的涂料组合物可以被解释为表示该涂料组合物中包含“一种或多种”添加剂。除本文中另有说明外，本文中单数形式的使用还意在包括复数形式。
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申请未涉及的可选组分，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申请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。
在本申请中，“低光泽度涂层”是指，光泽度为0.1到80、优选1到75的 涂层，所述光泽度借助于Sheen小孔光泽度仪在60°的反射角下测量。
当针对“双组分水性聚氨酯涂料组合物”使用时，术语“不含消光剂”是指，本申请的双组分水性聚氨酯涂料组合物完全不含额外添加的能够产生消光效果的试剂，所述试剂包括但不限于微米合成二氧化硅、微粉蜡、硬脂酸盐、滑石粉/绿泥石粉和本领域技术人员已知可用于消光的其它试剂。
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。
在本申请中，通过端点限定的数值范围包括该范围内的所有任何数值，例如1到5的范围涵盖了数值1、1.5、2、2.75、3、3.80、4、5等。而且，公开的数值范围包括在该较宽范围内的所有子集范围，例如1到5的范围包括了子范围1到4、1.5到4.5、1到2等。
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申请实施方案。然而，在相同或其他情况下，其他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申请范围外。
附图说明
图1示意性地示出了由实施例1的成膜树脂组合物与市售的
Figure PCTCN2019126608-appb-000001
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合而制备的双组分水性聚氨酯涂料组合物所形成的漆膜表面2D和3D图。
图2示意性地示出了由实施例2的成膜树脂组合物与市售的
Figure PCTCN2019126608-appb-000002
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合而制备的双组分水性聚氨酯涂料组合物所形成的漆膜表面2D和3D图。
图3示意性地示出了由实施例3的成膜树脂组合物与市售的
Figure PCTCN2019126608-appb-000003
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合而制备的双组分水性聚氨酯涂料组合物所形成的漆膜表面2D和3D图。
图4示意性地示出了由实施例4的成膜树脂组合物与市售的
Figure PCTCN2019126608-appb-000004
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合而制备的双组分水性聚氨酯涂料组合物所形成的漆膜表面2D和3D图。
图5示意性地示出了由实施例5的成膜树脂组合物与市售的
Figure PCTCN2019126608-appb-000005
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合而制备的双组分水性聚氨酯涂料组合物所形成的漆膜表面2D和3D图。
图6示意性地示出了市售的型号为
Figure PCTCN2019126608-appb-000006
XP 2470的水性羟基聚丙烯酸分散体与市售的
Figure PCTCN2019126608-appb-000007
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合所形成的漆膜表面2D图。
图7示意性地示出了根据CN107434842A实施例7制备的核壳结构羟基丙烯酸树脂乳液与市售的
Figure PCTCN2019126608-appb-000008
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合所形成的漆膜表面2D图。
图8示意性地示出了广东花果山环保科技有限公司型号为MT2008 #的成膜树脂与市售的
Figure PCTCN2019126608-appb-000009
XP 2655固化剂以OH/NCO摩尔比为1/1.5混合所形成的漆膜表面2D图。
具体实施方式
根据本申请的第一方面，本申请提供了一种双组分水性聚氨酯涂料组合物，包含：
成膜树脂组合物，包含具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体；和
多异氰酸酯交联剂，
其中，所述具有核壳结构的羟基丙烯酸聚合物颗粒包含由共聚物A形成的外壳和由共聚物B形成的内核，
所述共聚物A的玻璃化转变温度在-20℃到60℃范围内，所述共聚物B的玻璃化转变温度在20℃到100℃范围内，所述具有核壳结构的羟基丙烯酸 聚合物颗粒的玻璃化转变温度在10℃到90℃范围内。
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申请的双组分水性聚氨酯涂料组合物形成的涂层的主体的树脂组合物，其可以包含具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体、溶剂以及任选的附加添加剂。
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100重量％、优选约30重量％至约99重量％，更优选约60重量％至约90重量％的具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体。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35重量％、约45重量％、约55重量％、约65重量％、约75重量％、约85重量％、约95重量％或约99重量％的具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体。
在根据本申请的具有核壳结构的羟基丙烯酸聚合物颗粒中，外壳是软质的，其玻璃化转变温度(Tg)在-20℃到60℃范围内。
术语“Tg”在本文中表示玻璃化转变温度，其是聚合物从玻璃状、脆性状态转变为橡胶态的温度。Tg值可以通过使用诸如差示扫描量热法(DSC)的技术实验性测定或使用Fox方程计算。除非另有声明，本文中给出的Tg值和范围是基于使用Fox方程计算得到的Tg。
根据Fox方程，具有n种共聚的共聚单体的共聚物的Tg(以开式度计)通过各共聚单体类型的重量分数W和得自各共聚单体的均聚物的Tg(以开式度计)给出：
Figure PCTCN2019126608-appb-000010
以开氏度计算的Tg可以很容易地转化为摄氏度(℃)。
尽管不希望受到理论的束缚，发明人认为，外壳的Tg在很大程度上影响作为成膜树脂的具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体凝结成膜的能力。外壳的Tg越低，壳的柔韧性越好，聚合物颗粒也可以在较低的温度下凝结成膜。而且，在聚合物颗粒的涂装过程中，这种软质外壳能够耐受涂装过程中的剪切作用，不会发生破裂。根据本申请，为了使聚合物颗 粒获得所期望的成膜性以及耐涂装加工性，共聚物外壳被设计为具有较低的Tg。在本申请的实施方案中，聚合物颗粒的共聚物外壳具有60℃或更低的Tg，优选具有50℃或更低的Tg，更优选具有40℃或更低的Tg，甚至更优选具有30℃或更低的Tg。优选地，聚合物颗粒的共聚物外壳具有-20℃或更高的Tg，更优选具有0℃或更高的Tg，甚至更优选具有5℃或更高的Tg。
在本申请的优选实施方式中，聚合物颗粒被设计成软壳硬核结构。优选地，所述共聚物内核的玻璃化转变温度比所述共聚物外壳的玻璃化转变温度高至少10℃、优选高至少15℃、更优选高至少20℃、甚至更优选高至少25℃或更高。
在本申请的一个具体实施方式中，根据实验测定的具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体具有在0-30℃的范围内的Tg，优选地，Tg在10-30℃的范围内。
根据本申请，所述共聚物A的酸值在3-40mg KOH/g范围内，所述共聚物B的酸值在0-10mg KOH/g范围内，所述具有核壳结构的羟基丙烯酸聚合物颗粒的酸值在3-40mg KOH/g范围内。所述酸值是通过ISO 2114滴定测量的。
根据本申请，所述共聚物A的羟值在40-150mg KOH/g范围内，所述共聚物B的羟值在5-60mg KOH/g范围内，所述具有核壳结构的羟基丙烯酸聚合物颗粒的羟值在40-150mg KOH/g范围内，优选地所述具有核壳结构的羟基丙烯酸聚合物颗粒的羟值在42-80mg KOH/g范围内。所述羟值是通过ISO4629滴定测量的。
根据本申请，所述共聚物A和所述共聚物B中的每一个由以下单体形成：
a)(甲基)丙烯酸C1-C20烷基酯；
b)任选地具有至多20个碳原子的乙烯基芳族化合物；
c)具有酸官能团的烯属不饱和单体；以及
d)(甲基)丙烯酸羟基C1-C20烷基酯。
在本申请的范围内，术语“(甲基)丙烯酸酯”表示丙烯酸酯、甲基丙烯酸酯以及两者的混合物。适用于本申请的合适的甲基丙烯酸C1-C20烷基酯的 实例包括但不限于，甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸辛酯、甲基丙烯酸-2-辛酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸壬酯、甲基丙烯酸2-甲基辛酯、甲基丙烯酸-2-叔丁基庚酯、甲基丙烯酸-3-异丙基庚酯、甲基丙烯酸癸酯、甲基丙烯酸十一烷基酯、甲基丙烯酸-5-甲基十一烷基酯，甲基丙烯酸十二烷基酯、甲基丙烯酸-2-甲基十二烷基酯、甲基丙烯酸十三烷基酯、甲基丙烯酸-5-甲基十三烷基酯、甲基丙烯酸十四烷基酯、甲基丙烯酸十五烷基酯、甲基丙烯酸十六烷基酯、甲基丙烯酸-2-甲基十六烷基酯、甲基丙烯酸十七烷基酯、甲基丙烯酸-5-异丙基十七烷基酯、甲基丙烯酸5-乙基十八烷基酯、甲基丙烯酸十八烷基酯、甲基丙烯酸十九烷基酯、甲基丙烯酸二十烷基酯、甲基丙烯酸环烷基酯(例如甲基丙烯酸环戊酯、甲基丙烯酸环己酯、甲基丙烯酸-3-乙烯基-2-丁基环己酯、甲基丙烯酸环庚酯、甲基丙烯酸环辛酯)、甲基丙烯酸冰片酯和甲基丙烯酸异冰片酯。优选的是甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯或甲基丙烯酸叔丁酯，特别优选的是甲基丙烯酸甲酯、甲基丙烯酸叔丁酯或甲基丙烯酸丁酯。
适用于本申请的合适的丙烯酸C1-C20烷基酯的实例包括但不限于，丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸-2-辛酯、丙烯酸-2-乙基己酯、丙烯酸壬酯、丙烯酸-2-甲基-辛酯、丙烯酸-2-叔丁基庚酯、丙烯酸-3-异丙基庚酯、丙烯酸癸酯、丙烯酸十一烷基酯、丙烯酸-5-甲基十一烷基酯、丙烯酸十二烷基酯、丙烯酸-2-甲基十二烷基酯、丙烯酸十三烷基酯、丙烯酸-5-甲基十三烷基酯、丙烯酸十四烷基酯、丙烯酸十五烷基酯、丙烯酸十六烷基酯、丙烯酸-2-甲基十六烷基酯、丙烯酸十七烷基酯、丙烯酸-5-异丙基十七烷基酯、丙烯酸-5-乙基十八烷基酯、丙烯酸十八烷基酯，丙烯酸十九烷基酯，丙烯酸二十烷基酯，丙烯酸环烷基酯，例如丙烯酸环戊酯、丙烯酸环己酯、丙烯酸-3-乙烯基-2-丁基环己酯、丙烯酸环庚酯、丙烯酸环辛酯、丙烯酸冰片酯和丙烯酸异冰片酯。优选的是丙烯酸乙酯、丙烯酸正丁酯、丙烯酸-2-乙基己酯或丙烯酸环己酯， 特别优选的是丙烯酸乙酯、丙烯酸正丁酯或丙烯酸-2-乙基己酯。
合适的具有至多20个碳原子的乙烯基芳族化合物b)的实例包括但不限于，苯乙烯、乙烯基甲苯、邻甲基苯乙烯、对甲基苯乙烯、α-丁基苯乙烯、4-正丁基苯乙烯、4-正癸基苯乙烯、卤代苯乙烯(例如单氯苯乙烯、二氯苯乙烯、三溴苯乙烯或四溴苯乙烯)。苯乙烯是优选的。
合适的具有酸官能团的烯属不饱和单体c)的实例包括但不限于，磷酸盐官能化或羧酸官能化的单体，优选的是羧酸官能化的单体如丙烯酸、甲基丙烯酸、丙烯酸β-羧基乙酯、巴豆酸、富马酸、马来酸酐、衣康酸或二元酸的单烷基酯或酸酐(例如马来酸单烷基酯)。特别优选的是丙烯酸或甲基丙烯酸，甲基丙烯酸是最特别优选的。
同样适合作为组分c)的化合物的是具有磷酸根基团或膦酸根基团或磺酸基团或磺酸根基团的不饱和、可自由基聚合的化合物，这些已描述在例如WO 00/39181(第8页第13行至第9页第19行)中。
合适的(甲基)丙烯酸羟基C1-C20烷基酯的实例包括但不限于，甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯、丙烯酸羟乙酯、丙烯酸羟丙酯或丙烯酸羟丁酯。
在本申请的一个实施方式中，形成所述共聚物A的单体包括：以组分a)、b)、c)和d)的重量总和为百分之百重量计，45-75重量％的组分a)，0-10重量％的组分b)，4-15重量％的组分c)，以及10-45重量％的组分d)。
在本申请的一个实施方式中，形成所述共聚物A的单体包括：以组分a)、b)、c)和d)的重量总和为百分之百重量计，45-75重量％的组分a)，0-10重量％的组分b)，4-15重量％的组分c)，以及1-30重量％的组分d)。
在本申请的一个实施方式中，形成所述共聚物B的单体包括：以组分a)、b)、c)和d)的重量总和为百分之百重量计，50-85重量％的组分a)，0-20重量％的组分b)，0.5-5重量％的组分c)，以及10-35重量％的组分d)。
在本申请的一个实施方式中，形成所述共聚物A的单体与形成所述共聚物B的单体的重量比为1:5到4:1，优选1:2到2:1。
本申请的成膜树脂组合物还可以包含常规添加剂，这些添加剂不会不利地影响双组分水性聚氨酯涂料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、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)或者降低成本的那些试剂。可以包含的添加剂例如是填料、润滑剂、成膜助剂、润湿剂、增塑剂、消泡剂、着色剂、抗氧化剂、流动控制剂、触变剂、分散剂、粘着促进剂、UV稳定剂、增稠剂、pH调节剂、溶剂、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双组分水性聚氨酯涂料组合物或由其得到的固化涂层。在优选的实施方式中，本申请的成膜树脂组合物可以包含增稠剂、分散剂、消泡剂、润湿剂、pH调节剂、填料、成膜助剂、防霉剂、防腐剂或其任意组合作为常规添加剂。根据本申请，常规添加剂的总量相对于所述成膜树脂组合物的总重为0.1重量％至约10重量％。
在本申请的一个实施方式中，根据本申请所述的成膜树脂组合物包含相对于所述成膜树脂组合物的重量，
70-85重量％的具有核壳结构的羟基丙烯酸树脂聚合物颗粒的水性分散体；
5-15重量％的水；
2-8重量％的成膜助剂；和
0-2重量％的其它附加添加剂，选自消泡剂、表面活性剂、润湿剂和增稠剂中的一种或多种；
其中所有组分的总量为100重量％。
作为成膜助剂的实例，可以使用醇类，例如乙二醇、丙二醇、己二醇、苯甲醇等；醇酯类，例如十二碳醇酯；醇醚类，例如乙二醇丁醚、丙二醇甲醚、丙二醇乙醚、丙二醇正丙醚、丙二醇丁醚、二丙二醇甲醚、二丙二醇丙醚、二丙二醇丁醚、三丙二醇正丁醚等；醇醚酯类，例如己二醇丁醚醋酸酯等。作为消泡剂的实例，可以使用购自BYK公司的BYK 028。作为表面活性剂的实例，可以使用购自BYK公司的BYK 341。作为润湿剂的实例，可以使用购自BYK公司的BYK 348。作为增稠剂的实例，可以使用ACRYSOL RM TM-2020E。本申请的成膜树脂组合物包含具有特定核壳结构的羟基丙烯酸聚合物颗粒的水性分散体，其中具有核壳结构的羟基丙烯酸聚合物颗粒包 含由共聚物A形成的外壳和由共聚物B形成的内核，外壳是软质的、具有较低的玻璃化转变温度，而内核是硬质的、具有较高的玻璃化转变温度，并且核壳比例恰当。
这种软壳硬核结构的羟基丙烯酸聚合物颗粒的水性分散体提供了良好的成膜性，仅需要少量成膜助剂即可成膜，大大降低了涂料中的VOC含量，使得涂料更符合环保要求。发明人惊讶地发现，采用这种软壳硬核结构的羟基丙烯酸聚合物颗粒的水性分散体配制形成的涂层具有大量微孔结构，这在本申请之前是难以预见的。并非受缚于任何理论，申请人推测，这种表面微孔结构可能是导致涂层具有低光泽度的主要原因。
此外，在本申请的羟基丙烯酸聚合物颗粒的水性分散体中，羟基主要分布在乳液的外壳部分，从而增大了与多异氰酸酯交联剂接触的几率，提高了涂层的交联密度，因而涂层的硬度、耐化学性等得到明显提高，还显著减少固化所需的多异氰酸酯交联剂的用量。
由烯属不饱和单体制备水性胶乳的乳液聚合技术在聚合物领域中是公知的，可以使用任意常规的乳液聚合工艺，诸如单阶聚合工艺、多阶聚合工艺、连续工艺等等。众所周知，可以利用种子聚合工艺制备水性胶乳，以便控制水性胶乳所包含的聚合物颗粒的结构和组成。
在本申请的实施方式中，水性胶乳通过如下制备：a)在适当的乳化剂的作用下并借助于搅拌，使单体混合物在水中分散成乳状液，然后将配制好的乳状液滴加到含有引发剂的聚合反应器中进行聚合，从而形成种子乳液作为聚合物壳；b)接着，在种子乳液的存在下，用另一种单体混合物溶胀所形成的种子乳液，并且使上述另一种单体混合物进行原位乳液聚合，从而形成具有核-壳结构的聚合物颗粒。
因此，根据本申请的另一方面，提供了一种制备具有核壳结构的羟基丙烯酸树脂聚合物颗粒的水性分散体的方法，所述方法包括如下步骤：1)提供用于形成共聚物A的单体混合物：在水、乳化剂和一部分引发剂的存在下，计量添加相对于所述单体混合物的总重1-20重量％的用于形成共聚物A的单体混合物，然后再计量加入剩余的用于形成共聚物A的单体混合物和剩余的引发剂，乳液聚合得到含有共聚物A的水性乳液，其中所述水性乳液的固含 量被控制在20-30重量％的范围内；并且2)提供用于形成共聚物B的单体混合物：采用所述用于形成共聚物B的单体混合物溶胀所得到的水性乳液，然后使用于形成共聚物B的单体混合物进行原位乳液聚合，得到具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体，其中所述具有核壳结构的羟基丙烯酸聚合物颗粒包含共聚物A作为外壳和共聚物B作为内核，其中所述水性分散体的固含量控制为30-45重量％。
上述可聚合单体的分散可以在任何已知的乳化剂的协助下完成。可用的乳化剂的实例包括本领域公知的阴离子表面活性剂、非离子表面活性剂或其组合。例如McCutcheon’s Detergents and Emulsifers(MC Publishing Co.,Glen Rock,N.J.)中公开了一些适用于乳液聚合的表面活性剂。也可以使用其他类型的稳定试剂，诸如保护性胶体。优选地，使用阴离子表面活性剂和非离子表面活性剂的组合。非离子表面活性剂包括烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚。优选地，使用烷基酚聚氧乙烯醚。阴离子表面活性剂包括脂族羧酸盐、脂族磺酸盐、脂族硫酸盐和脂族磷酸盐。优选地，使用碱金属，例如Na、K或Li，或碱土金属盐，例如Ca或Ba。在具体的实施方式中，使用脂族磺酸盐，优选使用十二烷基磺酸碱金属盐，更优选使用十二烷基磺酸钠(SDS)。
可以使用任何已知的自由基引发剂引发聚合反应。可用引发剂的实例包括，在聚合温度下热分解产生自由基的引发剂。实例包括水溶性和水不溶性引发剂。产生自由基的引发剂的实例包括过硫酸盐类，诸如过硫酸铵或过硫酸碱金属(包括钾、钠或锂)；过氧化物，例如枯烯过氧化氢、叔丁基过氧化氢、二叔丁基过氧化物、二辛基过氧化物、过戊酸叔丁基酯、过异壬酸叔丁基酯、过辛酸叔丁基酯、过新癸酸叔丁基酯、过氧二碳酸二(2-乙基己基)酯、过氧二碳酸二(异十三烷基)酯；偶氮化合物，例如偶氮双(异丁腈)和偶氮双(4-氰基戊酸)；和常规的氧化还原体系。优选地，使用水溶性引发剂过硫酸盐。更具体地，使用过硫酸铵作为自由基引发剂。
根据本申请，在共聚物A的制备过程中，任选地加入链转移剂，所述链转移剂包括但不限于正十二烷基硫醇、3-巯基丙酸异辛酯和α-甲基苯乙烯二聚体等中的一种或多种，优选正十二烷基硫醇。
在本申请的具有核壳结构的羟基丙烯酸树脂聚合物颗粒的水性分散体的制备过程中，乳化剂和引发剂的用量以及诸如反应温度、搅拌速度等的反应条件可由本领域技术人员依经验确定。优选地，单体混合物的预乳化工艺在2000rpm或更高的搅拌速度下进行，优选在4000rpm或更高的搅拌速度下进行。
多异氰酸酯交联剂
本文使用的术语“多异氰酸酯交联剂”指多异氰酸酯化合物、异氰酸酯低聚物或其组合。所述多异氰酸酯交联剂含有两个或更多个异氰酸酯官能团，其能够与成膜树脂组合物发生扩链和交联反应，从而在涂层中形成三维网络结构。
适当的多异氰酸酯交联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。
优选的多异氰酸酯交联剂是未封闭的或封闭的多异氰酸酯，更优选是亲水基团改性的和/或至少部分地亲水基团改性的、未封闭的多异氰酸酯，甚至更优选是亲水基团改性的。
在本申请的一个实施方式中，所述多异氰酸酯交联剂是亲水基团改性的多异氰酸酯交联剂。
作为多异氰酸酯交联剂的实例，可以使用任合适当的可商购产品，诸如Coverstro公司的
Figure PCTCN2019126608-appb-000011
XP 2655(基于六亚甲基二异氰酸酯(HDI)的亲水性脂肪族聚异氰酸酯)。
根据本申请，多异氰酸酯交联剂与成膜树脂组合物的用量这样选择，使得所得体系中羟基(OH)与异氰酸酯基(NCO)的摩尔比在1:1至1:2.5的范围内变化。一般而言，当羟基(OH)与异氰酸酯基(NCO)的摩尔比小于1:2.5时，那么所得双组分聚氨酯面漆的操作性能以及/或者所得涂层的机械性质可能会下降。当羟基(OH)与异氰酸酯基(NCO)的摩尔比大于1:1时，所得涂层的固化性能不良。根据实际需要，可以在成膜树脂组合物和/或多异氰酸酯交联剂的制备期间添加额外的不会对以上成膜树脂组合物和多异氰酸酯交联剂剂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，成膜树脂组合物与多异氰酸酯固化剂的用量并不局限于上述范围，可以根据实际需要调整。
根据本申请，双组分水性聚氨酯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多异氰酸酯固化剂以预定重量比在混合装置中进行简单混合。混合的双组分水性聚氨酯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。在本申请的一个实施方式中，混合的双组分水性聚氨酯涂料组合物通过喷涂来进行涂覆。双组分水性聚氨酯涂料组合物可被涂成各种湿膜厚度。在本申请的实施方式中，湿膜厚度优选地提供约13至约260μm的干膜厚度，且更优选地是约75至约150μm。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。
在本申请的另一方面，提供了一种低光泽度涂层，其特征在于，所述低光泽度涂层在60 °下具有75 °或更小的光泽度，所述低光泽度涂层由根据本申请的双组分水性聚氨酯涂料组合物形成。
在本申请的实施方式中，所述低光泽度涂层在60 °下具有60 °或更小的光泽度。
根据本申请，所述低光泽度涂层的表面具有微孔，所述微孔的平均直径为1-10微米，优选5-10微米。
根据本申请，所述低光泽度涂层的表面具有微孔，所述微孔的平均深度为0.1-2微米，优选0.3-1.5微米。在本申请上下文中，“平均深度”是指在一个取样长度内，微孔的最大轮廓峰高Zp和最大轮廓谷深Zv之和，多次测量取平均。
因此，本申请还涉及根据本申请的双组分水性聚氨酯涂料组合物在制备低光泽度涂层中的用途，其中所述低光泽度涂层在60 °下的光泽度为60或更小。
测试方法
除非另外指出，以下实施例中采用下述测试方法。
粘度
根据ASTM D 4212使用NK-2粘度杯来测量聚合物颗粒的水性分散体的粘度，以秒(s)计。
空气干燥时间
根据GB/T 1728-1979(1989)测量空气干燥时间。
摆杆硬度
摆杆硬度用于衡量固化体系的固化性能。根据GB/T 1730-2007进行测定。
光泽度
该测试用于测量固化涂层的光泽度。根据ASTM D523使用Sheen小孔 光泽度仪来评估60°光泽度。
铅笔硬度
该测试用于测量固化涂层的硬度。使用ASTM D3363来评估铅笔硬度。数据被报告为在涂层破裂前最后一次成功进行测试的铅笔硬度。因此，例如，如果用2H铅笔测试时，涂层不破裂，但用3H铅笔进行测试时破裂，则涂层被报告为具有2H的铅笔硬度。
粘附性
进行粘附性测试以评估涂层是否粘附到经涂布的基材上。该粘附性测试根据ASTM D 3359-测试方法B进行。粘附性通常被分为0-5B的等级，其中5B表示最优的粘附性。
耐化学性测试
根据ASTM F2250-测试方法B，进行溶剂(诸如乙醇、咖啡、红酒等)的耐受性测试以评估涂层的“固化”或交联程度。最后，确定涂层的完整情况。耐化学性通常被分为0-5的等级，其中5＝涂层完整、无污渍、无分层(最好)，4＝几乎注意不到涂层污渍，3＝能够清晰地确认涂层有污渍，2＝涂层变色且部分分层，0＝涂层脱落(最差)。
表面成像
通过光学显微镜以暗视野模式对样品表面进行成像。所使用的显微镜是Keyence VHX-5000，具有Z1000型透镜。
实施例
下面，通过实施例更具体地描述本申请公开的内容。这些实施例仅仅用于阐述性说明，并且不能解释为限制本申请的保护范围，因为在本申请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。
材料
所使用的材料列于下表1中。
表1：所使用的材料及相关信息
Figure PCTCN2019126608-appb-000012
表2：对比用水性羟基丙烯酸分散体的性能
性能 WQ1321P OH-7 OH-8
固含量 44.3％ 41.5％ 42.4％
粘度(s) 13.39 15.62 17.01
pH值 8.01 8.25 8.33
Tg / 65 75
羟值(mg KOH/g) 40 16 16
具有核壳结构的羟基丙烯酸树脂聚合物颗粒的水性分散体的制备
按下表3所示的成分来配制具有核壳结构的羟基丙烯酸树脂聚合物颗粒 的水性分散体。具体步骤为：M1的混合单体首先用0.3wt％的SDS乳化剂和70wt％的DIW乳化。在氮气和氧气的混合气氛下，将5wt％的M1溶液加入装有SDS、APS和DIW并配备温度计、顶置式搅拌器、气体入口的四颈烧瓶中，然后加热至80-90℃并搅拌保持20分钟，然后分别在约100分钟和120分钟的时间内滴加剩余的M1溶液和APS溶液。然后在85℃下再搅拌1小时，冷却至50℃，用氢氧化铵调节pH至7.0-8.0，得到共聚物A。共聚物A的固体含量控制在20-30重量％范围内。
当将反应器中的溶液冷却至室温时，加入M2单体并搅拌30分钟，然后滴加到另一个装有SDS、APS和DIW并配备温度计、顶置式搅拌器、气体入口的四颈烧瓶中，然后加热至80-90℃并搅拌。同时，将APS溶液滴加到反应器中以引发聚合。滴加控制在100-120分钟。然后在85℃下再搅拌1小时，冷却至50℃，用氢氧化铵调节pH至7.0-8.0。将相应的胶乳溶液通过125μm过滤器排出，得到核-壳胶乳。胶乳的固含量控制在35-45wt％。
表3
Figure PCTCN2019126608-appb-000013
根据测试部分所述，测定了样品1的胶乳性能，包括固含量、粘度、pH、Tg和羟值，结果列在下表4中。
表4
样品1 固含量 粘度(s) pH值 Tg 羟值(mg KOH/g)
结果 40.5％ 14.01 7.57 25 44
成膜树脂组合物的制备
按下表5的成分制备成膜树脂组合物。在搅拌下将成膜助剂、水和附加添加剂加入样品1-5的具有核壳结构的羟基丙烯酸树脂聚合物颗粒的水性分散体中，从而形成成膜树脂组合物。为了比较，分别采用来自Valspar的水性羟基丙烯酸分散体WQ1321P、OH-7和OH-8配制成膜树脂组合物，作为对比例1-3。
表5：成膜树脂组合物的组成
Figure PCTCN2019126608-appb-000014
双组分水性聚氨酯涂料组合物的制备
在使用前，将上面制备的成膜树脂组合物与
Figure PCTCN2019126608-appb-000015
XP2655(得自Coverstro公司的基于六亚甲基二异氰酸酯(HDI)的亲水性脂肪族聚异氰酸酯)以一定的比例混合。
涂层的形成
将适当量的上述双组分水性聚氨酯涂料组合物在经老化的PU板上进行拉伸，以形成120微米的涂层。然后，将由此形成的带有涂层的面板先后在空气中干燥30分钟，在50℃下干燥10分钟，然后在空气中冷却。
根据测试方法中所列举的方法，测定固化涂层的摆杆硬度、光泽度、粘附性、耐化学性等性能，结果示于表6中。测试之前，将上述所形成的涂层在空气中干燥7天。
Figure PCTCN2019126608-appb-000016
从上表6的结果可以看出，与来自Valspar的其它丙烯酸类水性胶乳相比，根据本申请的双组分水性聚氨酯涂料组合物在固化之后，获得了具有明显更低光泽度的涂层，所述低光泽度涂层在60 °下具有75 °或更小的光泽度。此外，该涂层具有可接受的涂层性能，包括粘附性、硬度和耐化学性等。
为了进一步验证由本申请的水性丙烯酸胶乳形成的涂层具有低光泽的原因，发明人较之在性能上特别是光泽度上的差别，本申请人分别对实施例1-5和其它商购丙烯酸树脂乳液，例如型号为
Figure PCTCN2019126608-appb-000017
XP 2470的水性羟基丙烯酸分散体、广东花果山环保科技有限公司型号为MT2008 #成膜树脂以及根据CN107434842A实施例7制备的核壳结构羟基丙烯酸树脂乳液制成的涂层进行成像，图像示于图1-8中。
从附图结果可见，根据本申请的双组分水性聚氨酯涂料组合物在固化之后所得的涂层表面有大量微孔形成，与现有技术的涂层显著不同。
本文中引用的所有专利、专利申请和出版物以及可电子获得的材料的全部公开均通过引用并入本文。前述的发明详述和实施例仅仅是为了清楚理解而给出。不能从中理解为不必要的限定。本申请不限于所示和所描述的精确细节，对于本领域的技术人员明显的变化将被包括于由权利要求书所限定的本申请中。在一些实施方式中，本文中说明性地公开的本申请可以在本文中未明确公开的任何要素不存在的情况下实施。
尽管本申请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申请公开的内容能够认识到可以设计其它实施方式，这并未脱离本申请的保护范围和精神。

Claims (14)

  1. 一种双组分水性聚氨酯涂料组合物，包含：
    成膜树脂组合物，包含具有核壳结构的羟基丙烯酸聚合物颗粒的水性分散体；和
    多异氰酸酯交联剂，
    其中，所述具有核壳结构的羟基丙烯酸聚合物颗粒包含由共聚物A形成的外壳和由共聚物B形成的内核，
    所述共聚物A的玻璃化转变温度在-20℃到60℃范围内，所述共聚物B的玻璃化转变温度在20℃到100℃范围内，所述具有核壳结构的羟基丙烯酸聚合物颗粒的玻璃化转变温度在10℃到90℃范围内。
  2. 根据权利要求1所述的双组分水性聚氨酯涂料组合物，其特征在于，所述共聚物A的酸值在3-40mg KOH/g范围内，所述共聚物B的酸值在0-10mg KOH/g范围内，所述具有核壳结构的羟基丙烯酸聚合物颗粒的酸值在3-40mg KOH/g范围内。
  3. 根据权利要求1所述的双组分水性聚氨酯涂料组合物，其特征在于，所述共聚物A的羟值在40-150mg KOH/g范围内，所述共聚物B的羟值在5-60mg KOH/g范围内，所述具有核壳结构的羟基丙烯酸聚合物颗粒的羟值在40-150mg KOH/g范围内。
  4. 根据权利要求1所述的双组分水性聚氨酯涂料组合物，其特征在于，所述多异氰酸酯交联剂是亲水基团改性的多异氰酸酯交联剂。
  5. 根据权利要求1所述的双组分水性聚氨酯涂料组合物，其特征在于，所述共聚物A和所述共聚物B中的每一个由以下单体形成：
    a)(甲基)丙烯酸C1-C20烷基酯；
    b)任选地具有至多20个碳原子的乙烯基芳族化合物；
    c)具有酸官能团的烯属不饱和单体；以及
    d)(甲基)丙烯酸羟基C1-C20烷基酯。
  6. 根据权利要求5所述的双组分水性聚氨酯涂料组合物，其特征在于，形成所述共聚物A的单体包括：以组分a)、b)、c)和d)的重量总和为百分 之百重量计，45-75重量％的组分a)，0-10重量％的组分b)，4-15重量％的组分c)，以及10-45重量％的组分d)。
  7. 根据权利要求5所述的双组分水性聚氨酯涂料组合物，其特征在于，形成所述共聚物A的单体包括：以组分a)、b)、c)和d)的重量总和为百分之百重量计，45-75重量％的组分a)，0-10重量％的组分b)，4-15重量％的组分c)，以及1-30重量％的组分d)。
  8. 根据权利要求5所述的双组分水性聚氨酯涂料组合物，其特征在于，形成所述共聚物B的单体包括：以组分a)、b)、c)和d)的重量总和为百分之百重量计，50-85重量％的组分a)，0-20重量％的组分b)，0.5-5重量％的组分c)，以及10-35重量％的组分d)。
  9. 根据权利要求1所述的双组分水性聚氨酯涂料组合物，其特征在于，所述共聚物A与所述共聚物B的重量比为1:5到4:1。
  10. 根据权利要求1所述的双组分水性聚氨酯涂料组合物，其特征在于，不含消光剂。
  11. 一种低光泽度涂层，其特征在于，所述低光泽度涂层在60°下具有75°或更小的光泽度，所述低光泽度涂层由如权利要求1-10中任意一项所述的双组分水性聚氨酯涂料组合物形成。
  12. 根据权利要求11所述的低光泽度涂层，其特征在于，所述低光泽度涂层在60°下具有60°或更小的光泽度。
  13. 根据权利要求11所述的低光泽度涂层，其特征在于，所述低光泽度涂层的表面具有微孔，所述微孔的平均直径为1-10微米。
  14. 根据权利要求11所述的低光泽度涂层，其特征在于，所述低光泽度涂层的表面具有微孔，所述微孔的平均深度为0.1-2微米。
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