WO2023173849A1 - 一种良触感热塑性材料及其制备方法和应用 - Google Patents

一种良触感热塑性材料及其制备方法和应用 Download PDF

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WO2023173849A1
WO2023173849A1 PCT/CN2022/138880 CN2022138880W WO2023173849A1 WO 2023173849 A1 WO2023173849 A1 WO 2023173849A1 CN 2022138880 W CN2022138880 W CN 2022138880W WO 2023173849 A1 WO2023173849 A1 WO 2023173849A1
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polymer
thermoplastic material
good
touch
parts
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PCT/CN2022/138880
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French (fr)
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王琪
陈平绪
叶南飚
林荣涛
李欣达
季得运
李文龙
李明昆
张永
罗忠富
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金发科技股份有限公司
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    • 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

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  • the present invention relates to the technical field of polymer materials, and more specifically, to a thermoplastic material with good touch and its preparation method and application.
  • Automotive interior materials mainly refer to the parts used in the interior parts of the car cockpit and involve the surface perception of the car interior, such as instrument panels, sub-instruments, seat skins, ceilings and door trims.
  • This type of interior material is an area that has more contact with people, and its touch directly affects the perceived quality of the car and the consumer's driving experience. Therefore, the development of acrylonitrile-butadiene-styrene (ABS) materials with good touch is of great significance for promoting the development of automotive interior materials and improving the quality of automobiles.
  • ABS acrylonitrile-butadiene-styrene
  • the prior art discloses a matte, low-odor, heat-resistant and high-impact ABS material and its preparation method, which uses ABS as the base and adds 0.6 to 3 parts of styrene-acrylonitrile-glycidyl methacrylate.
  • the ternary random copolymer acts as a matting agent to reduce the surface gloss of the material.
  • the ABS material disclosed in the above technology contains ABS resin and styrene-acrylonitrile-glycidyl methacrylate components, but the ABS material provided is aimed at improving its gloss, and it does not aim at improving the surface of the ABS material. Roughness, the technical issue of having delicate, tiny bumps in a material that can be felt on contact.
  • the technical problem to be solved by the present invention is to overcome the defects and shortcomings of existing thermoplastic materials such as low surface roughness and lack of delicate micro-protrusions in touch, and provide a thermoplastic material with good touch by adding a larger amount of the third component to ABS resin.
  • the first polymer and the second polymer work together to create delicate micro-protrusions that can be felt when touched, and have high surface roughness, effectively improving the touch of the good-touch thermoplastic material.
  • Another object of the present invention is to provide a method for preparing a thermoplastic material with good touch.
  • Another object of the present invention is to provide an application of a good-touch thermoplastic material in the preparation of automobile interior decoration.
  • thermoplastic material including the following components in parts by weight:
  • ABS resin 50-90 parts ABS resin 50-90 parts
  • the first polymer is 5 to 25 parts;
  • the second polymer is 5 to 25 parts;
  • the weight ratio of the first polymer to the second polymer is 1:0.5-2;
  • the first polymer is an ethylene-acrylic acid copolymer.
  • the mass content of acrylic acid is 3% to 15%, and the test standard is ASTM D4094-07;
  • the second polymer is a polymer containing glycidyl methacrylate.
  • the mass content of glycidyl methacrylate in the second polymer is 1% to 10%.
  • the test standard is GB/T 1677 -2008.
  • the good-touch thermoplastic material of the present invention adds a larger amount of the first polymer and the second polymer to the ABS resin for synergy, and can feel delicate micro-protrusions when touched, and has high surface roughness, effectively improving the
  • the tactile thermoplastic material has a good tactile feel and is especially suitable for automotive interiors such as dashboards, passenger dashboards, seat skins, ceilings, door trims, and door handles.
  • each component of the good-touch thermoplastic material of the present invention is as follows:
  • the first polymer is an ethylene-acrylic acid copolymer with acrylic acid (AA) reactive functional groups
  • the second polymer is a high molecular polymer containing glycidyl methacrylate and has glycidyl methacrylate (GMA) reactive functional groups.
  • the first polymer and the second polymer are usually used as functional additives.
  • the amount of the first polymer generally accounts for 0.1 to 1% of the total mass of the formula
  • the amount of the second polymer generally accounts for 0.1% to 1% of the total mass of the formula. 1 ⁇ 3% of the total mass, the dosage will not be too much.
  • the second polymer is usually used as a matting agent.
  • the matting agent also forms fine unevenness on the surface of the material, the structural size of the fine unevenness is too small, making it difficult to achieve high surface roughness, and it does not have a delicate texture. The touch of tiny bumps.
  • the purpose of using 5 to 25 parts of the first polymer and 5 to 25 parts of the second polymer in the present invention is to combine a larger amount of acrylic functional groups in the first polymer with a larger amount of methacrylic acid in the second polymer.
  • the glycidyl ester functional group undergoes a chemical reaction to uniformly generate enough micro-phase separated small islands in the ABS resin, and the small islands have a certain cross-linked structure, a high modulus, and excellent surface effects similar to those of inorganic fillers. , and has good enough compatibility with ABS resin, so that after the material is molded, small islands form evenly distributed fine and tiny protrusions on the surface of the material, giving the material a high surface roughness and a good touch. .
  • the essence of the present invention is to in-situ generate microscopic phase-separated small islands with higher modulus in the ABS resin phase, that is, microphase components, while achieving control of the distribution uniformity of the microphase components and control of the dispersed phase domain size, solving the problem
  • the technical problem of accurately structuring microscopic phase separation within ABS resin is solved.
  • the second polymer cooperates with the first polymer to solve the problem of controlling the size of dispersed phase domains and maintaining appropriate system compatibility.
  • the mass content of acrylic acid in the first polymer is too small, the surface roughness of the material is reduced, the functionality of acrylic acid is low, there are fewer reaction sites with the second polymer, the reaction speed is slow, and in a short processing time , has a negative impact on the formation of sufficient and well-dispersed phase-separated small islands, thereby reducing the surface feel.
  • the mass content of acrylic acid in the first polymer is too high. Although it can improve the surface roughness of the material, it may reduce the overall melt index of the material and reduce the impact strength.
  • the mass content of glycidyl methacrylate in the second polymer is too small, the epoxy functional group is low, there are fewer reaction sites with the acrylic acid group in the first polymer, and the reaction speed is slow, which is not suitable for use in shorter polymers. It is difficult to form a sufficient number of well-dispersed phase-separated small islands during processing time, thereby reducing the surface feel.
  • the mass content of glycidyl methacrylate in the second polymer is too high. Although the surface roughness of the material will be improved to a certain extent, it will reduce the overall melt index of the material and reduce the impact strength.
  • thermoplastic material of the present invention Preferably, in the good-touch thermoplastic material of the present invention,
  • the first polymer is 10 to 15 parts;
  • the second polymer is 10 to 15 parts.
  • the mass content of acrylic acid in the first polymer is 5% to 12%.
  • the mass content of glycidyl methacrylate in the second polymer is 2% to 8%.
  • the second polymer can be one of styrene-acrylonitrile-glycidyl methacrylate; ethylene-butyl acrylate-glycidyl methacrylate or ethylene-methyl acrylate-glycidyl methacrylate. species or a mixture of several species.
  • the second polymer is styrene-acrylonitrile-glycidyl methacrylate.
  • the styrene-acrylonitrile segment in the second polymer has the same segment as the ABS resin, so it has good compatibility with the ABS resin and can improve the impact strength of the composite material.
  • the melt index of the ABS resin is 20 to 50g/10min.
  • Test The condition is 220°C/10kg, and the test standard is ISO 1133-2011.
  • the ABS resin has a lower melt index and a higher viscosity, and the degree of matching with the viscosity of the first polymer with higher fluidity is reduced. Therefore, the bicontinuous phase formed by the two is less effective, and the formation of fine micro-protrusions is reduced, and the material The surface roughness is reduced and the touch is smoother.
  • the phase structure In order to further improve the matching degree between the viscosity of the first polymer and the viscosity of the ABS resin, it is beneficial for the phase structure to evolve into a bicontinuous phase during the material melt blending reaction process 3/5 to 2/3, and the composite material has Higher mechanical properties, preferably, the melt index of the first polymer is 4-12g/10min, the test condition is 190°C/2.16kg, and the test standard is ISO 1133-2011.
  • the average particle size of butadiene rubber is 0.2-3 ⁇ m.
  • the average particle size of rubber is within this range, which is conducive to the formation of higher surface roughness.
  • the ABS resin can be prepared by bulk method.
  • additives such as antioxidants, lubricants, heat stabilizers, light stabilizers and colorants can also be added according to actual performance needs.
  • antioxidants in parts by weight, it also includes 0 to 0.3 parts of antioxidants, 0 to 0.5 parts of lubricants, 0 to 0.5 parts of heat stabilizers, 0 to 0.5 parts of light stabilizers and 0 to 0.3 parts of colorants.
  • Antioxidants can be selected from independent antioxidants and auxiliary antioxidants.
  • the main antioxidants can be hindered phenol antioxidants and/or secondary arylamine antioxidants, and the auxiliary antioxidants can be organic phosphate antioxidants. .
  • the lubricant can be selected from one or a mixture of amides, metal soaps or low molecular esters.
  • the heat stabilizer can be selected from one or a mixture of organic phosphites, phosphonates or phosphates.
  • the light stabilizer may be selected from one or a mixture of benzotriazoles and/or triazines.
  • Colorants may be selected from inorganic pigments and/or organic pigments.
  • Antioxidants can improve the antioxidant effect of good-touch thermoplastic materials
  • lubricants can improve the lubrication effect of good-touch thermoplastic materials
  • heat stabilizers can improve the thermal stabilization effect of good-touch thermoplastic materials
  • light stabilizers can improve the lubrication effect of good-touch thermoplastic materials.
  • Photoaging resistance, colorants can improve the color of good-touch thermoplastic materials.
  • the present invention also protects the above-mentioned preparation method of the good-touch thermoplastic material, which includes the following steps:
  • the present invention solves the problem of uniform distribution of the first polymer in the ABS resin by mixing the ABS resin and the first polymer uniformly first.
  • step S1 the present invention uniformly disperses the first polymer in the ABS resin matrix.
  • the phase structure evolves into a bicontinuous phase.
  • S1 should be 3/5 to 2/3 of the melt blending reaction process
  • the second polymer is side-fed into the twin-screw extruder in the middle section of the twin-screw extruder. , reacts with the ethylene-acrylic acid copolymer in the S1 mixture to generate uniform microscopic phase-separated small sea islands.
  • thermoplastic material with small islands When this kind of good-touch thermoplastic material with small islands is used to inject parts, the surface of the part forms fine and delicate micro-protrusions with high surface roughness. At the same time, the peaks of these micro-protrusions are uneven and appear The cliff-like morphological features give the parts a better touch and have no negative impact on the mechanical properties.
  • the good-touch thermoplastic material prepared by the present invention has a good touch feeling and has tiny protrusions on the surface that make people feel delicate when touching. It can be widely used in the preparation of plastic products.
  • the present invention especially protects the use of the good-touch thermoplastic material in the preparation of automobile interiors. Application in decoration.
  • Automotive interiors can be instrument panels, sub-instruments, seat skins, ceilings, door trims, door handles and other parts that come into contact with the human body, but are not limited to the above applications.
  • the invention also specifically protects a plastic product prepared from the good-touch thermoplastic material.
  • plastic hand mold of the present invention can be prepared by injection molding or blow molding.
  • the invention discloses a thermoplastic material with good touch, which is composed of an ABS resin base material, a first polymer and a second polymer. By adding a larger amount of the first polymer and the second polymer to the ABS resin for synergy, it is obtained
  • the good-touch thermoplastic material has a fine surface structure, and the delicate micro-protrusions can be felt when touched. It has a high surface roughness, which effectively improves the touch of the good-touch thermoplastic material.
  • the surface roughness of automobile interior materials prepared from the good-touch thermoplastic material of the present invention can reach more than 3.12 ⁇ m, has good touch, and has good impact performance.
  • Figure 1 is an optical microscope picture of the good-touch thermoplastic material in Example 1.
  • Figure 2 is a surface roughness change curve of the good-touch thermoplastic material in Example 1.
  • Example 3 is a colorful height rendering of an optical microscope of the good-touch thermoplastic material in Example 1.
  • Figure 4 is an optical microscope image of the thermoplastic material in Comparative Example 1.
  • Figure 5 is a surface roughness change curve of the thermoplastic material in Comparative Example 1.
  • Figure 6 is a colorful height rendering of an optical microscope of the thermoplastic material in Comparative Example 1.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • ABS resin 1 is ABS resin DG-MG94, melt index is 35g/10min, average rubber particle size is 0.29 ⁇ m, Dagu, Tianjin;
  • ABS resin 2 is ABS resin 8391, melt index is 25g/10min, rubber average particle size is 1.5 ⁇ m, Takahashi Petrochemical;
  • ABS resin 3 is ABS resin 8434, melt index is 15g/10min, rubber average particle size is 1.8 ⁇ m, Takahashi Petrochemical;
  • ABS resin 4 is ABS resin PA-757, with a melt index of 15g/10min and an average rubber particle size of 0.31 ⁇ m, produced by Taiwan Chi Mei;
  • ABS resin 5 is ABS resin HR-527, with a melt index of 60g/10min and an average rubber particle size of 0.30 ⁇ m, produced by Kingfa Technology.
  • the first polymer 1 is ethylene-acrylic acid copolymer Nucrel 3990, the mass content of acrylic acid is 9.5%, the melt index is 10g/10min, Dow Chemical;
  • the first polymer 2 is ethylene-acrylic acid copolymer Nucrel 0411HS, the mass content of acrylic acid is 4.0%, the melt index is 11g/10min, Dow Chemical;
  • the first polymer 3 is ethylene-acrylic acid copolymer Nucrel 31001, the mass content of acrylic acid is 9.5%, the melt index is 1.3g/10min, Dow Chemical;
  • the first polymer 4 is ethylene-acrylic acid copolymer Nucrel KF001, the mass content of acrylic acid is 6%, the melt index is 10g/10min, Dow Chemical;
  • the first polymer 5 is ethylene-acrylic acid copolymer Nucrel KF002, the mass content of acrylic acid is 1%, the melt index is 20g/10min, Dow Chemical;
  • the first polymer 6 is ethylene-acrylic acid copolymer Nucrel KF003, the mass content of acrylic acid is 18%, the melt index is 1g/10min, Dow Chemical;
  • the second polymer 1 is styrene-acrylonitrile-glycidyl methacrylate SAG-005, and the mass content of glycidyl methacrylate is 5%, which is good;
  • the second polymer 2 is styrene-acrylonitrile-glycidyl methacrylate SAG-002, the mass content of glycidyl methacrylate is 2%, Jiayirong;
  • the second polymer 3 is styrene-acrylonitrile-glycidyl methacrylate SAG-008, the mass content of glycidyl methacrylate is 8%, Jiayirong;
  • the second polymer 4 is styrene-acrylonitrile-glycidyl methacrylate SAG-001, and the mass content of glycidyl methacrylate is 1%, Jiayirong;
  • the second polymer 5 is styrene-acrylonitrile-glycidyl methacrylate SAG-010, and the mass content of glycidyl methacrylate is 10%, Jiayirong;
  • the second polymer 6 is styrene-acrylonitrile-glycidyl methacrylate SAG-0005, and the mass content of glycidyl methacrylate is 0.5%, Jiayirong;
  • the second polymer 7 is styrene-acrylonitrile-glycidyl methacrylate SAG-012, the mass content of glycidyl methacrylate is 12%, Jiayirong;
  • Antioxidant hindered phenolic antioxidant and phosphite antioxidant, the mass ratio of hindered phenolic antioxidant and phosphite antioxidant is 1:1, commercially available and all examples and The same one was used in the comparison example;
  • Lubricant stearate lubricant, commercially available and the same one is used in all examples and comparative examples.
  • thermoplastic material including the following components in parts by weight:
  • ABS resin ABS resin; first polymer; second polymer; antioxidant and lubricant.
  • the specific content of each component is shown in Table 1 below.
  • thermoplastic material The preparation method of the above-mentioned good-touch thermoplastic material is as follows:
  • the screw speed of the twin-screw extruder is 450r/min.
  • thermoplastic alloy material Mix each component evenly, perform melt extrusion and granulation through a twin-screw extruder at 220°C, and dry to obtain the thermoplastic alloy material.
  • the screw speed of the twin-screw extruder is 450r/min.
  • thermoplastic material in which the specific contents of each component are shown in Table 2 below.
  • thermoplastic material The preparation method of the above-mentioned thermoplastic material is as follows:
  • the screw speed of the twin-screw extruder is 450r/min.
  • thermoplastic materials of the above examples and comparative examples were injection molded into standard splines, and tested through the following performance testing methods:
  • Izod notch impact strength tested in accordance with ISO180/1eA-2000 standard
  • thermoplastic material is used to prepare a textured plate through injection molding, which is a standard Volkswagen K31 textured plate with very low roughness and extremely fine texture;
  • thermoplastic materials of the above examples and comparative examples were tested by the following performance testing methods:
  • thermoplastic materials The sample is scanned through the SJ-410 surface roughness meter, and the surface roughness is used to characterize the touch feel of the material.
  • the surface roughness meter can simultaneously summarize the degree and frequency of the unevenness into roughness Value, that is, when the undulations are high, the sharper the surface peaks, the higher the roughness, the finer the surface ridges, and the better the touch effect.
  • the surface peaks are typical steamed bun peaks, the surface ridges are smooth and the touch is smooth. Feeling, not delicate enough.
  • the surface roughness of the good-touch thermoplastic material of the present invention can reach more than 3.12 ⁇ m, has good touch, and has good impact performance.
  • the good-touch thermoplastic material of the present invention has cliff-like morphology characteristics, high surface roughness, and the overall peak shape of the surface roughness curve is sharp, showing a similar jagged morphology. , has a good touch.
  • Example 19 and Example 1 it can be seen from Example 19 and Example 1 that when the ABS resin, the first polymer amount and the second polymer are directly added to the twin-screw extruder, the roughness peak shape is between Example 1 and Comparative Example 1 , the overall surface roughness curve has less sharp peaks, it also feels slippery when touched, and the surface has certain unevenness.

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Abstract

本发明公开了一种良触感热塑性材料及其制备方法和应用，属于高分子材料技术领域。良触感热塑性材料按重量份数计，包括以下组分：ABS树脂50～90份；第一聚合物5～25份；第二聚合物5～25份；第一聚合物与第二聚合物的重量比为1:0.5～2；其中，第一聚合物为乙烯-丙烯酸共聚物，丙烯酸的质量含量为3％～15％；第二聚合物为含有甲基丙烯酸缩水甘油酯的高分子聚合物，甲基丙烯酸缩水甘油酯的质量含量为1％～10％。本发明的材料通过在ABS树脂中加入较大量的第一聚合物和第二聚合物协同作用，得到的具有精细表面结构的良触感热塑性材料，在触摸时能感觉到细腻的微小凸起，具有较高的表面粗糙度，有效提升了材料的触感。

Description

一种良触感热塑性材料及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，更具体地，涉及种一种良触感热塑性材料及其制备方法和应用。
背景技术
随着国民经济的发展，汽车在人们的日常生活中越来越大众化。同时，随着生活品质的提高，消费者对汽车内饰材料的高触感性要求也越来越高。汽车内饰材料主要是指用在汽车驾驶舱内部零部件上，涉及到汽车内饰表面感知的零件，比如仪表板、副仪表板、座椅表皮、顶棚和门饰板等。此类型的内饰材料是与人们接触较多的区域，其触感直接影响车内的感知品质和消费者的驾乘体验。因此，开发良触感的丙烯腈-丁二烯-苯乙烯(ABS)材料，对于促进汽车内饰材料的发展和汽车品质的提升都有重要意义。其中，良触感评价的重要表征方法就是表面有着令人触摸感觉细腻的微小凸起。
现有技术中公开了一种哑光低气味耐热高抗冲ABS材料及其制备方法，其以ABS作为基体，加入了0.6～3份的苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯的三元无规共聚物作为消光剂，实现材料表面光泽度的下降。上述技术公开的ABS材料包含有ABS树脂和苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯成分，但其所提供的ABS材料针对改善的是其光泽度，其并未针对解决提高ABS材料的表面粗糙度，使材料在接触时能感受到具有细腻的微小凸起的技术问题。
发明内容
本发明要解决的技术问题是克服现有热塑性材料的表面粗糙度低，触感不具有细腻的微小凸起的缺陷和不足，提供一种良触感热塑性材料，通过在ABS树脂中加入较大量的第一聚合物和第二聚合物协同作用，在触摸时能感觉到细腻的微小凸起，且具有较高的表面粗糙度，有效提升了良触感热塑性材料的触感。
本发明的还一目的在于提供一种良触感热塑性材料的制备方法。
本发明的另一目的在于提供一种良触感热塑性材料在制备汽车内饰中的应用。
本发明上述目的通过以下技术方案实现：
一种良触感热塑性材料，按重量份数计，包括以下组分：
ABS树脂                                  50～90份；
第一聚合物                               5～25份；
第二聚合物                               5～25份；
所述第一聚合物与第二聚合物的重量比为1:0.5～2；
其中，所述第一聚合物为乙烯-丙烯酸共聚物，所述第一聚合物中，丙烯酸的质量含量为3％～15％，测试标准为ASTM D4094-07；
所述第二聚合物为含有甲基丙烯酸缩水甘油酯的高分子聚合物，所述第二聚合物中甲基丙烯酸缩水甘油酯的质量含量为1％～10％，测试标准为GB/T 1677-2008。
其中需要说明的是：
本发明的良触感热塑性材料在ABS树脂中加入较大量的第一聚合物和第二聚合物协同作用，在触摸时能感觉到细腻的微小凸起，且具有较高的表面粗糙度，有效提升了良触感热塑性材料的触感，尤其适用于仪表板、副仪表板、座椅表皮、顶棚、门饰板、门把手等汽车内饰。
本发明的良触感热塑性材料各组分的作用机理具体如下：
第一聚合物为乙烯-丙烯酸共聚物，具有丙烯酸(AA)反应官能团，第二聚合物为含有甲基丙烯酸缩水甘油酯的高分子聚合物，具有甲基丙烯酸缩水甘油酯(GMA)反应官能团。
现有技术中，第一聚合物和第二聚合物通常都是作为功能助剂，第一聚合物的添加量一般占配方总质量的0.1～1％，第二聚合物的添加量一般占配方总质量的1～3％，用量均不会太多。而且，现有技术中，第二聚合物通常作为消光剂使用，虽然消光剂也是在材料的表面形成微细凹凸，但是微细凹凸的结构尺寸过小，难以实现高表面粗糙度，而且也不具有细腻微小凸起的触感。
本发明中采用5～25份的第一聚合物和5～25份的第二聚合物的作用是为了将第一聚合物中较大量的丙烯酸官能团和第二聚合物中较大量的甲基丙烯酸缩水甘油酯官能团发生化学反应，在ABS树脂内均匀生成足够多的微相分离的小海岛，且该小海岛具有一定的交联结构，具备较高的模量，既具备类似无机填料优异表面效果，又与ABS树脂相有足够好的相容性，使得材料成型后，小海岛在材料的表面形成了分布均匀的细腻微小的凸起，使得材料具有较高的表面粗糙 度，具有良好的触感。
本发明实质是在ABS树脂相中原位生成具有较高模量的微观相分离的小海岛，即微相组分，同时实现微相组分的分布均匀度控制和分散相畴尺寸的控制，解决了ABS树脂内部精确构造微观相分离的技术难题，通过第二聚合物协同第一聚合物解决了分散相畴尺寸控制和保持体系相容性适度的问题。
第一聚合物中丙烯酸的质量含量过少，材料的表面粗糙度降低，丙烯酸的官能度较低，与第二聚合物的反应位点较少，反应速度较慢，在较短的加工时间内，对形成数量充足且分散良好的相分离小海岛有负面影响，从而降低表面触感。
第一聚合物中丙烯酸的质量含量过高，虽然可以提高材料的表面粗糙度，但可能会降低材料的整体熔融指数，同时降低冲击强度。
第二聚合物中甲基丙烯酸缩水甘油酯的质量含量过少，环氧官能团较低，与第一聚合物中的丙烯酸基团的反应位点较少，反应速度较慢，对在较短的加工时间内难以形成数量充足且分散良好的相分离小海岛，从而降低表面触感。
第二聚合物中甲基丙烯酸缩水甘油酯的质量含量过高，虽然材料的表面粗糙度会有一定程度的提高，但会降低材料的整体熔融指数，同时降低冲击强度。
优选地，本发明的良触感热塑性材料中，
按重量份数计，包括以下组分：
ABS树脂                                  70～80份；
第一聚合物                               10～15份；
第二聚合物                               10～15份。
为了进一步提高复合材料的表面粗糙度且具有较高的熔融指数和冲击强度，优选地，所述第一聚合物中，丙烯酸的质量含量为5％～12％。
为了进一步提高复合材料的表面粗糙度且具有较高的熔融指数和冲击强度，优选地，所述第二聚合物中甲基丙烯酸缩水甘油酯的质量含量为2％～8％。
其中，所述第二聚合物可以为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯；乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯或乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯中一种或几种的混合物。
优选地，所述第二聚合物为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯。
第二聚合物中的苯乙烯-丙烯腈链段与ABS树脂具有相同的链段，因此与ABS树脂具有良好的相容性，而且能够提高复合材料的冲击强度。
为了进一步提高复合材料中ABS树脂的粘度与第一聚合物的粘度的匹配程度，且使得复合材料具有较高的力学性能，优选地，所述ABS树脂的熔融指数为20～50g/10min，测试条件为220℃/10kg，测试标准为ISO 1133-2011。
ABS树脂的熔融指数较低，粘度较高，与流动性较高的第一聚合物的粘度的匹配程度降低，故两者形成的双连续相效果较差，细腻的微小凸起形成减少，材料表面粗糙度降低，触感较为平滑。
为了进一步提高第一聚合物的粘度和ABS树脂粘度的匹配程度，有利于在材料熔融共混反应进程3/5～2/3的过程中，相态结构演化为双连续相，且复合材料具有较高的力学性能，优选地，所述第一聚合物的熔融指数为4～12g/10min，测试条件为190℃/2.16kg，测试标准为ISO 1133-2011。
优选地，所述ABS树脂中，丁二烯橡胶的平均粒径为0.2～3μm。
橡胶平均粒径在此范围内，有利于形成较高的表面粗糙度。
所述ABS树脂可以通过本体法制备。
在实际应用中，根据实际性能需要，还可以添加抗氧剂、润滑剂、热稳定剂、光稳定剂和着色剂等助剂。
其中，以重量份数计，还包括抗氧剂0～0.3份、润滑剂0～0.5份，热稳定剂0～0.5份、光稳定剂0～0.5份和着色剂0～0.3份。
抗氧剂可选自主抗氧剂和辅助抗氧剂，主抗氧剂可以为受阻酚抗氧剂和/或仲芳基胺抗氧剂，辅助抗氧剂可以为有机磷酸酯类抗氧剂。
润滑剂可选自酰胺类、金属皂类或低分子酯类中的一种或几种的混合物。
热稳定剂可选自有机亚磷酸酯类、膦酸酯类或磷酸酯类中的一种或几种的混合物。
光稳定剂可选自苯并***类和/或三嗪类中的一种或几种的混合物。
着色剂可选自无机颜料和/或有机颜料。
抗氧剂可提升良触感热塑性材料的抗氧化效果，润滑剂可提升良触感热塑性材料的润滑效果，热稳定剂可提升良触感热塑性材料的热稳定效果，光稳定剂可提升良触感热塑性材料的耐光老化效果，着色剂可改善良触感热塑性材料的颜色。
本发明还保护上述所述良触感热塑性材料的制备方法，包括如下步骤：
S1.将除第二聚合物以外的所有组分混合均匀，从双螺杆挤出机的主喂料口 喂入，在200～300℃熔融分散均匀；
S2.在S1进行到熔融共混反应进程的3/5～2/3时，将第二聚合物侧喂进入双螺杆挤出机，在200～300℃熔融挤出、造粒，干燥后即得所述良触感热塑性材料。
本发明通过将ABS树脂和第一聚合物先混合均匀的加料方式解决了第一聚合物在ABS树脂中分布均匀的问题，本发明在步骤S1将第一聚合物分散均匀在ABS树脂基体中，相态结构演化为双连续相，在S1应进行到熔融共混反应进程的3/5～2/3时，在双螺杆挤出机的中段将第二聚合物侧喂进入双螺杆挤出机，与S1混合物中的乙烯-丙烯酸共聚物发生反应，生成均匀的微观相分离的小海岛。这种带有小海岛的良触感热塑性材料在注塑零部件时，零件表面形成精细的细腻微小的凸起，具有较高的表面粗糙度，同时这种微小凸起的峰值具有不均匀性，呈现出断崖式形貌特征，赋予零件更好的触感，且对力学性能没有负面影响。
本发明制备得到的良触感热塑性材料具有很好的触感，表面有着令人触摸感觉细腻的微小凸起，可以广泛应用于塑料制品的制备，本发明尤其保护所述良触感热塑性材料在制备汽车内饰中的应用。
汽车内饰可以为仪表板、副仪表板、座椅表皮、顶棚、门饰板、门把手等与人体接触较多的制件，但不限于上述应用。
本发明还具体保护一种塑料制品，所述塑料制品由所述良触感热塑性材料制备得到。
其中，本发明的塑料手模的制备方式可以为注塑或吹塑。
与现有技术相比，本发明的有益效果是：
本发明公开了一种良触感热塑性材料，由ABS树脂基材、第一聚合物和第二聚合物组成，通过在ABS树脂中加入较大量的第一聚合物和第二聚合物协同作用，得到的具有精细表面结构的良触感热塑性材料，在触摸时能感觉到细腻的微小凸起，具有较高的表面粗糙度，有效提升了良触感热塑性材料的触感。
本发明的良触感热塑性材料制备得到的汽车内饰材料的表面粗糙度可达3.12μm以上，具有良好的触感，且具有较好的冲击性能。
附图说明
图1为实施例1中良触感热塑性材料的光学显微镜图。
图2为实施例1中良触感热塑性材料的表面粗糙度变化曲线。
图3为实施例1中良触感热塑性材料的光学显微镜的多彩高度渲染图。
图4为对比例1中热塑性材料的光学显微镜图。
图5为对比例1中热塑性材料的表面粗糙度变化曲线。
图6为对比例1中热塑性材料的光学显微镜的多彩高度渲染图。
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，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
ABS树脂1为ABS树脂DG-MG94，熔融指数为35g/10min，橡胶平均粒径为0.29μm，天津大沽；
ABS树脂2为ABS树脂8391，熔融指数为25g/10min，橡胶平均粒径为1.5μm，高桥石化；
ABS树脂3为ABS树脂8434，熔融指数为15g/10min，橡胶平均粒径为1.8μm，高桥石化；
ABS树脂4为ABS树脂PA-757，熔融指数为15g/10min，橡胶平均粒径为0.31μm，台湾奇美；
ABS树脂5为ABS树脂HR-527，熔融指数为60g/10min，橡胶平均粒径为0.30μm，金发科技。
第一聚合物1为乙烯-丙烯酸共聚物Nucrel 3990，丙烯酸的质量含量为9.5％，熔融指数为10g/10min，陶氏化学；
第一聚合物2为乙烯-丙烯酸共聚物Nucrel 0411HS，丙烯酸的质量含量为4.0％，熔融指数为11g/10min，陶氏化学；
第一聚合物3为乙烯-丙烯酸共聚物Nucrel 31001，丙烯酸的质量含量为9.5％，熔融指数为1.3g/10min，陶氏化学；
第一聚合物4为乙烯-丙烯酸共聚物Nucrel KF001，丙烯酸的质量含量为6％，熔融指数为10g/10min，陶氏化学；
第一聚合物5为乙烯-丙烯酸共聚物Nucrel KF002，丙烯酸的质量含量为1％，熔融指数为20g/10min，陶氏化学；
第一聚合物6为乙烯-丙烯酸共聚物Nucrel KF003，丙烯酸的质量含量为18％，熔融指数为1g/10min，陶氏化学；
第二聚合物1为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-005，甲基丙烯 酸缩水甘油酯的质量含量为5％，佳易容；
第二聚合物2为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-002，甲基丙烯酸缩水甘油酯的质量含量为2％，佳易容；
第二聚合物3为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-008，甲基丙烯酸缩水甘油酯的质量含量为8％，佳易容；
第二聚合物4为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-001，甲基丙烯酸缩水甘油酯的质量含量为1％，佳易容；
第二聚合物5为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-010，，甲基丙烯酸缩水甘油酯的质量含量为10％，佳易容；
第二聚合物6为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-0005，甲基丙烯酸缩水甘油酯的质量含量为0.5％，佳易容；
第二聚合物7为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-012，甲基丙烯酸缩水甘油酯的质量含量为12％，佳易容；
抗氧剂：受阻酚类抗氧剂和亚磷酸酯类抗氧剂，受阻酚类抗氧剂和亚磷酸酯类抗氧剂的质量比为1：1，市售可得且所有实施例和对比例用的是同一种；
润滑剂：硬脂酸酯类润滑剂，市售可得且所有实施例和对比例用的是同一种。
实施例1～18
一种良触感热塑性材料，按重量份数计，包括以下组分：
ABS树脂；第一聚合物；第二聚合物；抗氧剂和润滑剂，其中各组分的具体含量如下表1所示。
表1 各实施例的良触感热塑性材料组成(以重量份数计)
序号 1 2 3 4 5 6 7
ABS树脂1 70 50 90 80 70 70 70
第一聚合物1 15 25 5 10 10 20 15
第二聚合物1 15 25 5 10 20 10 15
抗氧剂 0.6 0.6 0.6 0.6 0.6 0.6 0
润滑剂 0.2 0.2 0.2 0.2 0.2 0.2 0
续表1
序号 8 9 10 11 12 13 14 15 16 17 18
ABS树脂1         70 70 70 70 70 70 70
ABS树脂2 70                    
ABS树脂3   70                  
ABS树脂4     70                
ABS树脂5       70              
第一聚合物1 15 15 15 15       15 15 15 15
第一聚合物2         15            
第一聚合物3           15          
第一聚合物4             15        
第二聚合物1 15 15 15 15 15 15 15        
第二聚合物2               15      
第二聚合物3                 15    
第二聚合物4                   15  
第二聚合物5                     15
抗氧剂 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
润滑剂 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
上述良触感热塑性材料的制备方法具体如下：
S1.将ABS树脂、第一聚合物和加工助剂混合均匀，再投入双螺杆挤出机中在220℃进行熔融挤出造粒，
S2.将第二聚合物从离喂料口距离为加热区域总长度的3/5～2/3处侧喂进入双螺杆挤出机，即从第7节螺筒(共十二节螺筒)侧喂进入双螺杆挤出机，继续熔融、造粒，干燥得到良触感热塑性树脂组合物；
其中，双螺杆挤出机的螺杆转速为450r/min。
实施例19
本实施例的各组分与实施例1相同，区别在于制备方法，具体如下：
将各组分混合均匀，通过双螺杆挤出机在220℃进行熔融挤出、造粒，干燥后即得所述热塑性合金材料。
其中，双螺杆挤出机的螺杆转速为450r/min。
对比例1～10
一种热塑性材料，其中各组分的具体含量如下表2所示。
表2 各对比例的热塑性材料组成(以重量份数计)
序号 1 2 3 4 5 6 7 8 9 10
ABS树脂1 70 70 70 70 70 70 70 70 70 70
第一聚合物1 0 3 30 7.5 23     15 15  
第一聚合物5           15        
第一聚合物6             15      
第二聚合物1 0 3 30 22.5 7 15 15     30
第二聚合物6               15    
第二聚合物7                 15  
抗氧剂 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
润滑剂 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
上述热塑性材料的制备方法具体如下：
S1.将ABS树脂、第一聚合物和加工助剂混合均匀，再投入双螺杆挤出机中在220℃进行熔融挤出造粒；
S2.将第二聚合物从第7节螺筒侧喂进入双螺杆挤出机，继续熔融、造粒，干燥得到良触感热塑性树脂组合物；
其中，双螺杆挤出机的螺杆转速为450r/min。
结果检测
将上述实施例和对比例的热塑性材料注塑成标准样条，通过下述性能测试方法进行测试：
(1)悬臂梁缺口冲击强度：按照ISO180/1eA-2000标准测试；
(2)熔融指数：按照1133-1-2011标准测试，测试条件为10kg，220℃；
将上述热塑性材料通过注塑方法制备皮纹板，为本身粗糙度很低的、皮纹为极细小的标准大众K31皮纹板；
上述实施例和对比例的热塑性材料通过下述性能测试方法进行测试：
(3)热塑性材料的表面粗糙度：通过SJ-410表面粗糙度仪对样板扫描，采用表面粗糙度表征材料的触感，该表面粗糙度仪可将凹凸起伏的变化程度和频率同时汇总到粗糙度数值，即凹凸起伏高的同时，表面峰型越尖锐，粗糙度越高， 表面凸起越细腻，触感效果越好，当表面峰型为典型的馒头峰时，表面凸起平滑，触感有滑感，不够细腻。
(4)光学显微镜图：通过莱卡光学显微镜(DVM6)观察热塑性材料的表面。
(5)样板表面凸起渲染图：通过莱卡光学显微镜(DVM6)扫描热塑性材料的表面，自动生成自带比例尺的多彩光学渲染图。
具体检测结果如下表3所述：
Figure PCTCN2022138880-appb-000001
从上述数据可以看出，本发明的良触感热塑性材料表面粗糙度可达3.12μm以上，具有良好的触感，且具有较好的冲击性能。
从实施例1和图1～3可以看出，本发明的良触感热塑性材料具有断崖式形貌特征，表面粗糙度较高，且表面粗糙度曲线整体峰型较尖锐，呈现类似锯齿状形貌，具有良好的触感。
从实施例19和实施例1可以看出，将ABS树脂、第一聚合物量和第二聚合物直接加入到双螺杆挤出机中，粗糙度峰型介于实施例1和对比例1之间，表面粗糙度曲线整体峰型尖锐较少，触摸时也有滑感，表面具有一定的凹凸起伏。
从对比例1、图4～6和实施例1可以看出，不加入第一聚合物和第二聚合物，表面粗糙度最低，仅为3.055μm，难以达到表面触感细腻的小凸起的触感。而且，表面粗糙度峰型曲线平滑，呈馒头峰，电镜图查看材料表面平整。
从对比例2和实施例1可以看出，加入的第一聚合物和第二聚合物的量过少，粗糙度提升不明显，始终小于3.12μm，无法达到高表面粗糙度的要求。
从对比例3和实施例1可以看出，加入的第一聚合物和第二聚合物的量过多，良触感效果虽然大幅提升，但ABS组合物整体性能下降明显，熔融指数下降了75％，冲击下降22％，已无法满足零部件的应用需求。
从对比例4和实施例1可以看出，第一聚合物量和第二聚合物量的重量比过小，导致第一聚合物在ABS相态中难以形成双连续相结构，两种聚合物反应的小海岛相结构在体系中数量较少，无法满足表面的富集度要求，因此，表面粗糙度效果大打折扣，仅有3.093μm。
从对比例5和实施例1可以看出，第一聚合物量和第二聚合物量的重量比过大，虽然第一聚合物在ABS相态中成功形成双连续相结构，但第二聚合物量过小，导致形成的海岛相结构尺寸太小，无法起到改变表面性能的作用，因此表面粗糙度仅有3.113μm。
从对比例6～7和实施例1可以看出，当第一聚合物的丙烯酸含量不在本发明的范围之内，与ABS树脂粘度不匹配，因此难以形成较好的双连续相结构，第一聚合物和第二聚合物反应形成的小海岛相结构无法分布均匀，难以满足表面的富集度要求，因此，表面粗糙度效果不佳。
从对比例8～9和实施例1可以看出，当第二聚合物的甲基丙烯酸缩水甘油酯的质量含量不在本发明的范围之内时，局部特性官能团含量过高或过低，都无法对表面粗糙度进行有效的提升，第二聚合物的甲基丙烯酸缩水甘油酯的质量含量过低导致反应不充分，第二聚合物的甲基丙烯酸缩水甘油酯的质量含量过高则导 致反应过度，形成过度交联点，影响小海岛相结构的均匀分布。
从对比例10和实施例1中可以看出，即使加入再大量的第二聚合物，也无法达到优异的表面粗糙效果，这是因为任何非交联的有机组分，即使与主体树脂相不相容，引起微观相分离，但是其模量也很低，也无法对材料表面产生足够大的影响，即不能构造精细的表面凸起结构，只能形成一个小鼓包，触感不够细腻。
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. 一种良触感热塑性材料，其特征在于，按重量份数计，包括以下组分：
    ABS树脂                                   50～90份；
    第一聚合物                                5～25份；
    第二聚合物                                5～25份；
    所述第一聚合物与第二聚合物的重量比为1:0.5～2；
    其中，所述第一聚合物为乙烯-丙烯酸共聚物，丙烯酸的质量含量为3％～15％，测试标准为ASTM D4094-07；
    所述第二聚合物为含有甲基丙烯酸缩水甘油酯的高分子聚合物，甲基丙烯酸缩水甘油酯的质量含量为1％～10％，测试标准为GB/T 1677-2008。
  2. 如权利要求1所述良触感热塑性材料，其特征在于，按重量份数计，包括以下组分：
    ABS树脂                                   70～80份；
    第一聚合物                                10～15份；
    第二聚合物                                10～15份。
  3. 如权利要求1所述良触感热塑性材料，其特征在于，所述第一聚合物中，丙烯酸的质量含量为5％～12％。
  4. 如权利要求1所述良触感热塑性材料，其特征在于，所述第二聚合物中甲基丙烯酸缩水甘油酯的质量含量为2％～8％。
  5. 如权利要求1所述良触感热塑性材料，其特征在于，所述第二聚合物为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯。
  6. 如权利要求1所述良触感热塑性材料，其特征在于，所述ABS树脂的熔融指数为20～50g/10min，测试条件为220℃/10kg，测试标准为ISO 1133-2011。
  7. 如权利要求6所述良触感热塑性材料，其特征在于，所述第一聚合物的熔融指数为4～12g/10min，测试条件为190℃/2.16kg，测试标准为ISO 1133-2011。
  8. 如权利要求1所述良触感热塑性材料，其特征在于，所述ABS树脂中，丁二烯橡胶的平均粒径为0.2～3μm。
  9. 权利要求1～8任一项所述良触感热塑性材料的制备方法，其特征在于，包括如下步骤：
    S1.将除第二聚合物以外的所有组分混合均匀，从双螺杆挤出机的主喂料口喂入，在200～300℃熔融分散均匀；
    S2.在S1进行到熔融共混反应进程的3/5～2/3时，将第二聚合物侧喂进入双螺杆挤出机，在200～300℃熔融挤出、造粒，干燥后即得所述良触感热塑性材料。
  10. 一种权利要求1～8任意一项所述良触感热塑性材料在制备汽车内饰中的应用。
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