WO2024082708A1 - 一种通用型纳米蓝相黑浆及其制备方法和应用 - Google Patents

一种通用型纳米蓝相黑浆及其制备方法和应用 Download PDF

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WO2024082708A1
WO2024082708A1 PCT/CN2023/104366 CN2023104366W WO2024082708A1 WO 2024082708 A1 WO2024082708 A1 WO 2024082708A1 CN 2023104366 W CN2023104366 W CN 2023104366W WO 2024082708 A1 WO2024082708 A1 WO 2024082708A1
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black
blue
pigment
blue phase
universal nano
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PCT/CN2023/104366
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English (en)
French (fr)
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刘志伟
潘昌艺
陈川
杨杰
高娟娟
崔亭
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立邦涂料（中国）有限公司
立邦新材料科技(上海)有限公司
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Publication of WO2024082708A1 publication Critical patent/WO2024082708A1/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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/002—Pigment pastes, e.g. for mixing in paints in organic medium
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
    • 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
    • C09D7/41—Organic pigments; Organic dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the invention relates to the field of nano color paste, and mainly relates to a universal nano black color paste which has a pure color, high blackness, and a blue hue after being diluted with aluminum powder, as well as a preparation method and application of the color paste.
  • the black style highlights low-key and luxury, restraint and surging.
  • the black series of each brand often represents a higher-end brand line positioning and higher-end performance; for example, the BMW VBX6 crossover car wears Vantablack VBx2 coating, which can absorb more than 99% of visible light and is considered to be the blackest car in the world.
  • the automotive industry's pursuit of extreme design with high blackness has greatly stimulated the development demand for nano high-pigment black paste.
  • the DIN55979 standard defines the test method for blackness value, that is, using Mc and My to evaluate the blackness of black paste (usually My>300 is defined as high blackness black paste, and the larger the My value, the higher the corresponding blackness).
  • Mc and My defines the black background color from brown to blue.
  • Gray especially metallic gray, accounts for a high proportion of automotive colors (according to Axalta's global automotive color trend report, the total proportion of gray has reached 19%).
  • Metallic gray is usually made by mixing high-pigment black paste with aluminum powder paint. Blue-phase metallic gray often reflects a sense of technology and is more popular with creative color designers. For high-pigment carbon black, the better the dispersion, the higher the pure color blackness, but the corresponding background color (aluminum powder diluted color) hue is more inclined to brown, which is contrary to the blue phase pursued by metallic gray.
  • oil-based automobile coatings usually design different systems and use different types of resins.
  • traditional oil-based color pastes often use co-grinded resins, which are usually the main resins of the corresponding coating system.
  • co-grinded resins are relatively insufficient in the wetting and dispersing properties of pigments, which also limits the color intensity of color pastes to a certain extent.
  • the industry has higher and higher requirements for the color paste grinding process and subsequent paint coating process, which directly leads to a substantial increase in production costs.
  • patent CN111574889B discloses a method for preparing a nano black color paste.
  • the black paste prepared by the method has high blackness and blue color.
  • the black paste to be protected is a water-based color paste, and the patent does not pay attention to the base color of the black paste (the hue diluted by aluminum powder).
  • high-pigment carbon black shows brown in the formula of automotive aluminum paint.
  • Patent CN114058085A discloses a method for preparing a blue-phase black CAB solid masterbatch. The patent uses CAB resin.
  • the blue phase carbon black powder is coated and dispersed by combining the three-roll mill process, but the patent does not describe the specific information of the blue phase carbon black powder and the base color of the black slurry (the hue diluted by aluminum powder), and introduces a large amount of CAB resin, which limits its versatility in different coating application systems.
  • the purpose of the present invention is to provide a universal nano blue phase black paste, which adopts the design concept of resin-free color paste and uses a high-performance dispersant to replace the co-grinding resin, which can not only further increase the pigment concentration in the grinding process, reduce production energy consumption, and be more energy-saving and environmentally friendly, but also improve the compatibility of the color paste in different resin systems, achieve better versatility, and be compatible with solvent-based coating systems such as acrylic acid, polyester, and alkyd resin.
  • the universal blue phase black paste provided by the present invention is a nano color paste, which takes into account both blackness and blue phase, and the pure color has a very excellent blackness, and has a clear blue phase background in aluminum powder paint.
  • the present invention also relates to the preparation method and application of the above-mentioned universal nano blue phase black paste.
  • the first aspect of the present invention provides a universal nano blue phase black slurry, which comprises, by weight percentage:
  • the total mass percentage of the above components is 100%.
  • the black pigment is high-pigment carbon black.
  • the primary particle size of the high-pigment carbon black is 7-17 nm.
  • the black pigment is selected from one or more of the black pigments of model numbers MONARCH 1300, MONARCH 1400, EMPEROR 1600, EMPEROR 1800, and EMPEROR 2000 provided by Cabot, model numbers RAVEN 5000U3 and RAVEN 5000U2 provided by BIRLA CARBON, and model numbers COLOUR BLACK FW 1, COLOUR BLACK FW 2, COLOUR BLACK FW 200, COLOUR BLACK FW 255, COLOUR BLACK FW 171, COLOUR BLACK FW 285, COLOUR BLACK FW 182, and COLOUR BLACK FW 310 provided by Orion.
  • the blue pigment is Pigment Blue PB60 (Indanthrene Blue), which is a reddish blue with high transparency and excellent light and weather fastness.
  • the blue pigment is selected from the models Paliogen Blue L6480, Paliogen Blue L6482, and Paliogen Blue L6400 provided by Sunchemical, the models LIONOGEN BLUE 6510 and LIONOGEN BLUE 6520 provided by Toyo Ink, and the models provided by Heubach MONOLITE BLUE 3RN, MONOLITE BLUE 3RH, one or more of the blue pigments provided by DCC Company with the model numbers DCC Blue A3R and DCC Blue A3RN.
  • the content of the blue pigment is 0.2-1.2 times the content of the black pigment in terms of mass percentage; more preferably, the content of the blue pigment is 0.5-1.0 times the content of the black pigment.
  • the dispersant is selected from one or more of an acrylate type polymer dispersant, a polyester type polymer dispersant, and a polyurethane type polymer dispersant.
  • the structures of the above dispersants all contain functional groups with excellent affinity to the pigment, and solvated chains that can be freely extended in the selected first solvent system.
  • the pigment affinity groups in these dispersants are generally polar groups, such as carboxylic acid groups, phosphoric acid or phosphate groups, amine groups, amide groups, carbamate groups, etc.
  • the solvated chains in the dispersant have similar polarity to the solvent system in the color paste.
  • the solvated chain segments of the dispersant have optimal extension, thereby preventing mutual flocculation between pigment particles to the greatest extent.
  • These solvated chains can be low-polarity alkane chains or polyester chains, medium-polarity polyester chains or acrylate chains.
  • the number average molecular weight of the dispersant is 5000-25000, preferably 10000-20000, and the PDI is 1.0-5.0, preferably 1.0-3.0.
  • the dispersant is selected from one or more of the following types of dispersants: Dispersants, including but not limited to BYK-161, BYK-163, BYK-170, BYK-180, BYK-2000, BYK-2013; Dispersants, including but not limited to Efka PU 4010, Efka PU 4050, Efka PA 4401, Efka PX 4780, PX 4310, PX 4330 dispersant; provided by Lubrizol
  • the dispersant includes but is not limited to the dispersants of model numbers Solsperse 24000 and Solosperse 32500.
  • the coupling agent is selected from one or more of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
  • the silane coupling agent is selected from the Dynasylan DAMO, Dynasylan 1124, Dynasylan 9116, Dynasylan VPS 4721, the model provided by Momentive is A-174NT, Coatosil MP200, one or more of the silane coupling agents of models KBE-9103, KBE-603, KBE-585, KBE-402, and KBE-403 provided by Shin-Etsu Co., Ltd. of Japan;
  • the titanate coupling agent is selected from one or more of the titanate coupling agents of models Plenact 44 and Plenact 55 provided by Ajinomoto Co., Ltd., and models KR-38S and KR-TTS provided by Kenrich Co., Ltd.
  • the aluminate coupling agent is selected from one or more of the aluminate coupling agents of model PLENACT AL-M provided by Ajinomoto Co., Ltd., model LK-AL181 provided by Longkai Chemical Co., Ltd., and model GR-AL18 provided by Nanjing Herun Coupling Agent Co., Ltd.
  • the organic solvent is selected from butyl acetate, S-150 solvent oil, S-100 solvent oil, One or more of mixed dibasic acid esters, methyl isobutyl ketone, xylene, propylene glycol methyl ether acetate, and diacetone alcohol.
  • the selected organic solvent is a mixed solvent of butyl acetate and methyl isobutyl ketone in a mass ratio of 1:1.
  • the second aspect of the present invention provides a method for preparing the universal nano blue phase black slurry described in the first aspect of the present invention, which mainly comprises the following steps:
  • step (2) Grinding and dispersing the mixed solution A pre-dispersed in step (1) using a horizontal sand mill, maintaining the grinding state until the material fineness is dispersed to less than 5 ⁇ m, and discharging the material to obtain the universal nano blue phase black slurry.
  • the grinding medium used for grinding and dispersing in step (2) of the universal nano blue phase black slurry preparation method is zirconia beads; preferably, the diameter of the zirconia beads is 0.3-1.0 mm, and the filling rate is 70%-90%; more preferably, the diameter of the zirconia beads is 0.6-0.8 mm, and the filling rate is 80%.
  • the third aspect of the present invention provides an application of the universal nano blue phase black slurry described in the first aspect of the present invention in the field of automotive coatings.
  • the automotive coating includes but is not limited to solvent-based coating systems such as acrylic, polyester, and alkyd resins.
  • the present invention provides a universal nano blue phase black slurry and a preparation method and application thereof.
  • the universal nano blue phase black slurry takes into account both blackness and blue phase, and the pure color has excellent blackness, and has a very obvious blue phase background in aluminum powder paint, and there is no problem of visual bluish effect.
  • the universal nano blue phase black slurry adopts a formula design concept of no grinding resin, which can not only further increase the pigment concentration in the grinding process, reduce production energy consumption, and be more energy-saving and environmentally friendly, but also improve the compatibility of the color paste in different resin systems.
  • the prepared nano blue phase black slurry has very excellent versatility and is compatible with solvent-based coating systems such as acrylic, polyester, and alkyd resins.
  • the universal nano blue phase black slurry 1 of the present invention is prepared according to the formula in Table 1 below:
  • the preparation of the universal nano blue phase black slurry 1 comprises the following steps:
  • step (2) Using a horizontal sand mill, using zirconium oxide beads as grinding media to grind and disperse the mixed solution A pre-dispersed in step (1), and maintaining the grinding state until the material fineness is dispersed to less than 5 ⁇ m, the material is discharged to obtain the universal nano blue phase black slurry 1.
  • Example 2 Repeat Example 1, with the only difference being that the black pigment RAVEN 5000 U3 is replaced by MONARCH 1300 and the other conditions and preparation methods remain unchanged to prepare a universal nano blue phase black paste 2.
  • Example 1 was repeated, with the only difference being that the coupling agent Dynasylan VPS 4721 was replaced by PLENACT AL-M, and the other conditions and preparation methods remained unchanged, to prepare universal nano blue phase black paste 4.
  • the universal nano blue phase black paste 5 of the present invention is prepared according to the formula in Table 2 below:
  • the universal nano blue phase black paste 6 of the present invention is prepared according to the formula of the following Table 3:
  • Comparative Example 1 Black slurry 1 as a comparative example
  • Black slurry 1 as a comparative example was prepared according to the formula in Table 4 below:
  • Table 4 Formula of black slurry 1 as a comparative example
  • the preparation of the black slurry 1 as a comparative example comprises the following steps:
  • step (2) Using a horizontal sand mill, zirconia beads are used as grinding media to grind the mixed solution A pre-dispersed in step (1), and the grinding state is maintained until the material fineness is dispersed to less than 5 ⁇ m, and the black slurry 1 as a comparative example is obtained.
  • the formula of the black paste 1 as a comparative example does not contain a coupling agent, which is not within the scope of the present invention, so this example is only comparative example 1.
  • the lack of a coupling agent will result in a decrease in the blackness of the prepared black paste.
  • Comparative Example 2 Black slurry 2 as a comparative example
  • Example 1 was repeated, with the only difference being that the blue pigment Paliogen Blue L6480 was replaced by pigment blue PB15:1 Heliogen Blue L6930, and other conditions and preparation methods remained unchanged, to prepare black slurry 2 as a comparative example.
  • the pigment blue PB15:1 Heliogen Blue L6930 used is not pigment blue PB60 (Indanthrene Blue), which is not within the scope of the present invention, so this example is only comparative example 2.
  • Comparative Example 3 Black slurry 3 as a comparative example
  • Example 1 was repeated, with the only difference being that the blue pigment Paliogen Blue L6480 was replaced by pigment blue PB15:4 Heliogen Blue L7101, and other conditions and preparation methods remained unchanged, to prepare black slurry 3 as a comparative example.
  • the pigment blue PB15:4 Heliogen Blue L7101 used is not pigment blue PB60 (Indanthrene Blue), which is not within the scope of the present invention, so this example is only comparative example 3.
  • Comparative Example 4 Black slurry 4 as a comparative example
  • Example 1 was repeated, with the only difference being that the blue pigment Paliogen Blue L6480 was replaced by pigment blue PB15:6 Helioqen Blue L6600F, and other conditions and preparation methods remained unchanged, to prepare black slurry 4 as a comparative example.
  • the pigment blue PB15:6 Helioqen Blue L6600F used is not pigment blue PB60 (Indanthrene Blue), which is not within the scope of the present invention, so this example is only comparative example 4.
  • Comparative Example 5 Black slurry 5 as a comparative example
  • Black slurry 5 as a comparative example was prepared according to the formula in Table 5 below:
  • Table 5 Formula of black slurry 5 as a comparative example
  • the preparation of the black slurry 5 as a comparative example comprises the following steps:
  • step (2) Using a horizontal sand mill, zirconia beads are used as grinding media to grind the mixed solution A pre-dispersed in step (1), and the grinding state is maintained until the material fineness is dispersed to less than 5 ⁇ m, and the black slurry 5 as a comparative example is obtained.
  • the formula of the black paste 5 as a comparative example does not contain a coupling agent and a blue pigment, which is not within the scope of the present invention, so this example is only comparative example 5.
  • the formula lacking a coupling agent and a blue pigment is a conventional general-purpose black paste, which will show an obvious brown phase in the automotive coating aluminum powder paint formula.
  • Automobile coating aluminum powder paint base material calculated by mass percentage, its components include 5.3% Toyo Aluminum 7640NS aluminum powder, 45.1% acrylic resin, 4.5% butyl acetate, and 45.1% automobile paint transparent base material.
  • Color card preparation The color paste and the aluminum powder paint base material of the automotive coating are mixed uniformly at a mass ratio of 2:15, and the color paste is applied on black and white cardboard using a 150 ⁇ m wet film preparation device. After the cardboard is placed in a 120°C oven for 30 minutes for drying, the color of the universal nano blue phase black paste of Examples 1-6 and the black paste of Comparative Examples 1-5 in the aluminum powder paint formula of the automotive coating is measured using a five-angle colorimeter (BYK-mac i five-angle colorimeter). According to the blackness value test method defined in the DIN55979 standard, the 45° color data (L, a, b) are taken to calculate the blackness (Mc, My) and the base color hue dM, and the results are shown in Table 8 below.
  • the universal nano blue phase black slurry prepared based on the technical route of the present invention has significantly improved physical properties.
  • the D50 particle size range of the universal nano blue phase black slurry provided in Examples 1-6 is 90-120nm, which belongs to the category of nano color paste, while the D50 particle size range of the color paste provided in Comparative Examples 1-5 is 300-900nm.
  • the universal nano blue phase black slurry provided in Examples 1-6 has a significantly reduced viscosity.
  • the universal nano blue phase black slurry provided based on the technical route of the present invention takes into account both blackness and blue phase, does not have the problem of visual bluish effect, expands the coating application window, is compatible with a variety of automotive coating systems, and can be widely used in the field of automotive coatings.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

一种通用型纳米蓝相黑浆，按质量百分含量计，其组分包含黑色颜料1-15%、蓝色颜料1-10%、分散剂1-50%、偶联剂1-5%、有机溶剂25-90%，以上各组分的质量百分含量合计为100%。所述通用型纳米蓝相黑浆兼顾了黑度和蓝相，纯色具有优异的黑度，且在铝粉漆中具有非常明显的蓝相底色，不存在目视效果发青的问题。同时，该通用型纳米蓝相黑浆采用无研磨树脂的配方设计理念，不仅可以进一步提高研磨过程中的颜料浓度，降低生产能耗，更为节能环保，而且可以提高色浆在不同树脂体系里的相容性，具有非常优异的通用性，可兼容于丙烯酸、聚酯、醇酸树脂等溶剂型涂料体系，可广泛应用于汽车涂料领域。还涉及上述通用型纳米蓝相黑浆的制备方法及应用。

Description

一种通用型纳米蓝相黑浆及其制备方法和应用 技术领域
本发明涉及纳米色浆领域，主要涉及一种纯色具有高黑度，同时铝粉冲淡具备蓝相色相的通用型纳米黑色色浆，以及该色浆的制备方法和应用。
背景技术
随着汽车行业的快速发展和消费升级，汽车车身的色彩也日趋多样化，更能凸显时尚和个性化潮流，这些色彩变幻的背后呈现的是涂料科技的升级和创新。如果说发动机、变速器等核心部件事关汽车的性能和操控体验，那么汽车涂料则可直接影响汽车的“颜值”和形象，乃至车体的视觉外形、机械性能、耐久性能以及环保等特性，其蕴藏的功能及发展潜力不可小觑。据艾仕得公司全球汽车色彩流行趋势报告统计显示，黑色是仅次于全球主流颜色白色的色系，其总占比高达19％，在欧洲和中国的比例更是达到了22％，可见对于黑色汽车涂料的产量需求是相当可观的。在汽车设计中，黑色格调彰显的是低调与奢华、内敛与澎湃，每个品牌的黑色系列往往代表更高端的品牌线定位和更高配的性能；例如宝马BMW VBX6跨界车穿着Vantablack VBx2涂层，其可以吸收超过99％的可见光，被认为是世界上最黑的汽车。
汽车行业对于高黑度的极致设计追求，大大激发了纳米高色素黑浆的开发需求。DIN55979标准定义了黑度值的测试方法，即使用Mc和My来评价黑浆的黑度(通常My＞300定义为高黑度黑浆，My数值越大，对应黑度越高)，Mc和My的差值(dM)给予了黑颜色底色以棕相到蓝相的定义；灰色尤其是金属灰颜色在汽车颜色中的占比也很高(据艾仕得公司全球汽车色彩流行趋势报告统计显示，灰色总占比也达到了19％)，金属灰通常是使用高色素黑浆与铝粉漆进行调色制得，蓝相金属灰往往更能体现科技感，更受创色设计师欢迎；对于高色素炭黑，当分散度越好时，纯色黑度越高，但对应的底色(铝粉冲淡色)色相就越偏向于棕色相，这与金属灰所追求的蓝相相悖。
此外，为了满足不同的汽车生产线和客户需求，油性汽车涂料通常会设计不同的体系，使用不同类型的树脂。传统的油性色浆为了与涂料体系更好的相容，往往都会使用共研磨树脂，通常为对应涂料体系的主体树脂。相比于结构设计更为精细的分散剂，共研磨树脂在颜料的润湿分散性能上相对不足，这也在一定程度上限制了色浆的颜色强度。现阶段，为了满足日益个性化、高饱和度、高黑度的车身色彩需求，行业对于色浆研磨工艺和后续的涂料涂装工艺的要求也越来越高，这直接导致了生产成本的大幅上升。
现有技术中，专利CN111574889B公开了一种纳米黑色色浆的制备方法，按所述方法制备的黑浆具有高黑度和蓝相面色，但其要求保护的黑浆为水性色浆，且专利中并未关注黑浆的底色(铝粉冲淡的色相)，通常而言，高色素炭黑在汽车铝粉漆配方中都表现出棕色。专利CN114058085A公开了一种蓝相黑CAB固体色母的制备方法，该专利使用CAB树脂， 结合三辊研磨机工艺对蓝相炭黑色粉进行包覆与分散，但该专利中并未描述其蓝相炭黑色粉的具体信息以及黑浆的底色(铝粉冲淡的色相)，且引入了大量的CAB树脂，限制了其在不同涂料应用体系里的通用性。
综上所述，亟需开发一种纯色具有高黑度，同时铝粉冲淡具备蓝相色相的通用型纳米黑浆，以满足汽车创色需求，解决现有纳米色浆领域中面临的问题。
发明内容
基于以上事实，本发明的目的在于提供一种通用型纳米蓝相黑浆，其采用了无树脂色浆的设计理念，使用高性能分散剂取代共研磨树脂，不仅可以进一步提高研磨过程中的颜料浓度，降低生产能耗，更为节能环保，而且可以提高色浆在不同树脂体系里的相容性，达到更好的通用性，可兼容于丙烯酸、聚酯、醇酸树脂等溶剂型涂料体系。相比于传统的黑色浆而言，本发明提供的通用型蓝相黑浆是一种纳米色浆，其兼顾了黑度和蓝相，纯色具有非常优异的黑度，且在铝粉漆中具有明显的蓝相底色。本发明还涉及上述通用型纳米蓝相黑浆的制备方法和应用。
本发明的第一方面提供了一种通用型纳米蓝相黑浆，按质量百分含量计，其组分包含：
以上各组分的质量百分含量合计为100％。
黑色颜料
在本发明的一些实施例中，所述黑色颜料为高色素炭黑，优选地，所述高色素炭黑的原生粒径为7-17nm。
具体地说，所述黑色颜料选自卡博特公司(Cabot)提供的型号为MONARCH 1300、MONARCH 1400、EMPEROR 1600、EMPEROR 1800、EMPEROR 2000，博拉公司(BIRLA CARBON)提供的型号为RAVEN 5000U3、RAVEN 5000U2，欧励隆公司(Orion)提供的型号为COLOUR BLACK FW 1、COLOUR BLACK FW 2、COLOUR BLACK FW 200、COLOUR BLACK FW 255、COLOUR BLACK FW 171、COLOUR BLACK FW 285、COLOUR BLACK FW 182、COLOUR BLACK FW 310的黑色颜料中的一种或几种。
蓝色颜料
在本发明的一些实施例中，所述蓝色颜料为颜料蓝PB60(阴丹士林蓝)，其为红光蓝色，且具有高透明度和优异的耐光、耐候牢度。
具体地说，所述蓝色颜料选自钛阳化学公司(Sunchemical)提供的型号为Paliogen Blue L6480、Paliogen Blue L6482、Paliogen Blue L6400，东洋油墨公司(Toyo ink)提供的型号为LIONOGEN BLUE 6510、LIONOGEN BLUE 6520，Heubach公司提供的型号为 MONOLITE BLUE 3RN、MONOLITE BLUE 3RH，DCC公司提供的型号为DCC Blue A3R、DCC Blue A3RN的蓝色颜料中的一种或几种。
在本发明的一些优选实施例中，在所述通用型纳米蓝相黑浆中，按质量百分含量计，所述蓝色颜料的含量为所述黑色颜料含量的0.2-1.2倍；更为优选地，所述蓝色颜料的含量为所述黑色颜料含量的0.5-1.0倍。
分散剂
在本发明的一些实施例中，所述分散剂选自丙烯酸酯类型的聚合物分散剂、聚酯类型的聚合物分散剂、聚氨酯类型的聚合物分散剂中的一种或几种。以上所述分散剂的结构都包含与颜料具有优异亲和性能的官能团，以及在选用的第一溶剂体系中可自由伸展的溶剂化链。这些分散剂中的颜料亲和性基团一般为极性基团，例如羧酸基团、磷酸或磷酸酯基团、胺基、酰胺基、氨基甲酸酯基等。分散剂中的溶剂化链与色浆中的溶剂体系具有类似的极性，在这种情况下，分散剂的溶剂化链段具有最佳的伸展，从而能最大限度的防止颜料粒子之间的互相絮凝，这些溶剂化链可以是低极性烷烃链或聚醋链、中等极性聚酯链或丙烯酸酯链。
在本发明的一些优选实施例中，所述分散剂的数均分子量为5000-25000，优选为10000-20000，PDI为1.0-5.0，优选为1.0-3.0。
具体的说，所述分散剂选自以下型号分散剂中的一种或几种：Byk Chemie公司提供的分散剂，包括但不限于型号为BYK-161、BYK-163、BYK-170、BYK-180、BYK-2000、BYK-2013的分散剂；BASF公司提供的分散剂，包括但不限于型号为Efka PU 4010、Efka PU 4050、Efka PA 4401、Efka PX 4780、PX 4310、PX 4330的分散剂；Lubrizol公司提供的分散剂，包括但不限于型号为Solsperse 24000、Solosperse32500的分散剂。
偶联剂
在本发明的一些实施例中，所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的一种或几种。
具体地说，所述硅烷偶联剂选自EVONIK公司提供的型号为Dynasylan DAMO、Dynasylan 1124、Dynasylan 9116、Dynasylan VPS 4721，迈图公司提供的型号为A-174NT、Coatosil MP200，日本信越公司提供的型号为KBE-9103、KBE-603、KBE-585、KBE-402、KBE-403的硅烷偶联剂中的一种或几种；所述钛酸酯偶联剂选自味之素公司提供的型号为Plenact 44、Plenact 55，美国肯瑞奇公司提供的型号为KR-38S、KR-TTS的钛酸酯偶联剂中的一种或几种；所述铝酸酯偶联剂选自味之素公司提供的型号为PLENACT AL-M，龙凯化工公司提供的型号为LK-AL181，南京和润偶联剂公司提供的型号为GR-AL18的铝酸酯偶联剂中的一种或几种。
有机溶剂
在本发明的一些实施例中，所述有机溶剂选自醋酸丁酯、S-150溶剂油、S-100溶剂油、 混合二元酸酯、甲基异丁基酮、二甲苯、丙二醇甲醚醋酸酯、二丙酮醇中的一种或几种。
在本发明的一些优选实施例中，所选有机溶剂为质量比为1:1的乙酸丁酯和甲基异丁基酮混合溶剂。
本发明的第二方面提供了一种制备本发明第一方面所述通用型纳米蓝相黑浆的方法，主要包括如下步骤：
(1)将配方重量的分散剂加入有机溶剂中，以600-1000r/min的速度搅拌5-15min，然后在同样的搅拌状态下加入黑色颜料和蓝色颜料，以1500-2000r/min的速度搅拌30min分钟后加入偶联剂，保持1500-2000r/min的速度继续搅拌30分钟，得到混合液A；
(2)使用卧式砂磨机研磨分散步骤(1)中预分散好的混合液A，保持研磨状态直至物料细度分散至5μm以下，出料即得所述通用型纳米蓝相黑浆。
在本发明的一些优选实施例中，所述通用型纳米蓝相黑浆制备方法步骤(2)中研磨分散所用的研磨介质为氧化锆珠；优选地，所述氧化锆珠的直径为0.3-1.0mm，填充率为70％-90％；更为优选地，所述氧化锆珠的直径为0.6-0.8mm，填充率为80％。
本发明的第三方面提供了一种本发明第一方面所述通用型纳米蓝相黑浆在汽车涂料领域中的应用。
在本发明的一些实施例中，所述汽车涂料包括但不限于丙烯酸、聚酯、醇酸树脂等溶剂型涂料体系。
本发明的有益效果如下：
本发明针对现有技术中存在的不足，提供了一种通用型纳米蓝相黑浆及其制备方法和应用。该通用型纳米蓝相黑浆兼顾了黑度和蓝相，纯色具有优异的黑度，且在铝粉漆中具有非常明显的蓝相底色，不存在目视效果发青的问题。同时，该通用型纳米蓝相黑浆采用无研磨树脂的配方设计理念，不仅可以进一步提高研磨过程中的颜料浓度，降低生产能耗，更为节能环保，而且可以提高色浆在不同树脂体系里的相容性，制得的纳米蓝相黑浆具有非常优异的通用性，可兼容于丙烯酸、聚酯、醇酸树脂等溶剂型涂料体系。
具体实施方式
为了更清楚地说明本发明，下面结合具体实施例和对比例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。下述实施例和对比例中所用的实验方法如无特殊说明，均为常规方法，所使用的原料和试剂如无特殊说明，均为可从常规商业途径购买的产品。
实施例1：通用型纳米蓝相黑浆1
根据以下表1的配方制备本发明所述的通用型纳米蓝相黑浆1：
表1通用型纳米蓝相黑浆1的配方

该通用型纳米蓝相黑浆1的制备包括如下步骤：
(1)将配方重量的分散剂加入有机溶剂中，以800r/min的速度搅拌10min，然后在同样的搅拌速度下加入黑色颜料和蓝色颜料，以1500r/min的速度搅拌30min分钟后加入偶联剂，保持1500r/min的速度继续搅拌30分钟，得到混合液A；
(2)使用卧式砂磨机，以氧化锆珠为研磨介质研磨分散步骤(1)中预分散好的混合液A，保持研磨状态直至物料细度分散至5μm以下，出料即得所述通用型纳米蓝相黑浆1。
实施例2：通用型纳米蓝相黑浆2
重复实施例1，区别仅在于将其中的黑色颜料RAVEN 5000 U3替换为MONARCH 1300，其余条件和制备方法不变，制备得到通用型纳米蓝相黑浆2。
实施例3：通用型纳米蓝相黑浆3
重复实施例1，区别仅在于将其中的蓝色颜料Paliogen Blue L6480替换为DCC Blue A3R，其余条件和制备方法不变，制备得到通用型纳米蓝相黑浆3。
实施例4：通用型纳米蓝相黑浆4
重复实施例1，区别仅在于将其中的偶联剂Dynasylan VPS 4721替换为PLENACT AL-M，其余条件和制备方法不变，制备得到通用型纳米蓝相黑浆4。
实施例5：通用型纳米蓝相黑浆5
根据以下表2的配方制备本发明所述的通用型纳米蓝相黑浆5：
表2通用型纳米蓝相黑浆5的配方
该通用型纳米蓝相黑浆5的制备步骤同实施例1。
实施例6：通用型纳米蓝相黑浆6
根据以下表3的配方制备本发明所述的通用型纳米蓝相黑浆6：
表3通用型纳米蓝相黑浆6的配方
该通用型纳米蓝相黑浆6的制备步骤同实施例1。
对比例1：作为对比例的黑浆1
根据以下表4的配方制备作为对比例的黑浆1：
表4作为对比例的黑浆1的配方
该作为对比例的黑浆1的制备包括如下步骤：
(1)将配方重量的分散剂加入有机溶剂中，以800r/min的速度搅拌10min，然后在同样的搅拌速度下加入黑色颜料和蓝色颜料，以1500r/min的速度搅拌30min分钟，得到混合液A；
(2)使用卧式砂磨机，以氧化锆珠为研磨介质研磨分散步骤(1)中预分散好的混合液A，保持研磨状态直至物料细度分散至5μm以下，出料即得作为对比例的黑浆1。
需要说明的是，在本对比例中，作为对比例的黑浆1的配方中不含偶联剂，其不在本发明的范围内，故该例仅为对比例1。缺少偶联剂会导致所制备的黑浆黑度有所降低。
对比例2：作为对比例的黑浆2
重复实施例1，区别仅在于将其中的蓝色颜料Paliogen Blue L6480替换为颜料蓝PB15:1 Heliogen Blue L6930，其余条件和制备方法不变，制备得到作为对比例的黑浆2。
需要说明的是，在本对比例中，所用颜料蓝PB15:1 Heliogen Blue L6930不是颜料蓝PB60(阴丹士林蓝)，其不在本发明的范围内，故该例仅为对比例2。
对比例3：作为对比例的黑浆3
重复实施例1，区别仅在于将其中的蓝色颜料Paliogen Blue L6480替换为颜料蓝PB15:4 Heliogen Blue L7101，其余条件和制备方法不变，制备得到作为对比例的黑浆3。
需要说明的是，在本对比例中，所用颜料蓝PB15:4 Heliogen Blue L7101不是颜料蓝PB60(阴丹士林蓝)，其不在本发明的范围内，故该例仅为对比例3。
对比例4：作为对比例的黑浆4
重复实施例1，区别仅在于将其中的蓝色颜料Paliogen Blue L6480替换为颜料蓝PB15:6 Helioqen Blue L6600F，其余条件和制备方法不变，制备得到作为对比例的黑浆4。
需要说明的是，在本对比例中，所用颜料蓝PB15:6 Helioqen Blue L6600F不是颜料蓝PB60(阴丹士林蓝)，其不在本发明的范围内，故该例仅为对比例4。
对比例5：作为对比例的黑浆5
根据以下表5的配方制备作为对比例的黑浆5：
表5作为对比例的黑浆5的配方
该作为对比例的黑浆5的制备包括如下步骤：
(1)将配方重量的分散剂加入有机溶剂中，以800r/min的速度搅拌10min，然后在同样的搅拌速度下加入黑色颜料，以1500r/min的速度搅拌30min分钟，得到混合液A；
(2)使用卧式砂磨机，以氧化锆珠为研磨介质研磨分散步骤(1)中预分散好的混合液A，保持研磨状态直至物料细度分散至5μm以下，出料即得作为对比例的黑浆5。
需要说明的是，在本对比例中，作为对比例的黑浆5的配方中不含偶联剂和蓝色颜料，其不在本发明的范围内，故该例仅为对比例5。缺少偶联剂和蓝色颜料的配方为常规的通用型黑浆，在汽车涂料铝粉漆配方中会表现出明显的棕色相。
为了评价实施例1-6通用型纳米蓝相黑浆和对比例1-5黑浆的性能，进行如下处理和测试。
1.测定实施例1-6通用型纳米蓝相黑浆和对比例1-5黑浆的细度、粘度(TVB-10MW数显粘度仪)、粒径D50(粒径分析仪Nanotrac Flex，Microtrac)，结果如下表6所示。
表6实施例1-6和对比例1-5的物理性能数据
2.测定实施例1-6通用型纳米蓝相黑浆和对比例1-5黑浆的颜色对比，包括纯色的黑度(Mc,My)和金属漆铝粉冲淡的底色色相(dM)。
(1)纯色的颜色评价
色卡制备：色浆与汽车漆透明基料按质量比1:4比例混合均匀，用150μm湿膜制备器在黑白卡纸上刮涂，卡纸放置于120℃烘箱15min烘干后，用五角度测色仪(BYK-mac i五角度测色仪)测定实施例1-6通用型纳米蓝相黑浆和对比例1-5黑浆的纯色颜色，按照DIN55979标准定义的黑度值测试方法，取45°颜色数据(L,a,b)计算黑度(Mc,My)，结果如下表7所示。
表7实施例1-6和对比例1-5的纯色颜色数据
(2)金属漆铝粉冲淡的颜色评价
测定实施例1-6通用型纳米蓝相黑浆和对比例1-5黑浆在汽车涂料铝粉漆配方中的五角度色相。
汽车涂料铝粉漆基料：按质量百分含量计，其组分包含5.3％东洋铝业7640NS铝粉，45.1％丙烯酸树脂，4.5％乙酸丁酯，45.1％汽车漆透明基料。
色卡制备：色浆与汽车涂料铝粉漆基料按质量比2:15的比例混合均匀，用150μm湿膜制备器在黑白卡纸上刮涂，卡纸放置于120℃烘箱30min烘干后，用五角度测色仪(BYK-mac i五角度测色仪)测定实施例1-6通用型纳米蓝相黑浆和对比例1-5黑浆在汽车涂料铝粉漆配方中的颜色。按照DIN55979标准定义的黑度值测试方法，取45°颜色数据(L,a,b)计算黑度(Mc，My)和底色色相dM，结果如下表8所示。
表8实施例1-6和对比例1-5应用于汽车涂料铝粉漆配方中颜色数据

从表6的结果可知，基于本发明技术路线制备的通用型纳米蓝相黑浆具有显著提升的物理性能，实施例1-6提供的通用型纳米蓝相黑浆的D50粒径范围为90-120nm，属于纳米色浆范畴，而对比例1-5提供的色浆的D50粒径范围为300-900nm。同时，实施例1-6提供的通用型纳米蓝相黑浆具有显著降低的粘度。
从表7的结果可知，从五角度色相中的45°的L值和My值对比可知，本发明实施例1-6提供的通用型纳米蓝相黑浆具有优异的黑度表现(My数值＞300，属于高黑度黑浆)，而对比例1没有使用偶联剂，所制备的黑浆黑度有所降低。
从表8的结果可知，从五角度色相中的45°的b*值和dM值对比可知，本发明实施例1-6提供的通用型纳米蓝相黑浆具有优异的蓝相金属灰颜色表现(b值小于0，dM数值都大于0)；而对比例2-4虽然具有较好的蓝相，但从其a值来看，绿相明显，导致目视明显发青；对比例5为常规的通用型黑浆，在汽车涂料铝粉漆配方中表现出明显的棕色相(dM＝-10.63)，这与金属灰所追求的蓝相相悖。
综上所述，基于本发明技术路线提供的通用型纳米蓝相黑浆兼顾了黑度和蓝相，不存在目视效果发青的问题，扩大了涂料应用端窗口，对多种汽车涂料体系具有兼容性，可以广泛应用于汽车涂料领域。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种通用型纳米蓝相黑浆，按质量百分含量计，其组分包含：
  2. 根据权利要求1所述的通用型纳米蓝相黑浆，其特征在于，所述黑色颜料为高色素炭黑；优选地，所述黑色颜料为原生平均粒径为7-17nm的高色素炭黑。
  3. 根据权利要求1所述的通用型纳米蓝相黑浆，其特征在于，所述蓝色颜料为颜料蓝PB60(阴丹士林蓝)；优选地，按质量百分含量计，所述蓝色颜料在所述通用型纳米蓝相黑浆中的含量为所述黑色颜料在所述通用型纳米蓝相黑浆中的含量的0.2-1.2倍；更为优选地，按质量百分含量计，所述蓝色颜料在所述通用型纳米蓝相黑浆中的含量为所述黑色颜料在所述通用型纳米蓝相黑浆中的含量的0.5-1.0倍。
  4. 根据权利要求1所述的通用型纳米蓝相黑浆，其特征在于，所述分散剂选自丙烯酸酯类型的聚合物分散剂、聚酯类型的聚合物分散剂、聚氨酯类型的聚合物分散剂中的一种或几种；优选地，所述分散剂的数均分子量为5000-25000，PDI为1.0-5.0；更为优选地，所述分散剂的数均分子量为10000-20000，PDI为1.0-3.0。
  5. 根据权利要求1所述的通用型纳米蓝相黑浆，其特征在于，所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的一种或几种。
  6. 根据权利要求1所述的通用型纳米蓝相黑浆，其特征在于，所述有机溶剂选自醋酸丁酯、S-150溶剂油、S-100溶剂油、混合二元酸酯、甲基异丁基酮、二甲苯、丙二醇甲醚醋酸酯、二丙酮醇中的一种或几种。
  7. 根据权利要求1所述的通用型纳米蓝相黑浆，其特征在于，所述有机溶剂为质量比为1:1的乙酸丁酯和甲基异丁基酮混合溶剂。
  8. 一种如权利要求1-7任一项所述的通用型纳米蓝相黑浆的制备方法，其特征在于，包括如下步骤：
    (1)将配方重量的分散剂加入有机溶剂中，以600-1000r/min的速度搅拌5-15min，然后在同样的搅拌状态下加入黑色颜料和蓝色颜料，以1500-2000r/min的速度搅拌30min分钟后加入偶联剂，保持1500-2000r/min的速度继续搅拌30分钟，得到混合液A；
    (2)使用卧式砂磨机研磨分散步骤(1)中预分散好的混合液A，保持研磨状态直至物料细度分散至5μm以下，出料即得所述通用型纳米蓝相黑浆。
  9. 根据权利要求8所述的通用型纳米蓝相黑浆的制备方法，其特征在于，步骤(2)中所述研磨分散过程中所用的研磨介质为氧化锆珠；优选地，所述氧化锆珠的直径为0.3-1.0mm，填充率为70％-90％；更为优选地，所述氧化锆珠的直径为0.6-0.8mm，填充率为80％。
  10. 一种如权利要求1-7任一项所述的通用型纳米蓝相黑浆在溶剂型涂料体系中的应用，其特征在于，所述溶剂型涂料体系包括但不限于丙烯酸、聚酯、醇酸树脂等汽车涂料应用领域常用的溶剂型涂料体系。
PCT/CN2023/104366 2022-10-20 2023-06-30 一种通用型纳米蓝相黑浆及其制备方法和应用 WO2024082708A1 (zh)

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JPS58167654A (ja) * 1982-03-29 1983-10-03 Toyo Ink Mfg Co Ltd 顔料組成物
US20030125488A1 (en) * 2001-08-22 2003-07-03 Shuichi Nakahara Pigment dispersing resins
JP2006273942A (ja) * 2005-03-28 2006-10-12 Sumitomo Osaka Cement Co Ltd 塗料および塗膜
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