WO2023174000A1 - 一种力学增强的免喷涂效果颜料及其制备方法和应用 - Google Patents

一种力学增强的免喷涂效果颜料及其制备方法和应用 Download PDF

Info

Publication number
WO2023174000A1
WO2023174000A1 PCT/CN2023/076933 CN2023076933W WO2023174000A1 WO 2023174000 A1 WO2023174000 A1 WO 2023174000A1 CN 2023076933 W CN2023076933 W CN 2023076933W WO 2023174000 A1 WO2023174000 A1 WO 2023174000A1
Authority
WO
WIPO (PCT)
Prior art keywords
spray
effect pigment
free
hyperbranched
parts
Prior art date
Application number
PCT/CN2023/076933
Other languages
English (en)
French (fr)
Inventor
朱秀梅
陈平绪
叶南飚
黄险波
刘鑫鑫
常欢
Original Assignee
金发科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Publication of WO2023174000A1 publication Critical patent/WO2023174000A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
    • C08K3/01—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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the present invention relates to the technical field of spray-free materials, and more specifically, to a mechanically enhanced 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 not only easily leads to serious weld marks and flow marks, but also deteriorates the mechanical properties of the plastic matrix.
  • Cikon patent application CN 103724926 A discloses 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.
  • the amount of thermosetting effect pigment masterbatch added is large, and it contains a large amount of thermosetting resin, which affects the mechanical properties of the matrix resin itself, limiting the application of spray-free materials in fields with high mechanical performance requirements.
  • helmet shells require materials that not only have good appearance but also have excellent mechanical properties.
  • existing spray-free materials are difficult to meet the requirements.
  • the present invention provides a mechanically enhanced spray-free effect pigment.
  • the capped hyperbranched resin is used to promote the compatibility between the effect pigment and the resin matrix, and on the other hand, steric hindrance is used. It avoids flow marks and weld lines caused by the flipping of effect pigments, and also improves the mechanical properties of spray-free materials.
  • 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:
  • a mechanically enhanced spray-free effect pigment including the following components by weight:
  • effect pigment 100 parts of effect pigment, 5 to 200 parts of coupling agent, 5 to 100 parts of hyperbranched resin;
  • the hyperbranched resin is an end-capped hyperbranched resin, and the branching degree of the hyperbranched resin is ⁇ 0.1.
  • Hyperbranched resins are generally divided into uncapped hyperbranched resins and capped hyperbranched resins.
  • the capped hyperbranched resins do not contain terminal functional groups.
  • the hyperbranched resin has a highly branched three-dimensional quasi-spherical three-dimensional structure. Through the action of the coupling agent, it can cooperate with the effect pigment to form steric hindrance and reduce the flipping of the effect pigment. , and improve the compatibility between effect pigments and organic resins.
  • hyperbranched resins unlike resins with linear structures, hyperbranched resins have lower viscosity and better solubility, which makes the effect pigments more fluid, further reducing flow marks and weld marks during the injection molding process of the material, and improving Improve the appearance of spray-free materials.
  • Uncapped hyperbranched resins are prone to chemical reactions and/or physical adsorption due to their large number of terminal functional groups. Especially under the action of coupling agents, it is easy to cause coupling and agglomeration between hyperbranched resins, causing them to self-agglomerate and become unable to disperse. Not only cannot it improve the appearance of spray-free materials, but it will also deteriorate the spray-free effect.
  • hyperbranched resin can mechanically strengthen the plastic matrix and improve the impact and tensile properties of the material. .
  • spray-free appearance effect will be weakened.
  • the branching degree of hyperbranched resin is detected and calculated by hydrogen nuclear magnetic resonance spectroscopy or carbon spectroscopy.
  • the spray-free effect pigment includes the following components by weight:
  • effect pigment 100 parts of effect pigment, 10-50 parts of coupling agent, 40-50 parts of hyperbranched resin.
  • the hyperbranched resin is one or more of hyperbranched polyester, hyperbranched polyamidoamine, hyperbranched polyamide, hyperbranched polyamide ester, hyperbranched polyurethane or hyperbranched polysiloxane. kind.
  • the degree of branching of the hyperbranched resin is 0.3-1.
  • the degree of branching refers to the molar fraction ratio of branch units to terminal units in the polymer molecular structure. Therefore, the theoretical maximum degree of branching is 1.
  • the higher the branching degree of the hyperbranched resin the better the overall performance of the spray-free effect pigment.
  • the coupling agent is a silane coupling agent and/or a titanate coupling agent.
  • the coupling agent is a silane coupling agent.
  • Titanate coupling agents contain long carbon bond alkyl hydroxyl groups, which can bend and tangle with organic polymers, causing local agglomeration.
  • the hyperbranched resin as a highly branched polymer, has a higher probability of entanglement with the titanate coupling agent, which will lead to local agglomeration of the hyperbranched resin and affect the spray-free effect. .
  • the silane coupling agent is aminopropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane One or more of silane, vinyltriethoxysilane, mercaptopropyltrimethyl(ethyl)oxysilane or ethylenediaminepropyltriethoxysilane.
  • 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 one or more of aluminum powder, copper powder, gold powder, silver powder, zinc powder, tin powder, iron powder or nickel powder.
  • the present invention also protects the preparation method of the above-mentioned mechanically enhanced spray-free effect pigment, which includes the following steps:
  • the effect pigment and the hyperbranched resin are dispersed in an organic solvent in which a coupling agent is dissolved. After stirring, the organic solvent is removed to obtain the mechanically enhanced spray-free effect pigment.
  • the organic solvent is one or more of ethanol, methanol, acetonitrile, dioxane or tetrahydrofuran.
  • 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, 1 to 10 parts of the mechanically enhanced 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 other additives.
  • the other auxiliary agents are one or more of antioxidants, toughening agents, nucleating agents or processing aids.
  • the present invention also protects the preparation method of the above-mentioned spray-free material, which includes the following steps:
  • thermoplastic resin and additives if any
  • the effect pigment is added to the side feeding port of the extruder, and after 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 invention develops a mechanically enhanced spray-free effect pigment and a spray-free material containing the spray-free effect pigment.
  • hyperbranched resins are used to have a highly branched three-dimensional quasi-spherical structure. Through the action of coupling agents, they can cooperate with effect pigments to form steric hindrance, reduce the flipping of effect pigments, and improve the appearance of spray-free materials.
  • the hyperbranched resin has lower viscosity and better solubility, which makes the effect pigment more fluid and further reduces flow marks and weld marks during the injection molding process of the material.
  • hyperbranched resin also has a mechanical reinforcement effect on the plastic matrix, improving the impact resistance and tensile strength of the material.
  • Figure 1 is a schematic diagram of the evaluation criteria for the visualization degree of flow marks and weld lines.
  • the raw materials in the examples and comparative examples are as follows;
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
  • Embodiments 1 to 11 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 hyperbranched resin were dispersed in an organic solvent (ethanol, commercially available) with a coupling agent dissolved in it. After stirring for 5 hours, the organic solvent was removed by heating to obtain a spray-free effect pigment.
  • organic solvent ethanol, commercially available
  • Embodiments 12 to 24 respectively provide a spray-free material, the component content is shown in Table 2, and 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 15.
  • 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 16 to 32.
  • 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 are: Level 1, almost no weld lines and flow marks; Level 2, acceptable Weak welding lines and flow marks; Level 3, more obvious welding lines and flow marks; Level 4, obvious welding lines and flow marks;
  • the schematic diagram of the judging criteria is shown in Figure 1;
  • the visual degree rating of flow marks and welding lines is determined by 3 people The tester makes a judgment and takes the average;
  • Izod notched impact strength tested according to ISO 180-2013 standard.
  • the spray-free materials prepared in Examples 12 to 24 of the present invention have excellent spray-free appearance, good mechanical properties, tensile strength ⁇ 35 MPa, and cantilever notch impact strength ⁇ 2.8 kJ/m 2 .
  • Example 12 According to Examples 12 to 17, combined with Examples 1 to 6, it can be seen that the higher the branching degree of the hyperbranched resin in the spray-free effect pigment, the better the appearance effect and better mechanical properties of the spray-free material.
  • the spray-free material prepared in Example 14 has a relatively optimal spray-free appearance effect, high tensile strength, and relatively higher Izod notch impact strength.
  • the coupling agent is preferably a silane coupling agent.
  • the hyperbranched resin as a highly branched polymer, has a higher probability of entanglement with the titanate coupling agent, which will lead to local agglomeration of the hyperbranched resin and affect the spray-free effect. .
  • the component content of the spray-free effect pigment is preferably: 100 parts of effect pigment, 10-50 parts of coupling agent, and 40-50 parts of hyperbranched resin.
  • the hyperbranched resin in the spray-free effect pigment is an uncapped hyperbranched resin.
  • the comprehensive appearance effect index of the spray-free material in Comparative Example 6 is low, indicating that the spray-free appearance effect is poor.
  • the amount of hyperbranched resin in the spray-free effect pigment used in Comparative Example 8 is too small, which not only has a low degree of improvement in the appearance of the spray-free material, but also has no obvious mechanical enhancement effect on the plastic matrix, and the mechanical properties of the spray-free material produced are relatively poor. Poor; the amount of hyperbranched resin in the spray-free effect pigment used in Comparative Example 9 is too much, which weakens the spray-free appearance effect brought by the effect pigment.
  • the spray-free effect pigment of Comparative Example 5 does not contain a coupling agent, and the hyperbranched resin cannot effectively connect with the effect pigment to synergistically act as a steric hindrance. As a result, the spray-free material produced in Comparative Example 10 has poor appearance.
  • 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 length of the welding lines is as high as 65mm, and the overall appearance effect index is poor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种力学增强的免喷涂效果颜料及其制备方法和应用。本发明所述力学增强的免喷涂效果颜料，包括如下重量份的组分：效应颜料100份，偶联剂5～200份，超支化树脂5～50份；所述超支化树脂为封端的超支化树脂，所述超支化树脂的支化度≥0.1。利用超支化树脂具有高度支化的三维准球形立体结构，通过偶联剂的作用，可以与效应颜料协同形成位阻，减少效应颜料的翻转、改善免喷涂材料的外观效果；超支化树脂的粘度更低、溶解性更优，使得效应颜料的流动性更好，进一步减少了材料的注塑过程中的流痕、熔接痕情况。与此同时，超支化树脂还对塑料基体有力学增强作用，提高了材料的抗冲击性能和拉伸强度。

Description

一种力学增强的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，涉及一种力学增强的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，不仅容易导致熔接痕和流痕现象严重，还会劣化塑料基体的力学性能。
中国专利申请CN 103724926 A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。但热固性效应颜料母粒的添加量大，其中含有大量的热固性树脂影响了基体树脂的自身力学性能，限制了免喷涂材料在力学性能要求高的领域中的应用。如头盔壳体，既要求材料具有良好的外观，又要求具有优异的力学性能，而现有的免喷涂材料难以满足要求。
因此，需要开发出一种力学增强的免喷涂效果颜料，在塑料基体中能带来良好的免喷涂金属效果，且具有优异的力学性能。
发明内容
本发明为克服上述现有技术所述的缺陷，提供一种力学增强的免喷涂效果颜料，利用封端的超支化树脂一方面促进了效应颜料与树脂基体的相容性，另一方面利用位阻作用避免了效应颜料的翻转造成的流痕和熔接线，同时还改善了免喷涂材料的力学性能。
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：
一种力学增强的免喷涂效果颜料，包括如下重量份的组分：
效应颜料100份，偶联剂5～200份，超支化树脂5～100份；
所述超支化树脂为封端的超支化树脂，所述超支化树脂的支化度≥0.1。
超支化树脂一般分为未封端的超支化树脂和封端的超支化树脂，其中封端的超支化树脂不含端官能团。
发明人研究发现，在本发明的免喷涂效果颜料中，超支化树脂具有高度支化的三维准球形立体结构，通过偶联剂的作用，可以与效应颜料协同形成位阻，减少效应颜料的翻转，且改善效应颜料与有机树脂的相容性。此外，与线性结构的树脂不同的是，超支化树脂的粘度更低、溶解性更优，使得效应颜料的流动性更好，进一步减少了材料的注塑过程中的流痕、熔接痕情况，改善了免喷涂材料的外观效果。
而未封端的超支化树脂，由于端官能团较多，易发生化学反应和/或物理吸附。尤其在偶联剂的作用下，易造成超支化树脂之间的偶联团聚，导致其自团聚、无法分散，不仅不能实现改善免喷涂材料的外观效果，反而会使得免喷涂效果劣化。
在5～100份的添加量下，由于超支化树脂对于流动性、分散性、相容性的优异改善，超支化树脂能够对塑料基体有力学增强作用，提高了材料的冲击性能和拉伸性能。而在更高的添加量下，会造成免喷涂外观效果的削弱。
超支化树脂的支化度经核磁共振氢谱法或者碳谱法检测、计算得到。
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10～50份，超支化树脂40～50份。
优选地，所述超支化树脂为超支化聚酯、超支化聚酰胺胺、超支化聚酰胺、超支化聚酰胺酯、超支化聚亚胺酯或超支化聚硅氧烷中的一种或几种。
优选地，所述超支化树脂的支化度为0.3～1。
支化度是指支化单元与末端单元在聚合物分子结构中所占的摩尔分数比。因此，支化度理论上最高为1。在本发明中，所述超支化树脂的支化度越高，免喷涂效果颜料的综合性能更优。
优选地，所述偶联剂为硅烷类偶联剂和/或钛酸酯类偶联剂。
更优选地，所述偶联剂为硅烷类偶联剂。
钛酸酯类偶联剂中含长碳键烷羟基，会与有机聚合物发生弯曲缠结，引起局部团聚。在本发明的免喷涂效果颜料中，超支化树脂作为高度支化的聚合物，与钛酸酯类偶联剂发生缠结的概率更高，会导致超支化树脂的局部团聚，影响免喷涂效果。
优选地，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。
所述效应颜料可以为免喷涂材料中常用的效果颜料。
优选地，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。
本发明还保护上述力学增强的免喷涂效果颜料的制备方法，包括如下步骤：
在常温下，将效应颜料和超支化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，得到所述力学增强的免喷涂效果颜料。
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。
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，所述力学增强的免喷涂效果颜料1～10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重量份的其他助剂。
优选地，所述其他助剂为抗氧剂、增韧剂、成核剂或加工助剂中的一种或几种。
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：
本发明开发了一种力学增强的免喷涂效果颜料，以及含有该免喷涂效果颜料的免喷涂材料。在免喷涂效果颜料中，利用超支化树脂具有高度支化的三维准球形立体结构，通过偶联剂的作用，可以与效应颜料协同形成位阻，减少效应颜料的翻转、改善免喷涂材料的外观效果；超支化树脂的粘度更低、溶解性更优，使得效应颜料的流动性更好，进一步减少了材料的注塑过程中的流痕、熔接痕情况。与此同时，超支化树脂还对塑料基体有力学增强作用，提高了材料的抗冲击性能和拉伸强度。
附图说明
图1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。
实施例及对比例中的原料具体如下；

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1～11
实施例1～11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，将效应颜料和超支化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1～11的免喷涂效果颜料的组分含量(重量份)
实施例12～24
实施例12～24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12～24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1～15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16～32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：
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1；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。
拉伸强度：按照ISO 527-2012标准测试；
悬臂梁缺口冲击强度：按照ISO 180-2013标准测试。
实施例12～24的测试结果见表5，对比例6～11的测试结果见表6。
表5实施例12～24的测试结果
根据表5的测试结果，本发明实施例12～24制得的免喷涂材料具有优异的免喷涂外观效果，且力学性能好，拉伸强度≥35MPa，悬臂梁缺口冲击强度≥2.8kJ/m2。
实施例12～22的免喷涂材料中，分别使用实施例1～11制得的免喷涂效果颜料。
根据实施例12～17，结合实施例1～6，可以看出，免喷涂效果颜料中超支化树脂的支化度越高，免喷涂材料的外观效果更优、力学性能更好。实施例14制得的免喷涂材料具有相对最优的免喷涂外观效果，且拉伸强度高、悬臂梁缺口冲击强度相对更高。
根据实施例19和实施例12的测试结果，偶联剂优选为硅烷类偶联剂。在本发明的免喷涂效果颜料中，超支化树脂作为高度支化的聚合物，与钛酸酯类偶联剂发生缠结的概率更高，会导致超支化树脂的局部团聚，影响免喷涂效果。
根据实施例12、20～22，免喷涂效果颜料的组分含量优选为：效应颜料100份，偶联剂10～50份，超支化树脂40～50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，免喷涂效果颜料中超支化树脂为未封端的超支化树脂，对比例6的免喷涂材料的综合外观效果指数低，表示免喷涂外观效果差。
对比例2中，免喷涂效果颜料中的超支化树脂的支化度过低，对比例7的免喷涂材料的流痕和熔接线较明显，且熔接线长度为50.2mm，外观效果差。
对比例8使用的免喷涂效果颜料中超支化树脂的量过少，既对免喷涂材料的外观效果改善程度低，且对塑料基体有力学增强作用不明显，制得的免喷涂材料力学性能较差；对比例9使用的免喷涂效果颜料中超支化树脂的量过多，削弱了效应颜料所带来的免喷涂外观效果。
对比例5的免喷涂效果颜料中不含偶联剂，超支化树脂无法与效应颜料有效连接、协同起到位阻作用。导致对比例10制得的免喷涂材料外观效果差。
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，且熔接线长度高达65mm，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. 一种力学增强的免喷涂效果颜料，包括如下重量份的组分：
    效应颜料100份，偶联剂5～200份，超支化树脂5～100份；
    所述超支化树脂为封端的超支化树脂，所述超支化树脂的支化度≥0.1。
  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10～50份，超支化树脂40～50份。
  3. 根据权利要求1所述免喷涂效果颜料，其特征在于，所述超支化树脂为超支化聚酯、超支化聚酰胺胺、超支化聚酰胺、超支化聚酰胺酯、超支化聚亚胺酯或超支化聚硅氧烷中的一种或几种。
  4. 根据权利要求1所述免喷涂效果颜料，其特征在于，所述超支化树脂的支化度为0.3～1。
  5. 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。
  6. 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。
  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，将效应颜料和超支化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任一项所述力学增强的免喷涂效果颜料1～10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。
PCT/CN2023/076933 2022-03-18 2023-02-17 一种力学增强的免喷涂效果颜料及其制备方法和应用 WO2023174000A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210277453.3A CN114806095B (zh) 2022-03-18 2022-03-18 一种力学增强的免喷涂效果颜料及其制备方法和应用
CN202210277453.3 2022-03-18

Publications (1)

Publication Number Publication Date
WO2023174000A1 true WO2023174000A1 (zh) 2023-09-21

Family

ID=82530324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/076933 WO2023174000A1 (zh) 2022-03-18 2023-02-17 一种力学增强的免喷涂效果颜料及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN114806095B (zh)
WO (1) WO2023174000A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114806095B (zh) * 2022-03-18 2024-05-14 金发科技股份有限公司 一种力学增强的免喷涂效果颜料及其制备方法和应用
CN115612178A (zh) * 2022-09-29 2023-01-17 金发科技股份有限公司 一种多面体特殊效应颜料及其制备方法和免喷涂材料

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009120789A (ja) * 2007-10-22 2009-06-04 Sumitomo Dow Ltd ウェルド部の外観に優れたポリカーボネート樹脂組成物及びそれからなる成形品。
WO2014044529A1 (en) * 2012-09-20 2014-03-27 Basf Se Hyperbranched phosphoric acid esters
CN103724926A (zh) * 2013-12-30 2014-04-16 上海锦湖日丽塑料有限公司 一种改善外观的美学树脂组合物及其制备方法
CN106189120A (zh) * 2016-08-18 2016-12-07 福建湄洲湾氯碱工业有限公司 免喷涂pbt‑as合金材料及其制备方法
CN106751756A (zh) * 2016-11-30 2017-05-31 上海中镭新材料科技有限公司 一种免喷涂具有金属效果的聚酰胺树脂及其制备方法
CN109370041A (zh) * 2018-08-09 2019-02-22 河南工程学院 一种兼具良好刚性和高断裂伸长率的聚丙烯改性材料及其制备方法
CN109456538A (zh) * 2018-10-12 2019-03-12 万华化学集团股份有限公司 一种低密度、低收缩率、银色金属质感的聚丙烯复合材料及其制备方法
CN111704748A (zh) * 2020-06-29 2020-09-25 上海中镭新材料科技有限公司 一种改性纳米氧化物粒子、其制备方法和包含其的免喷涂聚酰胺材料
CN113845720A (zh) * 2021-08-25 2021-12-28 武汉金发科技有限公司 一种高着色力低收缩率聚丙烯复合材料及其制备方法和应用
CN113999497A (zh) * 2021-10-25 2022-02-01 金发科技股份有限公司 一种有机黑色粉组合物及其制备方法和应用
CN114806095A (zh) * 2022-03-18 2022-07-29 金发科技股份有限公司 一种力学增强的免喷涂效果颜料及其制备方法和应用

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009120789A (ja) * 2007-10-22 2009-06-04 Sumitomo Dow Ltd ウェルド部の外観に優れたポリカーボネート樹脂組成物及びそれからなる成形品。
WO2014044529A1 (en) * 2012-09-20 2014-03-27 Basf Se Hyperbranched phosphoric acid esters
CN103724926A (zh) * 2013-12-30 2014-04-16 上海锦湖日丽塑料有限公司 一种改善外观的美学树脂组合物及其制备方法
CN106189120A (zh) * 2016-08-18 2016-12-07 福建湄洲湾氯碱工业有限公司 免喷涂pbt‑as合金材料及其制备方法
CN106751756A (zh) * 2016-11-30 2017-05-31 上海中镭新材料科技有限公司 一种免喷涂具有金属效果的聚酰胺树脂及其制备方法
CN109370041A (zh) * 2018-08-09 2019-02-22 河南工程学院 一种兼具良好刚性和高断裂伸长率的聚丙烯改性材料及其制备方法
CN109456538A (zh) * 2018-10-12 2019-03-12 万华化学集团股份有限公司 一种低密度、低收缩率、银色金属质感的聚丙烯复合材料及其制备方法
CN111704748A (zh) * 2020-06-29 2020-09-25 上海中镭新材料科技有限公司 一种改性纳米氧化物粒子、其制备方法和包含其的免喷涂聚酰胺材料
CN113845720A (zh) * 2021-08-25 2021-12-28 武汉金发科技有限公司 一种高着色力低收缩率聚丙烯复合材料及其制备方法和应用
CN113999497A (zh) * 2021-10-25 2022-02-01 金发科技股份有限公司 一种有机黑色粉组合物及其制备方法和应用
CN114806095A (zh) * 2022-03-18 2022-07-29 金发科技股份有限公司 一种力学增强的免喷涂效果颜料及其制备方法和应用

Also Published As

Publication number Publication date
CN114806095A (zh) 2022-07-29
CN114806095B (zh) 2024-05-14

Similar Documents

Publication Publication Date Title
WO2023174000A1 (zh) 一种力学增强的免喷涂效果颜料及其制备方法和应用
WO2023174010A1 (zh) 一种免喷涂效果颜料及其制备方法和应用
US7527750B2 (en) Electrically conductive additive system and method of making same
CN112375363B (zh) 一种玻纤增强的聚碳酸酯组合物及其制备方法和应用
EP3789456B1 (en) Polyamide resin composition having high metal texture and preparation method of polyamide resin composition
CN105331055B (zh) 用于nmt成型的pbt复合材料及其制备方法
CN103242637B (zh) 高光泽高硬度免喷涂的无卤阻燃pc/abs塑胶改性材料及其制备方法
CN104583330A (zh) 热塑性树脂组合物、树脂成型品和带镀层的树脂成型品的制造方法
CN102040773B (zh) 一种塑料合金、其制备方法和应用
CN102617997A (zh) 一种玻璃纤维增强pbt/pet复合材料及其制备方法
CN106916445A (zh) 一种免喷涂透明玻纤增强型尼龙树脂材料及其制备方法
CN101817967A (zh) 一种电镀用abs复合材料及其制备方法
CN110218432A (zh) 一种高韧性pc/pmma合金材料及其制备方法
CN112457645B (zh) 一种聚碳酸酯合金组合物及其制备方法和应用
WO2014178490A1 (ko) 강인화 에폭시 수지 조성물, 이의 제조방법 및 강인화 에폭시 수지
WO2013085246A1 (ko) 복합재 및 그 성형물
CN107163537A (zh) 一种透明抗划伤抗静电阻燃聚碳酸酯复合材料
CN104387740B (zh) 高性能矿物填充pc/abs合金材料及其制备方法
CN112341666A (zh) 一种改性lds镭雕助剂的制备方法和lds复合材料
WO2023174060A2 (zh) 一种免喷涂树脂及其制备方法和应用
CN104672756A (zh) Abs复合阻燃材料及其制备方法
CN108587154B (zh) 一种改性pa66复合材料及其制备方法
CN112375362B (zh) 一种pc/abs组合物及其制备方法和应用
CN102702721B (zh) 一种高流动高韧性导电聚苯醚聚酰胺组合物及其制备方法
CN104356737A (zh) 一种导电粉末涂料专用高导电材料及制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23769508

Country of ref document: EP

Kind code of ref document: A1