WO2023174010A1 - 一种免喷涂效果颜料及其制备方法和应用 - Google Patents

一种免喷涂效果颜料及其制备方法和应用 Download PDF

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Publication number
WO2023174010A1
WO2023174010A1 PCT/CN2023/077244 CN2023077244W WO2023174010A1 WO 2023174010 A1 WO2023174010 A1 WO 2023174010A1 CN 2023077244 W CN2023077244 W CN 2023077244W WO 2023174010 A1 WO2023174010 A1 WO 2023174010A1
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Prior art keywords
spray
effect pigment
free
parts
thermosetting resin
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PCT/CN2023/077244
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English (en)
French (fr)
Inventor
朱秀梅
陈平绪
叶南飚
黄险波
刘鑫鑫
常欢
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金发科技股份有限公司
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Publication of WO2023174010A1 publication Critical patent/WO2023174010A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper

Definitions

  • the present invention relates to the technical field of spray-free materials, and more specifically, to a spray-free effect pigment and its preparation method and application.
  • Spray-free metal effect materials can reduce the production process of spray painting or electroplating, avoid environmental pollution, and can achieve diversified metal effects to meet the diverse needs of consumers.
  • Spray-free effect pigments are usually added to the plastic matrix to achieve a spray-free metallic effect.
  • Conventionally used spray-free effect pigments include metal powder, pearlescent powder, etc., which are mainly in the form of flakes, so they are prone to flipping during the injection molding process; and inorganic substances and organic resins are naturally incompatible, and metal powder and pearlescent powder are compatible in the plastic matrix. Poor capacitance can easily lead to serious weld marks and flow marks.
  • the prior art discloses a polyolefin material that does not require spraying of metal effects, adding spherical particles modified with surfactants to suppress the deflection of the flaky metal effect pigments at the melt junction with the direction of the melt flow; however, Inorganic substances with modified spherical particles with a particle size of 10 to 80 ⁇ m are easily sheared and broken during the extrusion and injection molding process, causing the steric hindrance to disappear.
  • an aesthetic resin composition that improves appearance, including a thermosetting effect pigment masterbatch.
  • the effect pigment is coated with a thermosetting resin to increase its particle size and make it difficult to orient and flip; however, coating will cause local agglomeration of the effect pigment. This affects the spray-free appearance.
  • the present invention provides a spray-free effect pigment, which includes thermosetting resin microspheres, a coupling agent and an effect pigment.
  • a spray-free effect pigment which includes thermosetting resin microspheres, a coupling agent and an effect pigment.
  • Another object of the present invention is to provide a method for preparing the above-mentioned spray-free effect pigment.
  • Another object of the present invention is to provide a spray-free material, including the above-mentioned spray-free effect pigment.
  • Another object of the present invention is to provide a method for preparing the above-mentioned spray-free material.
  • Another object of the present invention is to provide the application of the above-mentioned spray-free materials.
  • the technical solution adopted by the present invention is:
  • effect pigment 10 to 200 parts of coupling agent, 10 to 200 parts of thermosetting resin microspheres;
  • the effect pigment is in the form of flakes, with an average particle size of 6 to 350 ⁇ m;
  • the ratio of the average particle diameters of the thermosetting resin microspheres and the effect pigments is 1: (3-100).
  • thermosetting resin microspheres are dispersed in the form of small micron-sized particles around the flaky effect pigments.
  • the effect pigments connect several small thermosetting resin microsphere particles through a coupling agent to form a spatial position. Resistance, reducing flipping during the injection molding process; and the small particle size of thermosetting resin microspheres can play a maximum directional anti-turning effect with a relatively minimum amount of addition, retaining the original physical properties of the spray-free material to the greatest extent.
  • thermosetting resin microspheres are connected to effect pigments through a coupling agent.
  • thermosetting resin has better compatibility with general plastic matrices, which improves the compatibility and dispersion of effect pigments in organic resins.
  • the synergistic effect allows the spray-free effect pigment of the present invention to be added to the plastic matrix, which can not only bring good spray-free metal effect, but also avoid welding marks and Flow mark phenomenon.
  • thermosetting resin in the thermosetting resin microspheres is one or more of thermosetting acrylic resin, thermosetting phenolic resin, thermosetting epoxy resin, thermosetting polyamide resin, thermosetting polyimide resin or silicone resin.
  • the coupling agent is a silane coupling agent and/or a titanate coupling agent.
  • the silane coupling agent is aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane.
  • the titanate coupling agent is tetrabutyl titanate, isopropyl triisostearyl titanate, isopropyl trititanate, ethyl diisostearyl phthalate, isopropyl titanate
  • dioleic acid acyloxy (dioctyl phosphate acyloxy) titanate or distearoyloxy isopropyl aluminate.
  • the effect pigments may be effect pigments commonly used in spray-free materials.
  • the effect pigment is metal powder and/or pearlescent powder.
  • the metal powder is aluminum powder, copper powder, gold powder, silver powder, zinc powder, tin powder, iron powder or nickel powder. one or more of them.
  • the spray-free effect pigment includes the following components by weight:
  • effect pigment 100 parts of effect pigment, 20-50 parts of coupling agent, 30-100 parts of thermosetting resin microspheres.
  • the ratio of the average particle diameters of the thermosetting resin microspheres and the effect pigments is 1: (6-30).
  • the present invention also protects the preparation method of the above-mentioned spray-free effect pigment, which includes the following steps:
  • the effect pigment and the thermosetting resin are dispersed in an organic solvent in which a coupling agent is dissolved. After stirring, the organic solvent is removed to obtain the spray-free effect pigment.
  • the organic solvent is one or more of ethanol, methanol, acetonitrile, dioxane or tetrahydrofuran.
  • the organic solvent is ethanol.
  • the normal temperature is 15-35°C
  • the stirring time is 2-8 hours.
  • the solvent removal refers to removal by heating or removal under reduced pressure.
  • the invention also protects a spray-free material, which includes the following components by weight:
  • thermoplastic resin 100 parts of thermoplastic resin, 0.5 to 10 parts of the spray-free effect pigment.
  • the thermoplastic resin is polyolefin resin, styrene resin, polyvinyl chloride resin, polyester resin, polycarbonate resin, polyamide resin, polymethylmethacrylate or polyurethane.
  • the thermoplastic resin is polyolefin resin, styrene resin, polyvinyl chloride resin, polyester resin, polycarbonate resin, polyamide resin, polymethylmethacrylate or polyurethane.
  • styrene resin polyvinyl chloride resin
  • polyester resin polycarbonate resin
  • polyamide resin polymethylmethacrylate or polyurethane
  • the spray-free material may also include 0.1 to 35 parts by weight of additives.
  • the additives may be functional additives commonly used in thermoplastic resins.
  • the auxiliary agent is one or more of flame retardants, antioxidants, toughening agents, nucleating agents, lubricants, compatibilizers, stabilizers, plasticizers or antistatic agents.
  • the present invention also protects the preparation method of the above-mentioned spray-free material, which includes the following steps:
  • thermoplastic resin and additives are mixed and then added to the main feeding port of the extruder.
  • the spray-free effect pigment is added to the side feeding port of the extruder, followed by melting, mixing, extrusion and granulation. The spray-free material is obtained.
  • the extruder is a twin-screw extruder.
  • the extrusion temperature is 170-320°C, and the screw speed is 350-450 rpm.
  • the present invention also protects the application of the above-mentioned spray-free materials in the fields of electronic appliances, sporting goods, office supplies, and transportation.
  • the present invention has developed a spray-free effect pigment.
  • the synergistic compatibility is improved, so that the spray-free effect pigment of the present invention is added to the plastic matrix, which can not only bring good spray-free effect Metal effect, and avoids weld marks and flow marks.
  • Figure 1 is an SEM scanning electron microscope image of the spray-free effect pigment prepared in Example 1.
  • Figure 2 is a schematic diagram of the evaluation criteria for the visualization degree of flow marks and weld lines.
  • the raw materials in the examples are all commercially available;
  • the reagents, methods and equipment used in the present invention are conventional reagents and methods in this technical field. Laws and equipment.
  • Embodiments 1 to 16 respectively provide a spray-free effect pigment.
  • the component content is shown in Table 1.
  • the preparation method is as follows:
  • the effect pigment and thermosetting resin are dispersed in an organic solvent (ethanol, commercially available) dissolved in a coupling agent. After stirring for 5 hours, the organic solvent is removed by heating to obtain a spray-free effect pigment.
  • organic solvent ethanol, commercially available
  • Table 1 Component contents (parts by weight) of the spray-free effect pigments of Examples 1 to 16
  • Embodiments 17 to 34 respectively provide a spray-free material.
  • the component contents are shown in Table 2.
  • the preparation method is as follows:
  • thermoplastic resin is added to the main feeding port of the twin-screw extruder, and the spray-free effect pigment is added to the side feeding port of the twin-screw extruder. After melting, mixing, extrusion and granulation, a spray-free material is obtained; The outlet temperature is 170 ⁇ 320°C, and the screw speed is 350 ⁇ 450rpm.
  • Comparative Examples 1 to 5 respectively provide a spray-free effect pigment, the component content is shown in Table 3, and the preparation method is the same as Examples 1 to 16.
  • Comparative Examples 6 to 11 respectively provide a spray-free material, the component content is shown in Table 4, and the preparation method is the same as Examples 17 to 34.
  • SEM scanning electron microscope Use a scanning electron microscope to observe the microstructure of the spray-free effect pigment prepared in Example 1, with a magnification of 1500 times;
  • Spray-free metal/pearl effect Inject the spray-free material into a 100*50*2mm color plate, and visually evaluate the spray-free effect.
  • the evaluation criteria are: Level 0, almost no metallic/pearl effect; 1 Level 2, a slightly weak metallic/pearlescent feel; Level 2, a moderate metallic/pearlescent feel; Level 3, a strong metallic/pearlescent feel; Level 2 or 3 is considered qualified; the spray-free effect rating value is determined by 3 testers Determine, average;
  • Visualization degree of flow marks and welding lines (V): Prepare a specific mold by modifying the 200*30*2mm spline mold, open a hole with a diameter of 5mm near the gate, and observe the welding lines and flow marks.
  • the evaluation criteria for visibility are: Level 1, almost no welding lines and flow marks; Level 2, acceptable weak welding lines and flow marks; Level 3, obvious welding lines and flow marks; Level 4, obvious welding. Lines and flow marks; the schematic diagram of the evaluation criteria is shown in Figure 2; the visual degree rating values of flow marks and weld lines are judged by 3 testers, and the average value is taken;
  • thermosetting resin microspheres prepared in Example 1 without spraying effect pigments are dispersed in the form of particles around the flaky effect pigments.
  • the inventor's research found that the effect pigment connects several small thermosetting resin microsphere particles through a coupling agent, which can form steric hindrance, reduce flipping during the injection molding process, and make the appearance of the spray-free material better.
  • the spray-free effect pigments prepared in various embodiments of the present invention can bring excellent spray-free metallic/pearlescent effects to thermoplastic resins, with low visibility of flow marks and weld lines, and small weld line lengths, containing
  • the spray-free material of the spray-free effect pigment of the present invention has excellent spray-free appearance effect.
  • Example 17 to 28 the comprehensive appearance effect index (I) of the spray-free materials of Examples 18, 19, 22, 23, 25, 27, and 28 is relatively higher, and the spray-free effect is better; followed by Example 17, Examples 20 and 21 again, and Examples 24 and 26 again. It can be seen that the ratio of the average particle size of the thermosetting resin microspheres to the effect pigment is different, and the average particle size of the effect pigment is different, which affects the spray-free appearance of the material.
  • the ratio of the average particle diameters of thermosetting resin microspheres and effect pigments is preferably 1:(6-30).
  • the spray-free appearance effect index of Embodiments 31 and 32 is slightly worse. Therefore, the component content of the spray-free effect pigment is preferably: effect pigment 100 parts, coupling agent 20-50 parts, thermosetting resin microspheres 30-100 parts.
  • the average particle size of the effect pigment in Comparative Example 1 is too small, the ratio of the average particle size of the effect pigment to the thermosetting resin microspheres in Comparative Examples 3 and 4 exceeds the scope of the technical solution of the present invention, and the free-form particles prepared in Comparative Examples 6, 8 and 9 are The spray-free effect of spray-coated materials is poor. This shows that thermosetting resin microspheres and effect pigments interact with each other. The particle size of the effect pigment itself, as well as the ratio of the average particle size of the thermosetting resin microspheres to the effect pigment, all significantly affect the spray-free effect pigment. The effect is exerted.
  • the effect pigment in Comparative Example 2 is not in the form of flakes, but in the form of spherical aluminum powder.
  • Thermosetting resin microspheres cannot cooperate with spherical effect pigments and form steric hindrance, making it difficult to reduce the flipping of effect pigments during the injection molding process.
  • Comparative ratio 7 The spray-free material produced has poor appearance.
  • the spray-free effect pigment used in Comparative Example 10 does not contain a coupling agent, and the connection between the effect pigment and the thermosetting resin microspheres is poor, resulting in a poor spray-free appearance of Comparative Example 10.
  • the spray-free material of Comparative Example 11 does not contain the spray-free effect pigment of the present invention, but directly adds aluminum powder. It can be seen that although the spray-free material has a level 3 metal effect, the welding lines and flow marks are very obvious, and the welding lines are too long, and the overall appearance effect index is poor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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Abstract

本发明公开了一种免喷涂效果颜料及其制备方法和应用。所述免喷涂效果颜料，包括如下重量份的组分：效应颜料100份，偶联剂10～200份，热固性树脂微球10～200份；所述效应颜料为片状，平均粒径为6～350μm；所述热固性树脂微球与效应颜料的平均粒径之比为1∶(3～100)。本发明通过小颗粒热固性树脂的位阻作用协同相容性的改善，使得本发明所述免喷涂效果颜料加至塑料基体中，既能带来良好的免喷涂金属效果，且避免了熔接痕和流痕现象。

Description

一种免喷涂效果颜料及其制备方法和应用 技术领域
本发明涉及免喷涂材料技术领域，更具体的，涉及一种免喷涂效果颜料及其制备方法和应用。
背景技术
随着社会各界对环保问题愈来愈关注，免喷涂金属效果材料也逐步获得人们的青睐。免喷涂材料可减少喷漆或电镀生产工艺流程，避免环境污染，而且可以实现多样化的金属效果，满足消费者的多样化需求。
通常在塑料基体中加入免喷涂效果颜料，以实现免喷涂金属效果。常规使用的免喷涂效果颜料包括金属粉、珠光粉等，主要为薄片状，故在注塑过程中容易发生翻转；并且无机物与有机树脂天然不相容，金属粉、珠光粉在塑料基体中相容性差，容易导致熔接痕和流痕现象严重。
现有技术公开了一种免喷涂金属效果的聚烯烃材料，添加了利用表面活性剂改性的球形微粒，以抑制熔体交界处的片状金属效果颜料的随熔体流动方向的偏转；但改性球形微粒粒径为10～80μm的无机物，在挤出注塑过程中易被剪切发生破碎，使得位阻作用消失。还有报道公开了一种改善外观的美学树脂组合物，包括热固性效应颜料母粒，利用热固性树脂包覆效应颜料，使其粒度增大，难以取向翻转；但包覆会导致效应颜料局部团聚，从而影响免喷涂外观效果。
因此，需要开发出一种免喷涂效果颜料，在塑料基体中能带来良好的免喷涂金属效果，且避免熔接痕和流痕现象。
发明内容
本发明为克服上述现有技术所述的缺陷，提供一种免喷涂效果颜料，包括热固性树脂微球、偶联剂和效应颜料，通过热固性树脂的位阻作用以及相容性的改善，协同作用使得本发明所述免喷涂效果颜料加至塑料基体中，既能带来良好的免喷涂金属效果，且避免了熔接痕和流痕现象。
本发明的另一目的在于提供上述免喷涂效果颜料的制备方法。
本发明的另一目的在于提供一种免喷涂材料，包括上述免喷涂效果颜料。
本发明的另一目的在于提供上述免喷涂材料的制备方法。
本发明的另一目的在于提供上述免喷涂材料的应用。
为解决上述技术问题，本发明采用的技术方案是：
一种免喷涂效果颜料，包括如下重量份的组分：
效应颜料100份，偶联剂10～200份，热固性树脂微球10～200份；
所述效应颜料为片状，平均粒径为6～350μm；
所述热固性树脂微球与效应颜料的平均粒径之比为1∶(3～100)。
在本发明的免喷涂效果颜料中，热固性树脂微球以微米级的小颗粒形态分散于片状的效应颜料周围，效应颜料通过偶联剂连接若干个热固性树脂微球小粒子，可形成空间位阻，减少注塑过程中的翻转；并且热固性树脂微球的粒径小，可以在相对最少添加量下起到最大的定向防翻转作用，最大程度保留免喷涂材料的原有物理性能。
热固性树脂微球通过偶联剂与效应颜料连接，热固性树脂作为有机物，与一般的塑料基体相容性较优，改善了效应颜料于有机树脂的相容性和分散性。
通过热固性树脂微球的位阻作用以及相容性的改善，协同作用使得本发明所述免喷涂效果颜料加至塑料基体中，既能带来良好的免喷涂金属效果，且避免了熔接痕和流痕现象。
优选地，所述热固性树脂微球中的热固性树脂为热固性丙烯酸树脂、热固性酚醛树脂、热固性环氧树脂、热固性聚酰胺树脂、热固性聚酰亚胺树脂或有机硅树脂中的一种或几种。
优选地，所述偶联剂为硅烷类偶联剂和/或钛酸酯类偶联剂。
可选地，所述硅烷类偶联剂为氨丙基三乙氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三乙氧基硅烷、巯丙基三甲(乙)氧基硅烷或乙二胺丙基三乙氧基硅烷中的一种或几种。
可选地，所述钛酸酯类偶联剂为钛酸四丁酯、三异硬脂酰基钛酸异丙酯、三钛酸异丙酯、二异硬酯酰基酞酸乙酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯或二硬脂酰氧异丙基铝酸酯中的一种或几种。
所述效应颜料可以为免喷涂材料中常用的效果颜料。
可选地，所述效应颜料为金属粉和/或珠光粉。
优选地，所述金属粉为铝粉、铜粉、金粉、银粉、锌粉、锡粉、铁粉或镍粉 中的一种或几种。
优选地，所述免喷涂效果颜料，包括如下重量份的组分：
效应颜料100份，偶联剂20～50份，热固性树脂微球30～100份。
优选地，所述热固性树脂微球与效应颜料的平均粒径之比为1∶(6～30)。
本发明还保护上述免喷涂效果颜料的制备方法，包括如下步骤：
在常温下，将效应颜料和热固性树脂分散于溶有偶联剂的有机溶剂中，搅拌后，去除有机溶剂，得到所述免喷涂效果颜料。
可选地，所述有机溶剂为乙醇、甲醇、乙腈、二氧六环或四氢呋喃中的一种或几种。
考虑到乙醇对于偶联剂有更优的溶解度，且经济性更好。优选地，所述有机溶剂为乙醇。
优选地，所述常温为15～35℃，搅拌时间为2～8h。
优选地，所述去除溶剂是指加热去除或减压去除。
本发明还保护一种免喷涂材料，包括如下重量份的组分：
热塑性树脂100份，所述免喷涂效果颜料0.5～10份。
优选地，所述热塑性树脂为聚烯烃类树脂、苯乙烯类树脂、聚氯乙烯类树脂、聚酯类树脂、聚碳酸酯类树脂、聚酰胺类树脂、聚甲基丙烯酸甲酯或聚氨酯中的一种或几种。
优选地，所述免喷涂材料还可以包括0.1～35重量份的助剂。
所述助剂可以为热塑性树脂中常用的功能助剂。
优选地，所述助剂为阻燃剂、抗氧剂、增韧剂、成核剂、润滑剂、相容剂、稳定剂、增塑剂或抗静电剂中的一种或几种。
本发明还保护上述免喷涂材料的制备方法，包括如下步骤：
将热塑性树脂和助剂(如有)混合后加至挤出机的主喂料口，将所述免喷涂效果颜料加至挤出机的侧喂料口，经熔融混合、挤出造粒，得到所述免喷涂材料。
优选地，所述挤出机为双螺杆挤出机。
优选地，所述挤出温度为170～320℃，螺杆转速为350～450rpm。
本发明还保护上述免喷涂材料在电子电器、体育用品、办公用品、交通运输领域中的应用。
与现有技术相比，本发明的有益效果是：
本发明开发了一种免喷涂效果颜料，通过小颗粒热固性树脂的位阻作用协同相容性的改善，使得本发明所述免喷涂效果颜料加至塑料基体中，既能带来良好的免喷涂金属效果，且避免了熔接痕和流痕现象。
附图说明
图1为实施例1制得的免喷涂效果颜料的SEM扫描电镜图。
图2为流痕及熔接线的可视化程度评价标准示意图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例中的原料均可通过市售得到；
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方 法和设备。
实施例1～16
实施例1～16分别提供一种免喷涂效果颜料，组分含量见表1，制备方法如下：
在30℃下，将效应颜料和热固性树脂分散于溶有偶联剂的有机溶剂(乙醇，市售)中，搅拌5h后，加热去除有机溶剂，得到免喷涂效果颜料。
表1实施例1～16的免喷涂效果颜料的组分含量(重量份)


实施例17～34
实施例17～34分别提供一种免喷涂材料，组分含量见表2，制备方法如下：
将热塑性树脂加至双螺杆挤出机的主喂料口，将免喷涂效果颜料加至双螺杆挤出机的侧喂料口，经熔融混合、挤出造粒，得到免喷涂材料；其中挤出温度为170～320℃，螺杆转速为350～450rpm。
表2实施例17～34的免喷涂材料的组分含量(重量份)


对比例1～5
对比例1～5分别提供一种免喷涂效果颜料，组分含量见表3，制备方法与实施例1～16相同。
表3对比例1～5的免喷涂效果颜料的组分含量(重量份)
对比例6～11
对比例6～11分别提供一种免喷涂材料，组分含量见表4，制备方法与实施例17～34相同。
表4对比例6～11的免喷涂材料的组分含量(重量份)
性能测试
对上述实施例和对比例制得的免喷涂材料进行性能测试，具体方法如下：
SEM扫描电镜：使用扫描电子显微镜观察实施例1制备的免喷涂效果颜料的微观结构，放大倍数为1500倍；
免喷涂金属/珠光效果(E)：将免喷涂材料注塑为100*50*2mm规格的色板，通过目视评判免喷涂效果，评价标准为：0级，几乎无金属感/珠光感；1级，金属感/珠光感稍弱；2级，适中金属感/珠光感；3级，强金属感/珠光感；认为2级或3级为合格；免喷涂效果评级数值由3名试验人员进行判定，取平均值；
流痕及熔接线的可视化程度(V)：通过对200*30*2mm的样条模具进行改造制备特定模具，在靠近浇口位置上开设一个直径为5mm的孔洞，观察熔接线和流痕的可视程度，评价标准为：1级，几乎无熔接线和流痕；2级，可接受的微弱熔接线和流痕；3级，较明显的熔接线和流痕；4级，明显的熔接线和流痕；评判标准示意图如图2；流痕及熔接线的可视化程度评级数值由3名试验人员进行判定，取平均值；
熔接线长度(L)：通过用卡尺测量可视化的熔接线从孔洞处延伸出来的长度；
综合外观效果指数(I)：用于评价免喷涂产品的综合外观效果，综合以上各项测试指标数据给出效果指数定义公式I＝E2/(V2*L0.5)，其中E代表免喷涂金属/珠光效果，V代表流痕和熔接线的可视化程度，L代表熔接线长度；I值越大代表综合外观效果越理想。
实施例17～34的测试结果见表5，对比例7～12的测试结果见表6。
根据图1的SEM扫描电镜所示，实施例1制备的免喷涂效果颜料的热固性树脂微球以颗粒形态分散于片状的效应颜料周围。发明人研究发现，效应颜料通过偶联剂连接若干个热固性树脂微球小粒子，可形成空间位阻，减少注塑过程中的翻转，使得免喷涂材料的外观效果更优。
表5实施例17～34的测试结果

根据表5的测试结果，本发明各实施例制得的免喷涂效果颜料能为热塑性树脂带来优异的免喷涂金属/珠光效果，流痕及熔接线可视化程度低，且熔接线长度小，含有本发明免喷涂效果颜料的免喷涂材料的免喷涂外观效果优。
实施例17～31的免喷涂材料中，分别使用实施例1～16制得的免喷涂效果颜料。
实施例17～28中，实施例18、19、22、23、25、27、28的免喷涂材料的综合外观效果指数(I)相对更高，免喷涂效果更优；其次为实施例17，再次为实施例20、21，再次为实施例24、26。可以看出，热固性树脂微球与效应颜料的平均粒径之比不同、效应颜料的平均粒径大小不同，影响材料的免喷涂外观效果。热固性树脂微球与效应颜料的平均粒径之比优选为1∶(6～30)。
根据实施例17、30、31、32结合实施例1、14、15、16，实施例31、32的免喷涂外观效果指数略差，因此，免喷涂效果颜料的组分含量优选为：效应颜料100份，偶联剂20～50份，热固性树脂微球30～100份。
表6对比例6～11的测试结果
对比例6～10的免喷涂材料中，分别使用对比例1～5制得的免喷涂效果颜料。
对比例1中效应颜料的平均粒径过小，对比例3、4中效应颜料与热固性树脂微球的平均粒径之比超出本发明技术方案范围，对比例6、8、9制得的免喷涂材料的免喷涂效果差。这说明热固性树脂微球与效应颜料是起到相互影响的作用，效应颜料自身的粒径大小，以及热固性树脂微球与效应颜料的平均粒径之比，均显著影响免喷涂效果颜料的免喷涂效果发挥。
对比例2中效应颜料非片状，而是球状铝粉。热固性树脂微球无法与球状效应颜料协同，形成空间位阻，从而难以减少注塑过程中效应颜料的翻转。对比例 7制得的免喷涂材料外观效果差。
对比例10中使用的免喷涂效果颜料不含偶联剂，效应颜料与热固性树脂微球的连接性差，造成对比例10的免喷涂外观效果较差。
对比例11的免喷涂材料中不含本发明的免喷涂效果颜料，而是直接添加铝粉。可以看出，免喷涂材料虽然具有3级金属效果，但熔接线和流痕非常明显，且熔接线长度过，综合外观效果指数较差。
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，而并非是对本发明的实施方式的限定。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。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种免喷涂效果颜料，其特征在于，包括如下重量份的组分：
    效应颜料100份，偶联剂10～200份，热固性树脂微球10～200份；
    所述效应颜料为片状，平均粒径为6～350μm；
    所述热固性树脂微球与效应颜料的平均粒径之比为1∶(3～100)。
  2. 根据权利要求1所述免喷涂效果颜料，其特征在于，包括如下重量份的组分：
    效应颜料100份，偶联剂20～50份，热固性树脂微球30～100份。
  3. 根据权利要求1所述免喷涂效果颜料，其特征在于，所述热固性树脂微球与效应颜料的平均粒径之比为1∶(6～30)。
  4. 根据权利要求1所述免喷涂效果颜料，其特征在于，所述效应颜料为金属粉和/或珠光粉。
  5. 根据权利要求1所述免喷涂效果颜料，其特征在于，所述热固性树脂微球中的热固性树脂为热固性丙烯酸树脂、热固性酚醛树脂、热固性环氧树脂、热固性聚酰胺树脂、热固性聚酰亚胺树脂或有机硅树脂中的一种或几种。
  6. 根据权利要求1所述免喷涂效果颜料，其特征在于，所述偶联剂为硅烷类偶联剂和/或钛酸酯类偶联剂。
  7. 权利要求1～6任一项所述免喷涂效果颜料的制备方法，其特征在于，包括如下步骤：
    在常温下，将效应颜料和热固性树脂分散于溶有偶联剂的有机溶剂中，搅拌后，去除有机溶剂，得到所述免喷涂效果颜料。
  8. 一种免喷涂材料，其特征在于，包括如下重量份的组分：
    热塑性树脂100份，权利要求1～6任一项所述免喷涂效果颜料0.5～10份。
  9. 权利要求8所述免喷涂材料的制备方法，其特征在于，包括如下步骤：
    将热塑性树脂加至挤出机的主喂料口，将所述免喷涂效果颜料加至挤出机的侧喂料口，经熔融混合、挤出造粒，得到所述免喷涂材料。
  10. 权利要求8所述免喷涂材料在电子电器、体育用品、办公用品、交通运输领域中的应用。
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