WO2023173849A1 - Matériau thermoplastique ayant une bonne sensation tactile, son procédé de préparation et application associée - Google Patents

Matériau thermoplastique ayant une bonne sensation tactile, son procédé de préparation et application associée Download PDF

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Publication number
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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English (en)
Chinese (zh)
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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

Definitions

  • 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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  • 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)

Abstract

La présente invention concerne le domaine technique des matériaux hauts polymères. L'invention concerne un matériau thermoplastique ayant une bonne sensation tactile, son procédé de préparation et une application associée. Le matériau thermoplastique ayant une bonne sensation tactile comprend les composants suivants en parties en poids : de 50 à 90 parties d'une résine ABS, de 5 à 25 parties d'un premier polymère et de 5 à 25 parties d'un second polymère, le rapport pondéral du premier polymère au second polymère étant de 1:0,5 à 2, le premier polymère étant un copolymère éthylène-acrylique, la teneur en masse de l'acide acrylique étant de 3 % à 15 %, le second polymère étant un polymère à haut poids moléculaire contenant du méthacrylate de glycidyle, et la teneur en masse du méthacrylate de glycidyle étant de 1 % à 10 %. Selon la présente invention, une grande quantité de premiers polymères et de seconds polymères est ajoutée à la résine ABS pour une action synergique, de façon à obtenir un matériau thermoplastique ayant une bonne sensation tactile et une fine structure de surface, de minuscules saillies fines peuvent être ressenties pendant le toucher et une haute rugosité de surface est obtenue, ce qui permet d'améliorer efficacement la sensation tactile du matériau.
PCT/CN2022/138880 2022-03-18 2022-12-14 Matériau thermoplastique ayant une bonne sensation tactile, son procédé de préparation et application associée WO2023173849A1 (fr)

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CN114702777B (zh) * 2022-03-18 2023-09-26 金发科技股份有限公司 一种良触感热塑性材料及其制备方法和应用

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