WO2019105452A1 - 水性柔软触感涂料组合物和由其形成的耐磨涂层 - Google Patents

水性柔软触感涂料组合物和由其形成的耐磨涂层 Download PDF

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Publication number
WO2019105452A1
WO2019105452A1 PCT/CN2018/118513 CN2018118513W WO2019105452A1 WO 2019105452 A1 WO2019105452 A1 WO 2019105452A1 CN 2018118513 W CN2018118513 W CN 2018118513W WO 2019105452 A1 WO2019105452 A1 WO 2019105452A1
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WIPO (PCT)
Prior art keywords
coating
resin
coating composition
acrylic resin
weight
Prior art date
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PCT/CN2018/118513
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English (en)
French (fr)
Inventor
许升志
刘海峰
高思齐
罗正松
Original Assignee
Ppg涂料(天津)有限公司
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Priority claimed from CN201711242794.2A external-priority patent/CN107892758B/zh
Priority claimed from CN201811435036.7A external-priority patent/CN111234620A/zh
Application filed by Ppg涂料(天津)有限公司 filed Critical Ppg涂料(天津)有限公司
Publication of WO2019105452A1 publication Critical patent/WO2019105452A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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

Definitions

  • the traditional soft touch coatings applied to 3C products are all oily products, and all of them are formulated with solvent-containing raw materials, and the VOC content is as high as 600-800 g/L, far exceeding the country.
  • the paint consumption tax is exempt from 420g/L. Therefore, there is a need in the art for aqueous soft touch coatings having low VOC content.
  • the invention provides a multilayer coating system comprising: (a) a first coating formed from a first coating composition comprising: (1) an acrylic resin; and (2) a hydroxyl group An acrylic resin; and (b) a second coating applied directly over at least a portion of the first coating, the second coating being formed from a second coating composition comprising: (1) an aliphatic hydroxy function Polyurethane urethane resin; and (2) water-dispersible polycarbonate diol resin.
  • the present invention provides a coated substrate comprising: (a) a substrate; (b) a first coating applied to at least a portion of the substrate, the first coating comprising The first coating composition described below is formed: (1) an acrylic resin; and (2) a hydroxy acrylic resin; and (c) a second coating directly coated on at least a portion of the first coating, the second The coating layer is formed of a second coating composition comprising: (1) an aliphatic hydroxy-functional polyester urethane resin; and (2) a water-dispersible polycarbonate diol resin.
  • the present invention provides a multilayer coating system comprising: (a) a first coating formed from a first coating composition comprising: (1) an acrylic resin; and (2) a flexible polyurethane resin; and (b) a second coating applied directly over at least a portion of the first coating, the second coating being formed from a second coating composition comprising: (1) an aliphatic a hydroxy-functional polyester urethane resin; and (2) a water-dispersible polycarbonate diol resin.
  • the present invention provides a coated substrate comprising: (a) a substrate; (b) a first coating applied to at least a portion of the substrate, the first coating being A first coating composition comprising: (1) an acrylic resin; and (2) a flexible polyurethane resin; and (c) a second coating directly coated on at least a portion of the first coating, said The second coating layer is formed of a second coating composition comprising: (1) an aliphatic hydroxy-functional polyester urethane resin; and (2) a water-dispersible polycarbonate diol resin.
  • aqueous refers to a coating composition that comprises at least a majority of water (content greater than > 50 wt%) based on the total solvent weight of the composition.
  • volatile organic compound refers to any organic compound having a boiling point less than or equal to 250 ° C (482 ° F) measured at a standard atmospheric pressure of 101.3 kPa.
  • Organic solvents are a typical source of VOCs.
  • emulsion refers to a form of resin that requires the addition of an emulsifier to emulsify in water.
  • disersion refers to a form of resin that can be emulsified in water by self-emulsification without the need for an additional emulsifier.
  • the invention relates to a coating system comprising at least a first coating and a second coating.
  • the first coating is formed from a first coating composition comprising an acrylic resin and a hydroxy acrylic resin.
  • the acrylic resin used in the first coating composition has a high glass transition temperature and a high film formation temperature.
  • the acrylic resin has a glass transition temperature of at least 80 °C.
  • the acrylic resin has a minimum film forming temperature of at least 80 °C.
  • the acrylic resin may have a glass transition temperature of 80 to 100 °C.
  • the glass transition temperature was determined by dynamic thermomechanical analysis (DMA) using a TA Instruments Q800 instrument with parameters of 10 Hz, amplitude 5 mm, temperature ramp of -100 ° C to 250 ° C, and Tg determined as tan ⁇ according to ASTM D7028. The peak value of the curve.
  • the term "minimum film forming temperature" is the lowest temperature at which a polymer emulsion can form a continuous transparent film, typically expressed as MFFT.
  • the minimum film forming temperature of the emulsion is an important application index of the emulsion. That is, after the moisture of the emulsion is lower than a certain temperature, the polymer particles are still in a discrete state and cannot be integrated, so the emulsion cannot form a continuous and uniform coating film due to evaporation of water; At a specific temperature, after evaporation of water, molecules in each polymer particle will penetrate, diffuse, deform, and aggregate to form a continuous transparent film.
  • the performance and quality of the emulsion and latex coatings can be determined by measuring the minimum film forming temperature of the emulsion.
  • the MFFT of the emulsion is determined by the internal structure of the polymer particles and the glass transition temperature.
  • the minimum film forming temperature can be measured according to the ASTM D 2354 and ISO 2115 standards using an MFFT-BAR minimum film forming temperature meter (UK RHOPOINT minimum film forming temperature tester MFFT-60/MFFT-90).
  • the acrylic resin comprises a styrene-modified acrylic resin having a number average molecular weight of from about 100,000 to 120,000, and the number average molecular weight is determined by gel permeation chromatography using polystyrene as a standard.
  • the styrene-modified acrylic resin includes a styrene-based acrylic resin in which the content of styrene is 50 to 80% by weight of the styrene-modified acrylic resin.
  • the acrylic resin used in the first coating composition is usually present in the form of an aqueous emulsion having a particle diameter in the range of 100 to 120 nm, and the particle diameter within the range increases the stability of the emulsion and imparts an excellent appearance to the coating.
  • the acrylic resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 50% by weight, suitably up to about 45% by weight, such as up to about, based on the weight of the first coating composition.
  • An amount of 40% by weight is present in the coating composition.
  • the amount of the acrylic resin is less than 10% by weight, the first coating layer formed from the coating composition has a low hardness, resulting in poor sanding property when reworked, and it is easy to stick sandpaper; at the same time, the adhesion to the substrate is deteriorated, resulting in the entire The paint film is easily peeled off.
  • the amount of the acrylic resin is more than 50% by weight, the hardness of the first coating layer formed of the coating composition is too high, resulting in deterioration of adhesion to the second coating layer and peeling.
  • acrylic resins are useful in the present invention.
  • acrylic resins that can be used in the present invention include, but are not limited to, Voncoat WHK-364 from DIC; Carboset CR-781 from Lubrizol, Carboset PC-23; from Wanhua 6318; NeoPac TM E-123 from DSM, NeoCryl A-662 and the like; AS 2610, and the AC 2508 from Alberdingk.
  • the hydroxy acrylic resin used in the first coating composition usually has a number average molecular weight of about 4,000 to 12,000, and the number average molecular weight is determined by gel permeation chromatography using polystyrene as a standard.
  • the hydroxy acrylic resin has a minimum film forming temperature of from about 20 to 60 ° C, effectively contributing to the film forming properties of the overall formulation.
  • the hydroxy acrylic resin suitable for use in the present invention usually has a hydroxyl value of 30 to 110 mgKOH/g, and the isocyanate curing agent thereof improves the crosslink density of the paint film, and provides excellent flexibility, interlayer adhesion, and chemical resistance. .
  • the hydroxy acrylic resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 50% by weight, suitably up to about 45% by weight, such as at most, based on the weight of the first coating composition.
  • An amount of about 40% by weight is present in the coating composition.
  • the amount of the hydroxy acrylic resin is less than 10% by weight, the cross-linking density of the first coating film formed from the coating composition is too low, resulting in poor adhesion to the upper coating film, and resistance to chemicals, hardness and RCA resistance. The grinding performance is deteriorated.
  • the amount is more than 50% by weight, the crosslinking density of the first coating layer formed of the coating composition is too high, resulting in deterioration of adhesion to the upper coating film.
  • hydroxy acrylic resins are useful in the present invention.
  • examples of such polyurethane resins useful in the present invention include, but are not limited to, UC 84, AC 2597, AC 2598, AC 2592, AC 31 and AC 3669 from Alberdingk; Bayhydrol A 2845 XP and Bayhydrol U XP 2755 from Covestro; WD-551, WD-554, WD-555 and WD-556; from Allnex VSM 6299W/42WA, SM 6817W, Setaqua 6510, Setaqua 6516, Setaqua 6520 and Setaqua 6522; from DSM XK-110, XK-103 and XK-102; Antkote 2033 and Antkote 2042 from Wanhua; WPA-4402, WPA-4403 and WPA-4407 from Huigu; Carboset 451 and Carboset 452 from Lubrizol.
  • the first coating composition further comprises various auxiliaries and cosolvents useful in aqueous systems including, but not limited to, surfactants, rheological auxiliaries, ethers and amine cosolvents, and the like.
  • the aliphatic hydroxy-functional polyester urethane resin used in the second coating composition employs a long-chain linear structure having an aliphatic group having a carbon number of about 15 to 25.
  • the ratio of polyester groups to polyurethane groups in the aliphatic hydroxy-functional polyester urethane resin is from about 1:1 to about 2.
  • the aliphatic hydroxy-functional polyester urethane resin may have a number average molecular weight of from about 8,000 to 10,000, and the number average molecular weight is determined by gel permeation chromatography using polystyrene as a standard.
  • the aliphatic hydroxy-functional polyester urethane resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 40% by weight, suitably up to about, based on the weight of the second coating composition.
  • the amount of the resin is less than 10% by weight, the second coating layer formed of the coating composition is too sticky, the slipperiness is deteriorated, and the anti-fingerprint property is deteriorated.
  • the amount is more than 40% by weight, the second coating layer formed of the coating composition deteriorates in scratch resistance and hardness.
  • aliphatic hydroxy functional polyester urethane resins are useful in the present invention.
  • examples of aliphatic hydroxy-functional polyester urethane resins useful in the present invention include, but are not limited to, from Covestor U XP2757, U XP 2698, Bayhydrol U 355, Bayhydrol UH340/1, DLC-F; Matt300 from Alberdingk; Sancure PC-55, 2060C from Lubrizol; NeoRez R-1000 from DSM, NeoRez R-1010; WSL from DIC 250; PD-802, PD-804 from Stahl; W 6110 from Mitsui; WPU-2501, WPU-2502 from Huigu Chemical, etc.; from Wanhua 6512 and 6110; PU40, PU471, PU 980, PU461, etc. from Lamberti.
  • the water-dispersible polycarbonate diol resin used in the second coating composition contains a sulfonate hydrophilic group and can be directly dispersed in water.
  • the water-dispersible polycarbonate diol has a number average molecular weight of 800 to 1,000 and a hydroxyl value of 90 to 110 mg KOH/g, and the number average molecular weight is measured by gel permeation chromatography using polystyrene as a standard. Method determination.
  • the water-dispersible polycarbonate diol resin is a clear 100% solids material that is completely free of VOC.
  • Suitable isocyanates include isophorone diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, tetraalkyl xylene diisocyanate such as m-tetramethylbenzene Methylene diisocyanate, p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, diphenylpentamethyl diisocyanate, 2,6-toluene diisocyanate, bisanisyl diisocyanate, toluene diisocyanate, naphthalene 1,4-diisocyanate, bis(4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate, hexamethylene diisocyanate, and how suitable, trimer of the above substances, for example, Isocyanate trimer of hexamethylene diisocyanate
  • the molar ratio of the isocyanate group in the isocyanate group-containing component to the hydroxyl group in the aliphatic hydroxy-functional polyester urethane resin is in the range of 1.5 to 2:1, in this range The internal molar ratio balances overall performance and appearance requirements.
  • the molar ratio of the isocyanate group in the isocyanate group-containing component to the hydroxyl group in the hydroxy acrylic resin is in the range of 1.3 to 2:1, and the molar ratio in this range is satisfied.
  • the reaction rate and resin activation period are required.
  • the second coating composition further comprises a thickening agent. It is preferred to use a polyether polyurethane associative thickener. Such thickeners are highly effective viscosity aids in the low to medium shear rate range that provide strong shear dilution characteristics to balance film buliding and fat edges.
  • the thickening agent is present in the coating composition in an amount of from about 1% to about 2% by weight, based on the weight of the second coating composition.
  • the second coating composition further comprises various auxiliaries and co-solvents useful in aqueous systems including, but not limited to, leveling agents, antifoaming agents, surfactants, wetting dispersants, matting agents, and the like.
  • the acrylic resin used in the first coating composition has a high film forming temperature (glass transition temperature).
  • the acrylic resin has a minimum film forming temperature of at least 80 °C.
  • the acrylic resin may have a glass transition temperature of between 80 and 100 °C.
  • the acrylic resin comprises a styrene-modified acrylic resin having a number average molecular weight of from about 100,000 to 120,000.
  • the acrylic resin used in the first coating composition is usually present in the form of an aqueous emulsion, and it is present in the emulsion in a particle size ranging from 100 to 120 nm. Such a particle size can increase the stability of the emulsion and impart an excellent appearance to the coating.
  • the acrylic resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 60% by weight, suitably up to about 55% by weight, such as up to about, based on the weight of the first coating composition.
  • An amount of 50% by weight is present in the coating composition.
  • the amount of the acrylic resin is less than 10% by weight, the first coating layer formed from the coating composition has a low hardness, resulting in poor sanding property when reworked, and it is easy to stick sandpaper; at the same time, the adhesion to the substrate is deteriorated, resulting in the entire The paint film is easily peeled off.
  • the amount of the acrylic resin is more than 60% by weight, the hardness of the first coating layer formed of the coating composition is too high, resulting in deterioration of adhesion to the second coating layer and peeling.
  • the flexible polyurethane resin used in the first coating composition typically has a number average molecular weight of from about 8,000 to 10,000. Such resins also have very low minimum film forming temperatures (glass transition temperatures). For example, the flexible polyurethane resin has a minimum film forming temperature of about -5 to 0 ° C, which effectively contributes to the film forming property of the overall formulation. Further, such resins generally have a tensile strength of 5,000 to 5,500 Psi, a tensile strength of 400 to 450 Psi, and an elongation of 900 to 950%. These properties help the coating to form a uniform, flat coating and provide excellent flexibility, interlayer adhesion and chemical resistance.
  • the flexible polyurethane resin may include a long-chain aliphatic urethane resin, a polycarbonate-modified urethane resin, or a combination thereof.
  • the long-chain aliphatic group in the long-chain aliphatic urethane resin usually has a carbon chain length of about 15 to 25 carbon atoms, imparting flexibility properties to the polyurethane resin.
  • the flexible polyurethane resin may comprise a mixture of a long-chain aliphatic urethane resin and a polycarbonate-modified urethane resin in a weight ratio of 60 to 80: 20 to 40.
  • the flexible polyurethane resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 40% by weight, suitably up to about 35% by weight, such as at most, based on the weight of the first coating composition.
  • An amount of about 30% by weight is present in the coating composition.
  • the amount of the flexible urethane resin is less than 10% by weight, the first coating paint film formed from the coating composition is hard, resulting in deterioration of adhesion to the upper coating film.
  • the first coating layer formed by the coating composition is too soft, causing the surface of the paint film to be unsatisfactory to scratch, and the sandpaper is severely viscous during polishing, which significantly reduces the grinding efficiency.
  • polyurethane resins are useful in the present invention.
  • examples of such polyurethane resins that can be used in the present invention include, but are not limited to, from Covestro UH 2952/1; PU 71, PU98 from Lamberti; WS-5100, WS-4300 from Mitsui; from Stahl PU-461, and the like.
  • the first coating composition further comprises a thickening agent.
  • a thickening agent which is an acid-containing crosslinked acrylic emulsion copolymer.
  • Such thickeners swell rapidly when diluted with water and neutralized with a base.
  • the polyacrylic thickener is effective for improving the low shear rate viscosity, so that the formed coating has high shear thinning characteristics, thereby ensuring excellent workability and avoiding fat.
  • the thickening agent is present in the coating composition in an amount of from about 0.5% to about 2% by weight, based on the weight of the first coating composition.
  • thickeners are useful in the present invention.
  • examples of such thickeners that can be used in the present invention include, but are not limited to, Rheolate 150 from Element, Rheolate 175; from Basf DS 6256, HV 30; ACRYSOL TM ASE-60 from Dow, TT-935, UCAR POLYPHONE T -900 and T-901 and the like.
  • the second coating is applied directly to at least a portion of the first coating.
  • the second coating layer is formed of a second coating composition comprising an aliphatic hydroxy functional polyester urethane resin and a water-dispersible polycarbonate diol resin.
  • the aliphatic hydroxy-functional polyester urethane used in the second coating composition employs a long-chain linear structure having an aliphatic group having a carbon number of about 15 to 25.
  • Such resins may have a number average molecular weight of from about 8,000 to 10,000.
  • the resin is typically a 50% solids aqueous dispersion, completely free of VOC, and is present in the dispersion in a particle size ranging from 120 to 150 nm. Such a particle size can increase the stability of the dispersion and impart an excellent appearance to the coating.
  • the aliphatic hydroxy-functional polyester urethane resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 40% by weight, suitably up to about, based on the weight of the second coating composition.
  • the amount of the resin is less than 10% by weight, the second coating layer formed of the coating composition is too sticky, the slipperiness is deteriorated, and the anti-fingerprint property is deteriorated.
  • the amount is more than 40% by weight, the second coating layer formed of the coating composition deteriorates in scratch resistance and hardness.
  • the water-dispersible polycarbonate diol resin used in the second coating composition contains a hydrophilic group and can be directly dispersed in water.
  • the water-dispersible polycarbonate diol is a transparent 100% solids material and is completely free of VOC.
  • the water-dispersible polycarbonate diol has a number average molecular weight of 800 to 1,000 and a hydroxyl value of 90 to 110 mgKOH/g.
  • its average particle diameter is from 100 to 130 nm. Such a particle size can increase the stability of the dispersion and impart an excellent appearance to the coating.
  • the water-dispersible polycarbonate diol resin is at least about 10% by weight, suitably at least about 15% by weight, such as at least about 20% by weight, and up to about 40% by weight, suitably up to about 40% by weight, based on the weight of the second coating composition.
  • the amount of the resin is less than 10% by weight, the second coating layer formed of the coating composition is deteriorated in scratch resistance, abrasion resistance, chemical resistance, and hardness.
  • the amount is more than 40% by weight, the second coating formed from the coating composition becomes sticky, and is not easily dull and gives a desired film thickness.
  • water-dispersible polycarbonate diol resins are useful in the present invention.
  • examples of the water-dispersible polycarbonate diol resin which can be used in the present invention include, but are not limited to, 6665 W from Changxing; PCDX-103 from Asahi Kasei; PU 98D from Lamberti, and the like.
  • the second coating composition further comprises an isocyanate group-containing component as a curing agent which reacts with the aliphatic hydroxy-functional polyester urethane to form a coating film.
  • isocyanate group-containing component and like terms as used herein includes cyclic trimers of isocyanates, polyisocyanates, and polyisocyanates.
  • Suitable isocyanates include isophorone diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, tetraalkyl xylene diisocyanate such as m-tetramethylbenzene Methylene diisocyanate, p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, diphenylpentamethyl diisocyanate, 2,6-toluene diisocyanate, bisanisyl diisocyanate, toluene diisocyanate, naphthalene 1,4-diisocyanate, bis(4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate, hexamethylene diisocyanate, and how suitable, trimer of the above substances, for example, Isocyanate trimer of hexamethylene diisocyanate
  • the molar ratio of the isocyanate groups in the isocyanate group-containing component to the hydroxyl groups in the aliphatic hydroxy-functional polyester polyurethane dispersion is in the range of from 1.5 to 2:1. The molar ratios within this range balance the overall performance and appearance requirements.
  • the isocyanate group-containing component is present in the coating composition in an amount of from about 15% to about 20% by weight based on the weight of the second coating composition.
  • the second coating composition further comprises a thickening agent.
  • a thickening agent Preference is given to using polyether polyurethane-associated thickeners. Such thickeners are a highly effective viscosity aid in the low to medium shear rate range that provides strong shear dilution characteristics to balance film buliding and fat edge.
  • the thickening agent is present in the coating composition in an amount of from about 1% to about 2% by weight, based on the weight of the second coating composition.
  • the second coating composition further comprises various auxiliaries and co-solvents useful in aqueous systems including, but not limited to, leveling agents, antifoaming agents, surfactants, wetting dispersants, matting agents, and the like.
  • the coating system of the present invention is applicable to a wide variety of substrates known in the coatings industry.
  • the coating system can be applied to automotive substrates, industrial substrates, aircraft and aircraft components, marine substrates and components, such as ships, ships, and onshore and offshore facilities, storage tanks, windmills, nuclear power plants, packaging substrates, Wood floors and furniture, clothing, electronic equipment, including casings and circuit boards, glass and transparencies, sports equipment, including golf balls, stadiums, buildings, bridges, etc.
  • the substrate can be, for example, metallic or non-metallic.
  • Non-metallic substrates include polymers, plastics, polyesters, polyolefins, polyamides, cellulose, polystyrene, polyacrylic acid, polyethylene naphthalate, polypropylene, polyethylene, nylon, EVOH, polylactic acid , other "green" polymer substrates, polyethylene terephthalate (PET), polycarbonate, polycarbonate propylene butadiene styrene (PC / ABS), polyamide, wood, veneer, Wood composites, particleboard, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, synthetic and natural leather.
  • the substrate can also include a metallized plastic substrate.
  • metallized plastic substrate refers to a substrate formed from both plastic and metal.
  • the metallized plastic substrate can comprise a plastic material comprising a metallic material incorporated into and/or coated on at least a portion of the plastic material.
  • the substrate includes, but is not limited to, polycarbonate (PC), acrylonitrile-2-butadiene-2-styrene terpolymer (ABS) + polycarbonate, polycarbonate + glass fiber (GF) And carbon fiber (CF).
  • PC polycarbonate
  • ABS acrylonitrile-2-butadiene-2-styrene terpolymer
  • GF polycarbonate + glass fiber
  • CF carbon fiber
  • the coating system is particularly useful when at least partially coated on a consumer electronic product.
  • the coatings of the present invention are applicable to substrates found on notebook computers, tablets, keyboards, mobile phones, other handheld electronic devices, and the like.
  • the present invention also encompasses electronic or electronic components having a surface at least partially coated with a coating as described herein.
  • the consumer electronic product may be formed from any of the foregoing materials, such as metallized plastic.
  • a first coating composition forming a first coating is applied to at least a portion of the substrate and cured by thermal dehydration at a temperature of 50 to 80 ° C to form a first coating.
  • the second coating composition forming the second coating is then applied to at least a portion of the first coating and cured by thermal dehydration at a temperature of 50 to 80 ° C to form a second coating.
  • the second coating can also be applied as a clear topcoat layer.
  • clear coating means a coating that is at least substantially transparent or completely transparent.
  • substantially transparent refers to a coating wherein the surface of the other side of the coating is at least partially visible to the naked eye when viewed through the coating.
  • completely transparent refers to a coating wherein the surface of the other side of the coating is completely visible to the naked eye when viewed through the coating.
  • the clear topcoat layer may include a colorant, such as a pigment, provided that the colorant does not interfere with the desired clarity of the clear topcoat layer.
  • the clear topcoat layer is free of colorants such as pigments (ie, unpigmented).
  • the coating composition of the present invention can be applied by any standard method in the art, such as electrocoating, spray coating, electrostatic spraying, dipping, roll coating, brushing, etc., and then cured to form a coating.
  • the first coating of the present invention can be applied to a dry film thickness of from 5 microns to 15 microns.
  • the second coating of the present invention can be applied to a dry film thickness of from 20 microns to 60 microns.
  • the ## coating system of the present invention was formed according to the following Table 1-2.
  • the #1 primer composition was prepared from the components listed in Table 1.
  • the #1 varnish composition was prepared from the components listed in Table 2.
  • Component Weight percentage Aliphatic hydroxy functional polyester polyurethane, WPU-2502 30 Water-dispersible polycarbonate diol, 6665W 30 Silicone leveling agent, Tego 410 1.00 Silicone defoamer, Byk 024 0.50 Silicone leveling agent, Byk 348 0.40 Silicone wetting and dispersing agent, Tego 752w 0.50 Modified matting powder, Tosoh E-1011 7.00 Polyurethane associative thickener, Element 299 0.10 Deionized water 30.5 total 100 Hardener, Covestro 2487/1 70 Thinner 30
  • the 2# coating system of the present invention was formed according to the following Table 3-4.
  • the 2# primer composition was prepared from the components listed in Table 3.
  • the 2# varnish composition was prepared from the components listed in Table 4.
  • the 3# primer composition was prepared from the components listed in Table 5.
  • the #3 varnish composition was prepared from the components listed in Table 6.
  • the 4# coating system of the present invention was formed according to the following Tables 7-8.
  • the 4# primer composition was prepared from the components listed in Table 7.
  • Component Weight percentage Aliphatic hydroxy-functional polyester polyurethane, WPU2502 30 Water soluble polycarbonate diol, 6665W 25 Silicone leveling agent, Tego 410 1.00 Silicone defoamer, Byk 024 0.50 Silicone leveling agent, Byk 348 0.40 Silicone wetting and dispersing agent, Tego 752w 0.50 Modified matting powder, Tosoh E-1011 7.00 Polyurethane associative thickener, Element 299 1.5 Deionized water 34.1 Hardener, Covestro 2487/1 70 Thinner 30
  • the components other than the hardener and diluent listed in Tables 1-8 were weighed and stirred in the vessel for about 15 minutes or at room temperature until homogeneous. The hardener and diluent were then added and mixed for five minutes prior to spraying to ensure thorough mixing of all components. The coating mixture was sprayed within two hours of mixing of all the components.
  • the coating systems 1# to 4# of the present invention are superior or at least comparable to the products on the market in terms of performance tested.
  • the pencil hardness of the coating system of the present invention can reach H grade or even 2H, which is significantly higher than the pencil hardness grade F of the existing commercial products (paste hardness: 2H>H>F>HB>B). Therefore, the coating system of the present invention has excellent scratch resistance.
  • the test results of the coating system of the present invention can reach at least 100, or even 200 cycles, comparable to or superior to those of the prior art solvent-based soft tactile coating compositions. s level.
  • the RCA abrasion resistance may be improved while the coating feel and workability may be deteriorated.
  • the coating system of the present invention can provide high RCA abrasion resistance while ensuring the feel and workability of the coating.

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Abstract

本发明提供一种多层涂层体系，其包括:(a)由第一涂料组合物形成的第一涂层；和(b)直接涂覆在第一涂层的至少一部分上的第二涂层；所述第二涂层由第二涂料组合物形成。本发明还提供用所述多层涂层体系涂覆的基材。

Description

水性柔软触感涂料组合物和由其形成的耐磨涂层 技术领域
本发明涉及一种具有低VOC的多层涂层体系，具体而言涉及包含第一涂层和第二涂层的多层涂层体系。本发明还涉及用所述多层涂层体系涂覆的基底。
背景技术
目前市场上应用于3C产品(包括电脑产品、通信产品和消费类电子产品)的传统柔软触感涂料均为油性产品，其配方全部采用含溶剂原料，VOC含量高达600～800g/L，远超出国家涂料消费税免征点420g/L。因此，在本领域对具有低VOC含量的水性柔软触感涂料存在需求。
本发明旨在开发水性色漆与水性弹性漆，其性能和手感接近油性漆水平，且抗指纹效果甚至更加优异，其VOC含量<200g/L，远低于420g/L。此外，在传统油性溶剂施工过程中，溶剂挥发到施工环境中，刺激性气味强，容易对施工人员的健康造成伤害，且油漆本身是易燃易爆物，要求周围环境具备高防火性能。本发明的水性漆，相对溶剂型气味小，对施工人员伤害小，且完全不助燃，更加安全。
发明内容
在一个方面，本发明提供了一种多层涂层体系，其包括:(a)由包含下述的第一涂料组合物形成的第一涂层：(1)丙烯酸树脂；和(2)羟基丙烯酸树脂；和(b)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：(1)脂肪族羟基官能聚酯聚氨酯树脂；和(2)水分散型聚碳酸酯二醇树脂。
在另一个方面，本发明提供了涂覆基材，其包括：(a)基材；(b)涂覆在所述基材的至少一部分上的第一涂层，该第一涂层由包含下述的第一涂料组合物形成：(1)丙烯酸树脂；和(2)羟基丙烯酸树脂；和(c)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：(1)脂肪族羟基官能聚酯聚氨酯树脂；和(2)水分散型聚碳酸酯二醇树脂。
仍在另一个方面，本发明提供了一种多层涂层体系，其包括:(a)由包含下述的第一涂料组合物形成的第一涂层：(1)丙烯酸树脂；和(2)柔性聚氨酯树脂；和(b)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：(1)脂肪族羟基官能聚酯聚氨酯树脂；和(2)水分散型聚碳酸酯二醇树脂。
又在另一个方面，本发明提供了涂覆基材，其包括：(a)基材；(b)涂覆在所述基材的至少一部分上的第一涂层，该第一涂层由包含下述的第一涂料组合物形成：(1)丙烯酸树脂；和(2)柔性聚氨酯树脂；和(c)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：(1)脂肪族羟基官能聚酯聚氨酯树脂；和(2)水分散型聚碳酸酯二醇树脂。
具体实施方式
为了下面的详细描述的目的，应当理解，本发明可采用各种替代的变化和步骤顺序，除非明确规定相反。此外，除了在任何操作实例中，或者以其他方式指出的情况下，表示例如说明书和权利要求中使用的成分的量的所有数字应被理解为在所有情况下被术语“约”修饰。因此，除非相反指出，否则在以下说明书和所附权利要求中阐述的数值参数是根据本发明所要获得的期望性能而变化的近似值。至少并不是试图将等同原则的适用限制在权利要求的范围内，每个数值参数至少应该根据报告的有效数字的个数并通过应用普通舍入技术来解释。
尽管阐述本发明的广泛范围的数值范围和参数是近似值，但是具体实例中列出的数值尽可能精确地报告。然而，任何数值固有地包含由其各自测试测量中发现的标准偏差必然产生的某些误差。
此外，应当理解，本文所述的任何数值范围旨在包括归入其中的所有子范围。例如，“1至10”的范围旨在包括介于(并包括)所述最小值1和所述最大值10之间的所有子范围，即具有等于或大于1的最小值和等于或小于10的最大值。
在本申请中，除非另有明确说明，单数的使用包括复数且复数包含单数。此外，在本申请中，除非另有明确说明，否则使用“或”表示“和/或”，即使在某些情况下可明确地使用“和/或”。此外，在本申请中， 除非另有明确说明，否则使用“一(a)”或“一(an)”表示“至少一”。例如，“一种”聚合物，“一种”涂料组合物等指这些物品中的任何的一种或多种。
如本文所用，术语“水性”是指基于组合物中的总溶剂重量包含至少大部分水(含量大于>50wt％)的涂料组合物。
如本文所用，术语“挥发性有机化合物(VOC)”是指在101.3kPa的标准大气压下测量的沸点小于或等于250℃(482℉)的任何有机化合物。有机溶剂是VOC的典型来源。
如本文所用，术语“乳液”是指需要加入乳化剂才能乳化于水中的树脂形式。如本文所用，术语“分散体”是指不需要额外的乳化剂而通过自乳化就能乳化于水中的树脂形式。
本发明涉及一种包括至少第一涂层和第二涂层的涂层体系。如前所述，第一涂层由包含丙烯酸树脂和羟基丙烯酸树脂的第一涂料组合物形成。
用于第一涂料组合物的丙烯酸树脂具有高玻璃化转变温度、高成膜温度。例如，所述丙烯酸树脂具有至少80℃的玻璃化转变温度。例如，所述丙烯酸树脂具有至少80℃的最低成膜温度。特别地，所述丙烯酸树脂可具有80～100℃的玻璃化转变温度。所述玻璃化转变温度通过动态热机械分析(DMA)使用TA Instruments Q800仪器测定，测定参数：频率为10Hz，振幅为5mm，温度斜坡为-100℃至250℃，Tg确定为根据ASTM D7028的tanδ曲线的峰值。
如本文所用，术语“最低成膜温度”为聚合物乳液能形成连续透明膜的最低温度，通常用MFFT表示。乳液的最低成膜温度是乳液的一个重要应用指标。即在低于某一特定温度以下，乳液的水分挥发以后，聚合物粒子仍是离散状态，不能融为一体，因而乳液并不能因为水的蒸发而形成连续、均匀的涂膜；在高于这一特定的温度时，水分蒸发后，各聚合物粒子中的分子会渗透、扩散、变形、聚集形成连续的透明薄膜。通过测定乳液的最低成膜温度可以判定乳液和乳胶涂料的性能及施工质量。乳液的MFFT是由聚合物粒子内部构造和玻璃化温度决定的。所述最低成膜温度可以根据ASTM D 2354和ISO 2115标准的规定，使用MFFT-BAR最低成膜温度仪(英国RHOPOINT最低成膜温度测试仪 MFFT-60/MFFT-90)测定。
合适地，所述丙烯酸树脂包括数均分子量约100,000～120,000的苯乙烯改性丙烯酸树脂，且所述数均分子量使用聚苯乙烯为标准品通过凝胶渗透色谱法测定。所述苯乙烯改性丙烯酸树脂包括含有苯乙烯基的丙烯酸树脂，其中苯乙烯的含量为苯乙烯改性丙烯酸树脂的50～80wt％。用于第一涂料组合物的丙烯酸树脂通常以水性乳液的形式存在，其具有100～120nm范围内的粒径，该范围内的粒径增加了乳液的稳定性并赋予了涂料优良的外观。
通常，所述丙烯酸树脂以基于第一涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约50wt％，合适地至多约45wt％，例如至多约40wt％的量存在于该涂料组合物中。当丙烯酸树脂的量低于10wt％时，由该涂料组合物形成的第一涂层硬度低，导致其返修重涂时打磨性差，易粘砂纸；同时，其对基材附着变差，导致整个漆膜容易剥离。当丙烯酸树脂的量高于50wt％时，由该涂料组合物形成的第一涂层硬度过高，导致其与第二涂层层间附着变差而发生剥离。
很多商业可得的丙烯酸树脂可用于本发明中。例如，可用于本发明的此类丙烯酸树脂的实例包括但不限于：来自DIC的Voncoat WHK-364；来自Lubrizol的Carboset CR-781、Carboset PC-23；来自万华的
Figure PCTCN2018118513-appb-000001
6318；来自DSM的NeoPac TM E-123、NeoCryl A-662等；来自Alberdingk的AS 2610和AC 2508。
用于第一涂料组合物的羟基丙烯酸树脂通常具有约4,000～12,000的数均分子量，且所述数均分子量使用聚苯乙烯为标准品通过凝胶渗透色谱法测定。合适地，所述羟基丙烯酸树脂树脂具有约20～60℃的最低成膜温度，有效地帮助了整体配方的成膜性。适合用于本发明的羟基丙烯酸树脂树脂通常具有30～110mgKOH/g的羟值，其配合异氰酸酯固化剂提高了漆膜交联密度，提供了优良的柔韧性、层间附着力和耐化学品性。
通常，所述羟基丙烯酸树脂以基于第一涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约50wt％，合适地至多约45wt％，例如至多约40wt％的量存在于该涂料组 合物中。当该羟基丙烯酸树脂的量低于10wt％时，由该涂料组合物形成的第一涂层漆膜交联密度太低，造成与上层涂膜附着变差，且耐化学品、硬度和RCA耐磨性能变差。当该量高于50wt％时，由该涂料组合物形成的第一涂层交联密度太高，造成与上层涂膜附着变差。
很多商业可得的羟基丙烯酸树脂可用于本发明中。例如，可用于本发明的此类聚氨酯树脂的实例包括但不限于：来自Alberdingk的UC 84、AC2597、AC2598、AC2592、AC31和AC3669；来自Covestro的Bayhydrol A 2845 XP和Bayhydrol U XP 2755；来自DIC的WD-551、WD-554、WD-555和WD-556；来自Allnex的
Figure PCTCN2018118513-appb-000002
VSM 6299W/42WA、SM 6817W、Setaqua 6510、Setaqua 6516、Setaqua 6520和Setaqua 6522；来自DSM的
Figure PCTCN2018118513-appb-000003
XK-110、
Figure PCTCN2018118513-appb-000004
XK-103和
Figure PCTCN2018118513-appb-000005
XK-102；来自万华的Antkote 2033和Antkote 2042；来自慧谷的WPA-4402、WPA-4403和WPA-4407；来自Lubrizol的Carboset 451和Carboset 452。
第一涂料组合物还包含增稠剂。优选使用碱溶性阴离子型增稠剂，其为含酸的交联丙烯酸乳液共聚物。此类增稠剂当用水稀释以及用碱中和时，其中的乳液颗粒迅速溶胀。所述聚丙烯酸型增稠剂能有效改善低剪切速率粘度，使得所形成的涂料具有高剪切稀释特性，从而可确保优良的可施工性并避免肥边。通常，所述增稠剂以基于第一涂料组合物的重量计约0.5～2wt％的量存在于该涂料组合物中。
很多商业可得的增稠剂可用于本发明中。例如，可用于本发明的此类增稠剂的实例包括但不限于：来自Element的Rheolate 150、Rheolate175；来自Basf的
Figure PCTCN2018118513-appb-000006
DS 6256、
Figure PCTCN2018118513-appb-000007
HV 30；来自Dow的ACRYSOL TM ASE-60、TT-935、UCAR POLYPHONE T-900和T-901等。
第一涂料组合物还包含可用于水性体系的各种助剂和助溶剂，其包括但不限于表面活性剂、流变助剂、醚类和胺类助溶剂等。
如前所述，第二涂层直接涂覆在第一涂层的至少一部分上。第二涂层由包括脂肪族羟基官能聚酯聚氨酯树脂和水分散型聚碳酸酯二醇树脂的第二涂料组合物形成。
用于第二涂料组合物的脂肪族羟基官能聚酯聚氨酯树脂采用脂肪族基团的碳原子数为约15～25的长链线性结构。合适地，所述脂肪族羟 基官能聚酯聚氨酯树脂中聚酯基团与聚氨酯基团的比例约为1:1～2。合适地，所述脂肪族羟基官能聚酯聚氨酯树脂可具有约8,000～10,000的数均分子量，且所述数均分子量使用聚苯乙烯为标准品通过凝胶渗透色谱法测定。所述脂肪族羟基官能聚酯聚氨酯树脂通常以水性分散体的形式存在，其具有120～150nm范围内的粒径，该范围内的粒径增加了分散体的稳定性并赋予了涂料优良的外观。并且，所述水性分散体形式的脂肪族羟基官能聚酯聚氨酯树脂的固含量可以为约40～60wt％，诸如50wt％。所述水性分散体形式的脂肪族羟基官能聚酯聚氨酯树脂可以完全不含VOC。
通常，所述脂肪族羟基官能聚酯聚氨酯树脂以基于第二涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约40wt％，合适地至多约35wt％，例如至多约30wt％的量存在于该涂料组合物中。当该树脂的量低于10wt％时，由该涂料组合物形成的第二涂层手感太粘，爽滑性变差，抗指纹性变差。当该量高于40wt％时，由该涂料组合物形成的第二涂层抗刮性和硬度变差。
很多商业可得的脂肪族羟基官能聚酯聚氨酯树脂可用于本发明中。例如，可用于本发明的脂肪族羟基官能聚酯聚氨酯树脂的实例包括但不限于：来自Covestor的
Figure PCTCN2018118513-appb-000008
U XP2757、
Figure PCTCN2018118513-appb-000009
U XP 2698、Bayhydrol U 355、Bayhydrol UH340/1、DLC-F；来自Alberdingk的Matt300；来自Lubrizol的Sancure PC-55、2060C；来自DSM的NeoRez R-1000、NeoRez R-1010；来自DIC的WSL-250；来自Stahl的PD-802、PD-804；来自Mitsui的W 6110；来自来自慧谷化工的WPU-2501、WPU-2502等；来自万华的
Figure PCTCN2018118513-appb-000010
6512和
Figure PCTCN2018118513-appb-000011
6110；来自Lamberti的PU40、PU471、PU 980、PU461等。
用于第二涂料组合物的水分散型聚碳酸酯二醇树脂含有磺酸盐亲水基团，可直接分散于水中。合适地，所述水分散型聚碳酸酯二醇具有800～1,000的数均分子量和90～110mg KOH/g的羟值，且所述数均分子量使用聚苯乙烯为标准品通过凝胶渗透色谱法测定。通常，所述水分散型聚碳酸酯二醇树脂为透明的100％固含量物质，完全不含VOC。当所述水分散型聚碳酸酯二醇分散于水中后其平均粒径为100～130nm，这样范围的粒径增加了分散体的稳定性并赋予了涂料优良的外观。
通常，所述水分散型聚碳酸酯二醇树脂以基于第二涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约40wt％，合适地至多约35wt％，例如至多约30wt％的量存在于该涂料组合物中。当该树脂的量低于10wt％时，由该涂料组合物形成的第二涂层抗刮擦性、耐磨、耐化学品性及硬度变差。当该量高于40wt％时，由该涂料组合物形成的第二涂层手感变粘，且不易消光以及得到所需的膜厚。
很多商业可得的水分散型聚碳酸酯二醇树脂可用于本发明中。例如，可用于本发明的水分散型聚碳酸酯二醇树脂的实例包括但不限于：来自长兴的6665W；来自AsahiKasei的PCDX-103；来自Lamberti的PU 98D；来自Adaka的HUX-516S和HUX-564；来自UBE的UW-3039E、UW-1077和UW-2001A等。
第一和第二涂料组合物还包含作为固化剂的含异氰酸酯基团的组分，其与脂肪族羟基官能聚酯聚氨酯和羟基丙烯酸酯反应形成涂膜。本文使用的术语“含异氰酸酯基团的组分”和类似术语包括异氰酸酯、多异氰酸酯和多异氰酸酯的环状三聚体。
适宜的异氰酸酯包括异佛尔酮二异氰酸酯、1,3-或1,4-环己烷二异氰酸酯、二环己基甲烷二异氰酸酯、四烷基苯二甲撑二异氰酸酯例如间-四甲基苯二甲撑二异氰酸酯、对-苯二异氰酸酯、多亚甲基多苯基异氰酸酯、二苯基五甲基二异氰酸酯、2,6-甲苯二异氰酸酯、联茴香苯二异氰酸酯、联甲苯二异氰酸酯、萘-1,4-二异氰酸酯、双(4-异氰酸酯基苯基)甲烷、4,4’-二苯基丙烷二异氰酸酯、六亚甲基二异氰酸酯，以及如何合适，上述物质的三聚体，例如，六亚甲基二异氰酸酯的异氰酸酯三聚体。
在一个方面，所述含异氰酸酯基团的组分中的异氰酸酯基团与所述脂肪族羟基官能聚酯聚氨酯树脂中的羟基基团的摩尔比在1.5～2:1的范围内，在此范围内的摩尔比平衡了综合性能与外观要求。
在一个方面，所述含异氰酸酯基团的组分中的异氰酸酯基团与所述羟基丙烯酸树脂中的羟基基团的摩尔比在1.3～2:1的范围内，在此范围内的摩尔比满足了反应速率和树脂活化期的要求。
第二涂料组合物还包含增稠剂。优选使用聚醚聚氨酯缔合型增稠 剂。此类增稠剂是一种在低至中等剪切速率范围内高度有效的粘度助剂，其能够提供强剪切稀释特性，以便平衡膜形成(film buliding)和肥边(fat edge)。通常，所述增稠剂以基于第二涂料组合物的重量计约1～2wt％的量存在于该涂料组合物中。
很多商业可得的增稠剂可用于本发明中。例如，可用于本发明的此类增稠剂的实例包括但不限于：来自Element的WT-105A、299；来自Basf的
Figure PCTCN2018118513-appb-000012
PU 1191；来自Dow的RM-12W；来自Evonik的3060；来自Borchers的BORCHI GEL 0620等。
第二涂料组合物还包含可用于水性体系的各种助剂和助溶剂，其包括但不限于流平剂、消泡剂、表面活性剂、湿润分散剂、消光剂等。
本发明还涉及一种包括至少第一涂层和第二涂层的涂层体系。如前所述，第一涂层由包含丙烯酸树脂和柔性聚氨酯树脂的第一涂料组合物形成。
用于第一涂料组合物的丙烯酸树脂具有高成膜温度(玻璃化转变温度)。例如，所述丙烯酸树脂具有至少80℃的最低成膜温度。特别地，所述丙烯酸树脂可具有80～100℃之间的玻璃化转变温度。优选地，所述丙烯酸树脂包括数均分子量约100,000～120,000的苯乙烯改性丙烯酸树脂。用于第一涂料组合物的丙烯酸树脂通常以水性乳液的形式存在，且其以100～120nm范围内的粒径存在于乳液中。这样的粒径能够增加乳液的稳定性并赋予涂料优良的外观。
通常，所述丙烯酸树脂以基于第一涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约60wt％，合适地至多约55wt％，例如至多约50wt％的量存在于该涂料组合物中。当丙烯酸树脂的量低于10wt％时，由该涂料组合物形成的第一涂层硬度低，导致其返修重涂时打磨性差，易粘砂纸；同时，其对基材附着变差，导致整个漆膜容易剥离。当丙烯酸树脂的量高于60wt％时，由该涂料组合物形成的第一涂层硬度过高，导致其与第二涂层层间附着变差而发生剥离。
很多商业可得的丙烯酸树脂可用于本发明中。例如，可用于本发明的此类丙烯酸树脂的实例包括但不限于：来自DIC的Voncoat WHK-364；来自Lubrizol的Carboset CR-781、Carboset PC-23；来自万 华的
Figure PCTCN2018118513-appb-000013
6318；来自DSM的NeoPac TM E-123、NeoCryl A-662等；来自Alberdingk的AS 2610和AC 2508。
用于第一涂料组合物的柔性聚氨酯树脂通常具有约8,000～10,000的数均分子量。此类树脂还具有非常低的最低成膜温度(玻璃化转变温度)。例如，所述柔性聚氨酯树脂具有约-5～0℃的最低成膜温度，有效帮助了整体配方的成膜性。此外，此类树脂通常具有5,000～5,500Psi的抗张强度、400～450Psi的拉伸强度以及900～950％的延伸率。这些特性有助于涂料形成均匀平整的涂膜，并且能提供优良的柔韧性、层间附着力和耐化学品性。所述柔性聚氨酯树脂可包括长链脂肪族聚氨酯树脂、聚碳酸酯改性聚氨酯树脂或其组合。长链脂肪族聚氨酯树脂中的长链脂肪族基团通常具有约15-25个碳原子的碳链长度，赋予了该聚氨酯树脂柔韧性特性。特别地，所述柔性聚氨酯树脂可包含重量比为60～80:20～40的长链脂肪族聚氨酯树脂和聚碳酸酯改性聚氨酯树脂的混合物。
通常，所述柔性聚氨酯树脂以基于第一涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约40wt％，合适地至多约35wt％，例如至多约30wt％的量存在于该涂料组合物中。当该柔性聚氨酯树脂的量低于10wt％时，由该涂料组合物形成的第一涂层漆膜偏硬，造成与上层涂膜附着变差。当该量高于40wt％时，由该涂料组合物形成的第一涂层过软，造成漆膜表面不耐受刮擦，打磨返修时严重粘砂纸，明显降低打磨效率。
很多商业可得的聚氨酯树脂可用于本发明中。例如，可用于本发明的此类聚氨酯树脂的实例包括但不限于：来自Covestro的
Figure PCTCN2018118513-appb-000014
UH 2952/1；来自Lamberti的PU 71、PU98；来自Mitsui的WS-5100、WS-4300；来自Stahl PU-461等。
第一涂料组合物还包含增稠剂。优选使用碱溶性阴离子型增稠剂，其为含酸的交联丙烯酸乳液共聚物。此类增稠剂当用水稀释以及用碱中和时，其中的乳液颗粒迅速溶胀。所述聚丙烯酸型增稠剂能有效改善低剪切速率粘度，使得所形成的涂料具有高剪切稀释特性，从而可确保优良的可施工性并避免肥边。通常，所述增稠剂以基于第一涂料组合物的重量计约0.5～2wt％的量存在于该涂料组合物中。
很多商业可得的增稠剂可用于本发明中。例如，可用于本发明的此类增稠剂的实例包括但不限于：来自Element的Rheolate 150、Rheolate175；来自Basf的
Figure PCTCN2018118513-appb-000015
DS 6256、
Figure PCTCN2018118513-appb-000016
HV 30；来自Dow的ACRYSOL TM ASE-60、TT-935、UCAR POLYPHONE T-900和T-901等。
第一涂料组合物还包含可用于水性体系的各种助剂和助溶剂，其包括但不限于表面活性剂、流变助剂、醚类和胺类助溶剂等。
如前所述，第二涂层直接涂覆在第一涂层的至少一部分上。第二涂层由包括脂肪族羟基官能聚酯聚氨酯树脂和水分散型聚碳酸酯二醇树脂的第二涂料组合物形成。
用于第二涂料组合物的脂肪族羟基官能聚酯聚氨酯采用脂肪族基团的碳原子数为约15～25的长链线性结构。此类树脂可具有约8,000～10,000的数均分子量。该树脂通常为50％固含量的水性分散体，完全不含VOC，且其以120～150nm范围内的粒径存在于分散体中。这样的粒径能够增加分散体的稳定性并赋予涂料优良的外观。
通常，所述脂肪族羟基官能聚酯聚氨酯树脂以基于第二涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约40wt％，合适地至多约35wt％，例如至多约30wt％的量存在于该涂料组合物中。当该树脂的量低于10wt％时，由该涂料组合物形成的第二涂层手感太粘，爽滑性变差，抗指纹性变差。当该量高于40wt％时，由该涂料组合物形成的第二涂层抗刮性和硬度变差。
很多商业可得的脂肪族羟基官能聚酯聚氨酯树脂可用于本发明中。例如，可用于本发明的脂肪族羟基官能聚酯聚氨酯树脂的实例包括但不限于：来自Covestor的Bayhydrol UH340/1；来自Lubrizol的Sancure PC-55；来自DSM的NeoRez R-1000；来自慧谷化工的WPU-2501等；来自万华的
Figure PCTCN2018118513-appb-000017
6512和
Figure PCTCN2018118513-appb-000018
6110；来自Lamberti的PU40和PU471等。
用于第二涂料组合物的水分散型聚碳酸酯二醇树脂含有亲水基团，可直接分散于水中。所述水分散型聚碳酸酯二醇为透明的100％固含量物质，完全不含VOC。该水分散型聚碳酸酯二醇具有800～1,000的数均分子量和90～110mgKOH/g的羟值。当该树脂分散于水中后其平均粒径为100～130nm。这样的粒径能够增加分散体的稳定性并赋予涂料 优良的外观。
通常，所述水分散型聚碳酸酯二醇树脂以基于第二涂料组合物的重量计至少约10wt％，合适地至少约15wt％，例如至少约20wt％，以及至多约40wt％，合适地至多约35wt％，例如至多约30wt％的量存在于该涂料组合物中。当该树脂的量低于10wt％时，由该涂料组合物形成的第二涂层抗刮擦性、耐磨、耐化学品性及硬度变差。当该量高于40wt％时，由该涂料组合物形成的第二涂层手感变粘，且不易消光以及得到所需的膜厚。
很多商业可得的水分散型聚碳酸酯二醇树脂可用于本发明中。例如，可用于本发明的水分散型聚碳酸酯二醇树脂的实例包括但不限于：来自长兴的6665W；来自AsahiKasei的PCDX-103；来自Lamberti的PU 98D等。
第二涂料组合物还包含作为固化剂的含异氰酸酯基团的组分，其与脂肪族羟基官能聚酯聚氨酯反应形成涂膜。本文使用的术语“含异氰酸酯基团的组分”和类似术语包括异氰酸酯、多异氰酸酯和多异氰酸酯的环状三聚体。适宜的异氰酸酯包括异佛尔酮二异氰酸酯、1,3-或1,4-环己烷二异氰酸酯、二环己基甲烷二异氰酸酯、四烷基苯二甲撑二异氰酸酯例如间-四甲基苯二甲撑二异氰酸酯、对-苯二异氰酸酯、多亚甲基多苯基异氰酸酯、二苯基五甲基二异氰酸酯、2,6-甲苯二异氰酸酯、联茴香苯二异氰酸酯、联甲苯二异氰酸酯、萘-1,4-二异氰酸酯、双(4-异氰酸酯基苯基)甲烷、4,4’-二苯基丙烷二异氰酸酯、六亚甲基二异氰酸酯，以及如何合适，上述物质的三聚体，例如，六亚甲基二异氰酸酯的异氰酸酯三聚体。
在一个方面，所述含异氰酸酯基团的组分中的异氰酸酯基团与所述脂肪族羟基官能聚酯聚氨酯分散体中的羟基基团的摩尔比在1.5-2:1的范围内。在此范围内的摩尔比能够平衡综合性能与外观要求。
所述含异氰酸酯基团的组分以基于第二涂料组合物的重量计约15～20％的量存在于该涂料组合物中。
第二涂料组合物还包含增稠剂。优选使用聚醚聚氨酯缔合型增稠剂。此类增稠剂是一种在低至中等剪切速率范围内高度有效的粘度助剂，其能够提供强剪切稀释特性，以便平衡膜形成(film buliding)和肥边 (fat edge)。通常，所述增稠剂以基于第二涂料组合物的重量计约1～2wt％的量存在于该涂料组合物中。
很多商业可得的增稠剂可用于本发明中。例如，可用于本发明的此类增稠剂的实例包括但不限于：来自Element的WT-105A、299；来自Basf的
Figure PCTCN2018118513-appb-000019
PU 1191；来自Dow的RM-12W；来自Evonik的3060；来自Borchers的BORCHI GEL 0620等。
第二涂料组合物还包含可用于水性体系的各种助剂和助溶剂，其包括但不限于流平剂、消泡剂、表面活性剂、湿润分散剂、消光剂等。
本发明的涂层体系可应用于涂料工业已知的各种各样的基材。例如，该涂层体系可应用于汽车基材，工业基材，飞行器和飞行器部件，船舶基材和部件，诸如舰、船舶以及岸上和离岸设施，储罐，风车，核电站，包装基材，木地板和家具，服装，电子设备，包括外壳和电路板，玻璃和透明胶片，运动器材，包括高尔夫球，体育场馆，建筑物，桥梁等。所述基材例如可以是金属或非金属的。金属基材包括但不限于锡、钢(包括电镀锌钢、冷轧钢、热浸镀锌钢等)、铝、铝合金、锌-铝合金、涂有锌-铝合金的钢和镀铝钢。非金属基材包括聚合物、塑料、聚酯、聚烯烃、聚酰胺、纤维素、聚苯乙烯、聚丙烯酸、聚萘二甲酸乙二醇酯、聚丙烯、聚乙烯、尼龙、EVOH、聚乳酸、其他“绿色”聚合物基材、聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯、聚碳酸酯丙烯丁二烯苯乙烯(PC/ABS)、聚酰胺、木材、单板、木质复合材料、刨花板、中密度纤维板、水泥、石材、玻璃、纸、纸板、纺织品、合成和天然皮革等。
基材还可包括金属化塑料基材。如本文所用，“金属化塑料基材”是指由塑料和金属两者形成的基材。例如，金属化塑料基材可包括塑料材料，其包含并入到塑料材料中和/或涂覆在塑料材料的至少一部分上的金属材料。
特别地，基材包括但不限于聚碳酸酯(PC)、丙烯腈-2-丁二烯-2-苯乙烯三元共聚物(ABS)+聚碳酸酯、聚碳酸酯+玻璃纤维(GF)和碳纤维(CF)。
当至少部分涂覆在消费性电子产品之上时，所述涂层体系是特别有用的。例如，本发明的涂层可应用于见于笔记本电脑、平板电脑、键盘、移动电话、其他手持电子设备等上的基材。基于上述，本发明还包括具 有至少部分地涂覆有本文所述涂层的表面的电子产品或电子部件。应当理解，消费性电子产品可由任何的前述材料形成，诸如金属化塑料。
在涂层体系施用期间，形成第一涂层的第一涂料组合物被施加到基材的至少一部分上，并且在50～80℃温度下用热脱水固化，形成第一涂层。然后将形成第二涂层的第二涂料组合物施用在第一涂层的至少一部分上，并在50～80℃温度下用热脱水固化，形成第二涂层。
应当理解，第一涂层可作为底漆层涂覆到基材上，并且第二涂层可作为面漆层涂覆在第一涂层上。如本文所用，“底漆涂层”是指可沉积到基材上以便制备用于涂覆保护性或装饰性涂层的表面的底涂层。此外，“面漆”是指沉积在另一涂层诸如底漆上以提供保护和/或装饰层的顶涂层。
第二涂层也可作为透明的面漆层涂覆。如本文所用，“透明涂层”是指至少基本上透明或完全透明的涂层。术语“基本透明”是指这样的涂层，其中当透过涂层观察时，涂层另一边的表面是至少部分地肉眼可见的。术语“完全透明”是指这样的涂层，其中当透过涂层观察时，涂层另一边的表面是完全地肉眼可见的。应当理解，透明面漆层可包括着色剂，诸如颜料，条件是着色剂不干扰透明面漆层的期望透明度。或者，透明面漆层不含着色剂，诸如颜料(即，未着色的)。
本发明的涂料组合物可通过本领域任何标准的方法涂覆，例如电涂、喷涂、静电喷涂、浸渍、辊涂、刷涂等，然后固化形成涂层。本发明的第一涂层可涂覆至5微米至15微米的干膜厚度。此外，本发明的第二涂层可涂覆至20微米至60微米的干膜厚度。
实施例
提供下述实施例进一步阐述本发明，但不应认为其将本发明限制在实施例所述的细节。除另外说明之外，下述实施例以及通篇说明书中所有的份数和百分数均以重量计。
实施例1.
根据下表1-2形成本发明的1#涂层体系。
1#底漆组合物由表1中列出组分制备。
表1. 1#底漆组合物
Figure PCTCN2018118513-appb-000020
1#清漆组合物由表2中列出组分制备。
表2. 1#清漆组合物
组分 重量百分比
脂肪族羟基官能聚酯聚氨酯，WPU-2502 30
水分散型聚碳酸酯二醇，6665W 30
有机硅流平剂，Tego 410 1.00
有机硅消泡剂，Byk 024 0.50
有机硅流平剂，Byk 348 0.40
有机硅润湿分散剂，Tego 752w 0.50
改性消光粉，Tosoh E-1011 7.00
聚氨酯缔合型增稠剂，Element 299 0.10
去离子水 30.5
总计 100
   
硬化剂，Covestro 2487/1 70
稀释剂 30
实施例2.
根据下表3-4形成本发明的2#涂层体系。
2#底漆组合物由表3中列出组分制备。
表3. 2#底漆组合物
Figure PCTCN2018118513-appb-000021
2#清漆组合物由表4中列出组分制备。
表4. 2#清漆组合物
Figure PCTCN2018118513-appb-000022
Figure PCTCN2018118513-appb-000023
实施例3.
根据下表5-6形成本发明的3#涂层体系。
3#底漆组合物由表5中列出组分制备。
表5. 3#底漆组合物
Figure PCTCN2018118513-appb-000024
3#清漆组合物由表6中列出组分制备。
表6. 3#清漆组合物
Figure PCTCN2018118513-appb-000025
Figure PCTCN2018118513-appb-000026
实施例4.
根据下表7-8形成本发明的4#涂层体系。
4#底漆组合物由表7中列出组分制备。
表7. 4#底漆组合物
Figure PCTCN2018118513-appb-000027
4#清漆组合物由表8中列出组分制备。
表8. 4#清漆组合物
组分 重量百分比
脂肪族羟基官能聚酯聚氨酯，WPU2502 30
水溶性聚碳酸酯二醇，6665W 25
有机硅流平剂，Tego 410 1.00
有机硅消泡剂，Byk 024 0.50
有机硅流平剂，Byk 348 0.40
有机硅润湿分散剂，Tego 752w 0.50
改性消光粉，Tosoh E-1011 7.00
聚氨酯缔合型增稠剂，Element 299 1.5
去离子水 34.1
   
硬化剂，Covestro 2487/1 70
稀释剂 30
将表1-8中列出的除了硬化剂和稀释剂的组分称重并在容器中搅拌约15分钟或在室温下直至均匀。然后在喷涂之前加入硬化剂和稀释剂并混合五分钟以确保所有组分的充分混合。在所有组分的混合两小时内喷涂涂料混合物。
实施例5.多层涂层的涂覆和评估
将基材(ABS+PC)进行包括擦拭和静电除尘在内的前处理。然后通过手动或者机器(包括往复机、机器人、自动流水线)喷涂实施例1-4制备的底漆组合物，形成第一涂层。使该涂层在60-80℃的温度下烘烤约20-30分钟，得到干膜厚度为5～15微米的涂层。然后在该第一涂层之上通过手动或者机器(包括往复机、机器人、自动流水线休)喷涂实施例1-4中制备的清漆组合物，形成第二涂层。使所形成的涂层在室温下闪干流平3-10分钟，之后在60-80℃的温度下烘烤约20-30分钟，得到干膜厚度为20～60微米的涂层。最后将经涂覆的基材在60-80℃的温度下烘烤约6-8小时，制得测试样板。
根据下述表9中的各项测试，测试所述样板的各项性能指标。测试结果示于表9中。表9中还测试了两种市售产品的各项性能，该两种产品是主要应用汽车内饰和普通家电市场的产品。
表9.测试结果
Figure PCTCN2018118513-appb-000028
通过上表9可见，本发明的涂层体系1#至4#在所测试的各项性能上优于或至少可比得上市售产品。其中，本发明的涂层体系的铅笔硬度可以达到H等级甚至2H，明显高于现有市售产品的铅笔硬度等级F(铅 笔硬度：2H>H>F>HB>B)。因此，本发明的涂层体系具有优异的耐刮性。并且，对于RCA耐磨性，本发明的涂层体系的测试结果可以达到至少100个，甚至200个循环，比得上甚至优于现有技术中性能优异的溶剂型柔软触感涂料组合物可以达到的水平。通常，对于水性涂料组合物，RCA耐磨性提高的同时可能会使涂料的手感以及施工性变差。本发明的涂层体系能够在提供了高RCA耐磨性的同时，保证了涂料的手感和施工性。
尽管已解释和描述了本发明的特定方面，对本领域技术人员来说很明显的是可做出多种其它改变和修饰而不会背离本发明的精神和范围。因此所附权利要求意图涵盖落入本发明范围内的所有这些改变和修饰。

Claims (20)

  1. 一种多层涂层体系，其包括:
    (a)由包含下述的第一涂料组合物形成的第一涂层：
    (1)丙烯酸树脂；和
    (2)羟基丙烯酸树脂；和
    (b)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：
    (1)脂肪族羟基官能聚酯聚氨酯树脂；和
    (2)水分散型聚碳酸酯二醇树脂。
  2. 如权利要求1所述的多层涂层体系，其中所述丙烯酸树脂包括数均分子量约100,000～120,000的苯乙烯改性丙烯酸树脂。
  3. 如权利要求1所述的多层涂层体系，其中所述羟基丙烯酸树脂具有30～110mgKOH/g的羟值。
  4. 如权利要求1所述的多层涂层体系，其中所述羟基丙烯酸树脂具有4,000～12,000的数均分子量，具有约20～60℃的最低成膜温度。
  5. 如权利要求1所述的多层涂层体系，其中所述第一涂料组合物还包含碱溶性阴离子增稠剂。
  6. 如权利要求5所述的多层涂层体系，其中所述碱溶性阴离子增稠剂为聚丙烯酸型增稠剂。
  7. 如权利要求1所述的多层涂层体系，其中所述脂肪族羟基官能聚酯聚氨酯树脂具有8,000～10,000的数均分子量，以及所述水分散型聚碳酸酯二醇树脂具有800～1000的数均分子量。
  8. 如权利要求1所述的多层涂层体系，其中所述第二涂料组合物还包含聚酯聚氨酯缔合型增稠剂。
  9. 如权利要求1所述的多层涂层体系，其中所述第一和第二涂料组合物还包括含异氰酸酯基团的组分。
  10. 如权利要求9所述的多层涂层体系，其中所述含异氰酸酯基团的组分中的异氰酸酯基团与所述脂肪族羟基官能聚酯聚氨酯树脂中的羟基基团的摩尔比在1.5-2:1的范围内。
  11. 如权利要求9所述的多层涂层体系，其中所述含异氰酸酯基团的组分中的异氰酸酯基团与所述羟基丙烯酸树脂中的羟基基团的摩尔比在1.3～2:1的范围内。
  12. 一种经涂覆的基材，包括：
    (a)基材；
    (b)涂覆在所述基材的至少一部分上的第一涂层，该第一涂层由包括以下的第一涂料组合物形成：
    (1)丙烯酸树脂；和
    (2)羟基丙烯酸树脂；和
    (c)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：
    (1)脂肪族羟基官能聚酯聚氨酯树脂；和
    (2)水分散型聚碳酸酯二醇树脂。
  13. 如权利要求12所述的经涂覆的基材，其中所述基材包括由下述物质形成的基材：聚碳酸酯、丙烯腈-2-丁二烯-2-苯乙烯三元共聚物+聚碳酸酯、聚碳酸酯+玻璃纤维和碳纤维。
  14. 一种多层涂层体系，其包括:
    (a)由包含下述的第一涂料组合物形成的第一涂层：
    (1)丙烯酸树脂；和
    (2)柔性聚氨酯树脂；和
    (b)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：
    (1)脂肪族羟基官能聚酯聚氨酯树脂；和
    (2)水分散型聚碳酸酯二醇树脂。
  15. 如权利要求14所述的多层涂层体系，其中所述丙烯酸树脂包括数均分子量约100,000～120,000的苯乙烯改性丙烯酸树脂。
  16. 如权利要求14所述的多层涂层体系，其中所述柔性聚氨酯树脂包括重量比为60～80:20～40的长链脂肪族聚氨酯树脂和聚碳酸酯改性聚氨酯树脂的混合物。
  17. 如权利要求14所述的多层涂层体系，其中所述脂肪族羟基官能聚酯聚氨酯树脂具有8,000～10,000的数均分子量，以及所述水分散型聚碳酸酯二醇树脂具有800～1000的数均分子量。
  18. 如权利要求14所述的多层涂层体系，其中所述第二涂料组合物还包括含异氰酸酯基团的组分。
  19. 如权利要求18所述的多层涂层体系，其中所述含异氰酸酯基团的组分中的异氰酸酯基团与所述脂肪族羟基官能聚酯聚氨酯树脂中的羟基基团的摩尔比在1.5-2:1的范围内。
  20. 一种经涂覆的基材，包括：
    (a)基材；
    (b)涂覆在所述基材的至少一部分上的第一涂层，该第一涂层由包括以下的第一涂料组合物形成：
    (1)丙烯酸树脂；和
    (2)柔性聚氨酯树脂；和
    (c)直接涂覆在第一涂层的至少一部分上的第二涂层，所述第二涂层由包含下述的第二涂料组合物形成：
    (1)脂肪族羟基官能聚酯聚氨酯树脂；和
    (2)水分散型聚碳酸酯二醇树脂。
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