WO2022095362A1 - 一种pcabs组合物及其制备方法和应用 - Google Patents

一种pcabs组合物及其制备方法和应用 Download PDF

Info

Publication number
WO2022095362A1
WO2022095362A1 PCT/CN2021/090751 CN2021090751W WO2022095362A1 WO 2022095362 A1 WO2022095362 A1 WO 2022095362A1 CN 2021090751 W CN2021090751 W CN 2021090751W WO 2022095362 A1 WO2022095362 A1 WO 2022095362A1
Authority
WO
WIPO (PCT)
Prior art keywords
pcabs
parts
composition
silicone rubber
polyurethane
Prior art date
Application number
PCT/CN2021/090751
Other languages
English (en)
French (fr)
Inventor
岑茵
黄险波
艾军伟
陈勇文
王培涛
董相茂
田征宇
丁超
叶南飚
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 WO2022095362A1 publication Critical patent/WO2022095362A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the field of engineering plastics, and in particular relates to a PCABS composition, a preparation method and application thereof.
  • PCABS is a traditional high-performance alloy with beneficial characteristics such as high surface gloss, good toughness, and good processing fluidity. It is used in various fields, especially in the fields of electronic appliances, transportation, and building materials. With the development of the industry, the requirements for the diversification of material appearance are getting higher and higher. For example, car interior parts need to pay attention to the reflectivity of the instrument panel when designing, not only to improve the visibility of the instrument, but also to reduce the glare through the diffuse reflection method of the cover, and to prevent the high point on the instrument panel from being on the front windshield.
  • the inner surface forms a reflective image so as not to interfere with the driver's vision, so the surface of the instrument panel must be matt or matte to obtain a comfortable and safe driving feeling.
  • PCABS with proper matte effect is one of the key factors for design optimization. Therefore, the development of PCABS with matte effect has broad application prospects in different industries.
  • PCABS that achieves a matte finish by adding epoxide and mica powder.
  • the surface of the material can also have a certain roughness through the pattern design of the injection mold, so as to achieve a matte effect.
  • the above matte technologies all have certain limitations.
  • the addition of fillers will lead to inconsistencies in the continuous phase of the matrix, which may easily cause other performance defects such as mechanical properties and appearance, especially the hidden danger of weld lines during processing; a large amount of rubber and epoxy
  • the addition will greatly affect the fluidity of the resin and reduce the rigidity of the material, so it limits the application of the material to a certain extent, especially under the thin-walled industry development trend, lower fluidity will cause greater disadvantages; Relying on the mold design is strongly dependent on the processing conditions of the material, and the applicability is not wide.
  • the purpose of the present invention is to overcome the defects or deficiencies that PCABS in the prior art is difficult to take into account matteness, fluidity, strength and toughness and depends on processing conditions, and provides a PCABS composition.
  • the invention can greatly improve the processing fluidity of PCABS, while maintaining high strength and toughness, and can achieve satisfactory dumbness in both injection molding and extrusion processes. light effect.
  • Another object of the present invention is to provide a preparation method of the above PCABS composition.
  • Another object of the present invention is to provide the application of the above PCABS composition in the preparation of engineering plastics.
  • a PCABS composition comprising the following components by weight:
  • the rubber D50 of the acrylic shell silicone rubber is not less than 350nm.
  • ABS has the advantages of good strength and toughness, and is easy to be processed and formed. Its compounding with polycarbonate (PC) can effectively reduce the melt viscosity of the resin system and improve the processing performance of polycarbonate; acrylic shell silicone rubber and poly Carbonate has good compatibility, and polyurethane (PU) has shape memory function; adding polyurethane to PCABS can greatly improve the processing fluidity of PCABS while maintaining high strength and toughness.
  • PC polycarbonate
  • PU polyurethane
  • the acrylic shell silicone rubber has a better compatibility tendency with the PC phase in the PCABS alloy phase.
  • the addition of acrylic shell silicone rubber with a certain particle size will partially reduce the gloss of PCABS and achieve a weak matte effect; polyurethane
  • the addition of ABS can adjust the compatibility between polycarbonate and other components, and the addition of ABS can reduce the melt viscosity of the composition and achieve better dispersion of acrylic shell silicone rubber and polyurethane, so that the rubber particles in the system can be better dispersed. Micro-shrinkage is easier to form on the surface of the composition, ABS, polyurethane and acrylic shell silicone rubber have a synergistic effect on the reduction of gloss, giving PCABS a better matte effect.
  • the ASTM notched impact of the PCABS composition provided by the invention is greater than 600J/m, the injection glossiness is less than 15, the extrusion glossiness is less than 20, and the melt index at 260°C/2.16kg is greater than 20, which can meet the requirements of different processing techniques (extrusion, injection molding, etc.). etc.) matte effect requirements.
  • the PCABS composition comprises the following components by weight:
  • PCABS Polycarbonates, ABS, tougheners, antioxidants and lubricants conventionally used in the art to prepare PCABS can be used in the present invention.
  • the weight-average molecular weight of the polycarbonate is 40,000-52,000, and the content of terminal hydroxyl groups is less than 100 ppm.
  • the content of terminal hydroxyl groups is measured by the following method: take a specific content of the test sample to prepare a 1% concentration (mass concentration) clear solution, rinse with neutral ethanol, add quantitative phenolphthalein indicator, and titrate with 0.5mol/L hydrochloric acid solution The content of terminal hydroxyl group is obtained according to the consumption of hydrochloric acid.
  • the rubber content of ABS is not less than 12% (eg, 12%-65%), and the particle size is not less than 100 nm (eg, 100-1000 nm).
  • the silica gel content of the acrylic shell silicone rubber is greater than 10%.
  • the acrylic shell silicone rubber is one or both of S-2130 or S-2100.
  • the Tg temperature of the polyurethane is lower than -30°C, the refractive index is 1.52, the oil absorption value is 50-150, and the D50 is 3-40 ⁇ m.
  • the Tg temperature of polyurethane is measured by the following method: take a specific weight of the polyurethane test sample and put it in a differential calorimeter, set the heating rate to 10 °C/min, and the heating range to -60 to 200 °C. Cycle to read the Tg temperature from the analytical curve.
  • the refractive index of the polyurethane was measured directly by an Abbe refractometer with a thickness of 2 mm.
  • the oil absorption value of the polyurethane is measured by the following method: gradually add dioctyl phthalate to the polyurethane of a fixed weight, stir well until no reagent is precipitated, and the oil absorption value of the polyurethane can be obtained by adding the quality of the reagent.
  • the D50 of the polyurethane is 5-8 ⁇ m.
  • the toughening agent is a rubber-containing graft polymer.
  • Toughening agents are generally prepared by emulsion polymerization.
  • component A is grafted onto component B.
  • the dosage of component A and component B is 5-95% of component A and 5-95% of component B based on the weight of the toughening agent; preferably 10-70% of component A and 30-90% of component B ; It is particularly preferred that the component A is 20 to 60%, and the component B is 40 to 80%.
  • component A consists of the following: vinyl aromatic compounds (eg styrene, alpha-methyl styrene), vinyl aromatic compounds substituted on the ring (eg p-methyl styrene, p-chlorostyrene) and methyl styrene
  • vinyl aromatic compounds eg styrene, alpha-methyl styrene
  • vinyl aromatic compounds substituted on the ring eg p-methyl styrene, p-chlorostyrene
  • methyl styrene At least one monomer of (C1-C8)-alkyl methacrylate (such as methyl methacrylate, ethyl methacrylate) (the amount of which is 65-85% by weight of component A, preferably 70-80%) %), as well as vinyl cyanide (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (C1-C8)-alkyl (meth)
  • Component B provides the elastomeric graft base.
  • the graft base preferably has a glass transition temperature of ⁇ 0°C, more preferably ⁇ 20°C, particularly preferably ⁇ 60°C.
  • component B can be one or more of the following substances: diene rubber, diene-vinyl block copolymer rubber, EP(D)M rubber, polyurethane rubber, silicone rubber, chloroprene Ethylene rubber, ethylene/vinyl acetate rubber, etc.
  • the toughening agent is one or both of HR-181 or M722.
  • the antioxidants are hindered phenolic antioxidants (such as 1010, 176, etc.), phosphite antioxidants (such as 168, 626, 9228, etc.) or hindered amine antioxidants (such as 1098, etc.) ) one or more of them.
  • hindered phenolic antioxidants such as 1010, 176, etc.
  • phosphite antioxidants such as 168, 626, 9228, etc.
  • hindered amine antioxidants such as 1098, etc.
  • the lubricant is one or more of PETS, GTS, GMS, silicone oil or white oil.
  • the PCABS composition of the present invention may also include some other functional additives to achieve more diverse properties.
  • flame retardants such as BDP, RDP, phenoxyphosphazene, etc., 1 to 20% by weight
  • antistatic agents such as conductive carbon black, conductive graphite, polyamide polyether block copolymer, ionic liquid, etc., 1 to 30% by weight
  • antibacterial agents such as silver ion antibacterial agents with a certain carrier, etc., 0.01 to 5% by weight
  • fillers such as calcium carbonate, talc, wollastonite, titanium dioxide, barium sulfate, Glass fibers, etc., 0.1-90% by weight
  • color powder such as inorganic pigments such as carbon black, zinc sulfide, and organic dyes such as anthraquinone, 0.001-20% by weight).
  • the ASTM notched impact of the PCABS composition is greater than 600 J/m; the injection gloss is less than 15; the extrusion gloss is less than 20; and the melt index at 260° C./2.16 kg is greater than 20.
  • the PCABS composition provided by the present invention can be obtained by extrusion or injection molding.
  • PCABS composition The process that utilizes extrusion technology to prepare PCABS composition is as follows:
  • the preparation method of the above-mentioned PCABS composition comprises the following steps: mixing polycarbonate, ABS, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, extruding and granulating to obtain the PCABS combination.
  • polycarbonate, ABS, acrylic shell silicone rubber, toughening agent, antioxidant and lubricant are mixed through a high-mixer and then added from the main feeding port, and the polyurethane component is separately added through the side feeding port , extrusion, and granulation to obtain the PCABS composition.
  • the heat resistance of the polyurethane component is poor, and adding it through the side feed port can better ensure the performance of the polyurethane.
  • the preparation method of the above PCABS composition comprises the following steps: mixing polycarbonate, ABS, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, and injection molding to obtain the PCABS composition.
  • the preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.
  • the PCABS composition is used in the fields of electronic appliances, transportation, and building materials.
  • the present invention has the following beneficial effects:
  • the PCABS composition provided by the invention improves the gloss by adding ABS, acrylic shell silicone rubber and polyurethane, gives the PCABS composition a better matte effect, and can meet the needs of various processes for gloss;
  • the addition can also greatly improve the processing fluidity of PCABS while maintaining high strength and toughness.
  • the preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.
  • PC resin S-2000F, Shanghai Mitsubishi, the weight average molecular weight is 48000, and the terminal hydroxyl content is 10ppm;
  • PC resin E-1000F, Shanghai Mitsubishi, the weight average molecular weight is 50000, and the terminal hydroxyl content is 25ppm;
  • ABS resin PA747S, Chi Mei, rubber content 18%, particle size 285nm;
  • ABS resin 8391, Shanghai Gaoqiao, rubber content 11%, particle size 385nm;
  • Acrylic shell silicone rubber S-2130, Japan Mitsubishi Rayon, the content of silica gel is 30%, and the rubber particle size D50 is 800nm;
  • Acrylic shell silicone rubber S-2100, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 850nm;
  • Acrylic shell silicone rubber Sx-006, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 100nm;
  • Polyurethane PC-8 innovative chemical industry, Tg is -48°C, refractive index is 1.52, oil absorption value is 80, D50 is 5 ⁇ m;
  • Polyurethane PC-5 innovative chemical industry, Tg is -35°C, refractive index is 1.52, oil absorption value is 52, D50 is 38 ⁇ m;
  • Tg is -35°C
  • refractive index is 1.52
  • oil absorption value is 40
  • D50 is 38 ⁇ m
  • Antioxidants 1076 and 168, BASF;
  • Toughening agent HR-181 Taiwan Chi Mei
  • toner carbon black BP800, Cabot.
  • PCABS compositions of each example and comparative example were prepared by the following methods.
  • Extrusion process Polycarbonate, ABS, acrylic shell silicone rubber, toughening agent, antioxidant, lubricant and other functional additives (if any) are mixed through a high mixer and added from the main feeding port.
  • the polyurethane component is separately added through the side feeding port, extruded, and pelletized to obtain the PCABS composition.
  • Injection molding process Mix polycarbonate, ABS, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant, lubricant and other functional additives (if any), and injection molding to obtain the PCABS composition.
  • Impact strength 3.0mmIZOD notched impact strength is tested according to ASTM D256-2010 standard; the notch type is injection notch, and the injection temperature is 260°C; the higher the impact strength, the better the material toughness.
  • Injection Gloss According to ASTM-D523-2014 standard, test the injection molding plate with a thickness of 3.0mm and a diameter of not less than 60mm. The injection temperature is 260°C. Use a gloss meter to test the gloss at 60°. The smaller the gloss, the better the matte effect. Well, when the injection gloss is less than 20° and the extrusion gloss is less than 25°, the comprehensive matte effect is the best.
  • Extrusion gloss The sheet with a film thickness of 3.0mm is formed at an extrusion temperature of 240°C. After cooling at room temperature for 48 hours, the gloss at 60° is tested with a gloss meter according to the ASTM-D523-2014 standard. The smaller, the better the matte finish.
  • melt index On a melt index meter with a set temperature of 260 °C, according to the ISO1133-2011 standard, select the test conditions of 2.16kg load, weigh the set weight of the particles to be tested, and conduct the melt index test at a residence time of 240s; It is best to control the melt index between 22 and 30. If it is too small, injection molding defects will occur, and if it is too large, it will cause extrusion rupture.
  • This example provides a series of PCABS compositions whose components are shown in Table 1.
  • This example provides a series of PCABS compositions whose components are shown in Table 2.
  • This comparative example provides a series of PCABS compositions whose components are shown in Table 3.
  • Comparative Example 5 developed serious cosmetic defects after extrusion/injection molding.
  • the PCABS compositions provided by the embodiments of the present invention have good processing fluidity, high strength and toughness, and excellent matte properties; ), when the addition amount of acrylic shell silicone rubber increases, the impact strength is gradually improved, and the matte effect becomes more and more obvious; when the addition amount of acrylic shell silicone rubber is 5 parts, and the addition amount of polyurethane is 10 parts, The synergistic effect of the two is the best (Example 1), with the most excellent matte effect; when the addition amount of acrylic shell silicone rubber continues to increase, the processing flow performance will deteriorate, and the matte effect is also due to the acrylic shell silicone rubber.
  • Comparative Example 1 because the PCABS composition was not modified, and the traditional PCABS material was high gloss, the matte surface texture could not be achieved, and the matte effect could not be achieved by adding a single toughening agent, but brought The risk of processing defects and phase separation; Comparative Example 3 can achieve good toughness due to only adding acrylic shell silicone rubber, but the matte effect cannot be achieved by adding amount; Comparative Example 2 only adds polyurethane, although It can reduce the gloss but does not meet the requirements of uniform matte. At the same time, adding polyurethane alone will cause the PCABS matrix to not have enough toughness, which will lead to application limitations, and excessive fluidity will easily lead to unstable extrusion; Comparative Example 6 is due to the addition of acrylic shells.
  • the rubber particle size (D50) of the silicone-like rubber is too small, and the fluidity is further improved, which will easily lead to unstable extrusion; when subjected to external force, the thickness of the resin layer between the rubber particles is not enough to effectively prevent crack propagation, so the toughness is poor; At the same time, the PCABS composition cannot form rubber particles with sufficient surface quality to achieve a certain diffuse reflection effect, and the effect of improving gloss is not good.
  • Comparative example 7 has poor processing fluidity and poor toughness because ABS is not added; and the composition has high melt viscosity and poor fluidity, which cannot allow polyurethane and acrylate to achieve good dispersion and thus affect the surface quality.
  • the synergy of rubber cannot achieve a matte finish.

Landscapes

  • 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

本发明涉及一种PCABS组合物及其制备方法和应用。该PCABS组合物包括聚碳酸酯、ABS、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂等组分。本发明提供的PCABS组合物通过添加丙烯酸壳类硅橡胶和聚氨酯来改善光泽，赋予PCABS组合物较好的哑光效果，可满足多种工艺对光泽度的需求；另外，还可大幅度提高PCABS的加工流动性，同时保持较高的强度和韧性。

Description

一种PCABS组合物及其制备方法和应用 技术领域
本发明属于工程塑料领域，具体涉及一种PCABS组合物及其制备方法和应用。
背景技术
PCABS是一种传统的高性能合金，具有表面光泽度高，韧性好，加工流动性好等有益特点，应用于各个领域当中，特别是电子电器，交通运输，建筑材料等领域工程塑料技术领域。随着行业的发展，对材料外观多元化的要求也越来越高。例如汽车内饰件，设计时需要注意仪表板的反光度，既要提高仪表的可见度，又要通过表罩的漫反射方法减少眩光，还要防止仪表板上的高点在前风窗玻璃的内表面形成反射影像，以免干扰驾驶员的视觉，所以必须对仪表板表面进行消光或哑光处理，以获得舒适安全的驾驶感觉。在家用电器外壳上，由于视觉的舒适性角度考虑，适当的哑光效果的PCABS是设计优化的考虑关键因素之一，因此开发具有哑光效果的PCABS在不同行业中均具有广泛的应用前景。
目前常用哑光技术有以下几种：
1)添加无机材料，如纳米二氧化硅，通过利用填料表面和基体树脂之间的不相容性和不易浸润性，在加工的过程中填料会迁移，形成凹凸不平的的表面，从而产生哑光效果；CN103937271A(公开日20140723)就公开通过添加ACS和纳米二氧化硅来实现哑光效果的PCABS。
2)加入含量较高的橡胶，尤其是粒径较大或者具有一定交联度的橡胶，在加工过程中橡胶和树脂基体会发生分相，通过橡胶发生的微收缩导致材料表面形成粗糙的效果而产生哑光效果；
3)加入环氧类物质，通过环氧基团的引入，降低了ABS和PC树脂之间的相容性，从而降低材料表面的光泽度，从而产生哑光效果；CN108587106A(公开日20180928)就公开了通过添加环氧化物和云母粉来实现哑光效果的PCABS。
4)也可通过注塑模具的纹路设计，使材料表面具有一定的粗糙度，从而实现哑光效果。
以上的哑光技术均具有一定的局限性，如填料的加入会导致基体连续相的不 一致，容易引起力学性能和外观等其它性能缺陷，尤其是加工过程中熔接线隐患；橡胶和环氧的大量加入会大幅度影响树脂的流动性，以及降低材料的刚性，因此在一定程度上限制了材料的应用，尤其是薄壁化的行业发展趋势下，较低的流动性将产生较大的弊端；依靠模具设计对材料的加工条件依赖性强，适用性不广。
因此，开发一种兼具哑光、流动性、强度和韧性，且易于加工的PCABS具有重要的研究意义和经济价值。
发明内容
本发明的目的在于克服现有技术中PCABS难以兼顾哑光、流动性、强度和韧性及依赖加工条件的缺陷或不足，提供一种PCABS组合物。本发明通过丙烯酸壳类硅橡胶和聚氨酯的协同增效作用，可以大幅度提高PCABS的加工流动性，同时保持较高的强度和韧性，并在注塑和挤出的工艺上均可实现满意的哑光效果。
本发明的另一目的在于提供上述PCABS组合物的制备方法。
本发明的另一目的在于提供上述PCABS组合物在制备工程塑料中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种PCABS组合物，包括如下重量份数的组分：
Figure PCTCN2021090751-appb-000001
所述丙烯酸壳类硅橡胶的橡胶D50不小于350nm。
ABS具有强度好，韧性好的优点，且易于加工成型，其与聚碳酸酯(PC)复配能有效降低树脂体系的熔体粘度，改善聚碳酸酯的加工性能；丙烯酸壳类硅橡胶与聚碳酸酯具有较好的相容性，聚氨酯(PU)具有形状记忆功能；本发明向PCABS中添加聚氨酯，可以大幅度提高PCABS的加工流动性，同时保持较高的强度和韧性。
另外，丙烯酸壳类硅橡胶与PCABS合金相中PC相有更好的相容性倾向， 一定粒径大小丙烯酸壳类硅橡胶的加入会部分降低PCABS的光泽度，实现微弱的哑光效果；聚氨酯的加入可以调节聚碳酸酯和其它组分之间的相容性，ABS的加入可以降低组合物的熔体粘度，实现丙烯酸壳类硅橡胶和聚氨酯的较好分散，从而让体系中的橡胶粒子微收缩在组合物的表面上更加容易固定形成，ABS、聚氨酯和丙烯酸壳类硅橡胶在光泽的降低上具有协同增效作用，赋予PCABS具有较好的哑光效果。
本发明提供的PCABS组合物的ASTM缺口冲击大于600J/m，注塑光泽度小于15，挤出光泽度小于20，260℃/2.16kg的熔融指数大于20，可满足不同加工工艺(挤出、注塑等)的哑光效果需求。
优选地，所述PCABS组合物包括如下重量份数的组分：
Figure PCTCN2021090751-appb-000002
本领域常规用来制备PCABS的聚碳酸酯、ABS、增韧剂、抗氧剂和润滑剂均可用于本发明中。
优选地，所述聚碳酸酯的重均分子量为40000～52000，端羟基含量小于100ppm。
端羟基的含量通过如下方法测得：取特定含量的测试样配制1％浓度(质量浓度)的澄清溶液，用中性乙醇冲洗，并加入定量的酚酞指示剂，用0.5mol/L盐酸溶液滴定量至红色消失，根据盐酸消耗量即得到端羟基含量。
优选地，ABS的橡胶含量不小于12％(例如12％～65％)，粒径不小于100nm(例如100～1000nm)。
优选地，所述丙烯酸壳类硅橡胶的硅胶含量大于10％。
优选地，所述丙烯酸壳类硅橡胶为S-2130或S-2100中的一种或两种。
优选地，所述聚氨酯的Tg温度低于-30℃，折射率为1.52，且吸油值在50～150， D50为3～40μm。
聚氨酯的Tg温度通过如下方法测得：取特定重量的聚氨酯测试样放入示差热量分析仪器中，设定升温速率为10℃/min，升温范围为-60～200℃，氮气氛围并进行两个循环，从分析曲线中读取Tg温度。
聚氨酯的折射率通过厚度为2mm的测试样板阿贝折射仪直接测得。
聚氨酯的吸油值通过如下方法测得：在固定重量的聚氨酯中逐步加入邻苯二甲酸二辛酯，充分搅拌直至无试剂析出，通过添加试剂的质量即可得到聚氨酯的吸油值。
更为优选地，所述聚氨酯的D50为5～8μm。
优选地，所述增韧剂为含橡胶的接枝聚合物。
增韧剂一般通过乳液聚合制备得到。
具体地，由组分A接枝至组分B上。组分A和组分B的用量按增韧剂重量计，为组分A 5～95％，组分B 5～95％；优选为组分A 10～70％，组分B 30～90％；特别优选为组分A 20～60％，组分B 40～80％。
其中组分A组成如下：乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯)、在环上取代的乙烯基芳族化合物(例如对甲基苯乙烯、对氯苯乙烯)和甲基丙烯酸(C1～C8)-烷基酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯)的至少一种单体(其用量为组分A重量的65～85％，优选为70～80％)，以及乙烯基氰(例如不饱和腈，如丙烯腈和甲基丙烯腈)、(甲基)丙烯酸(C1～C8)-烷基酯(例如甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和不饱和羧酸的衍生物(例如酐和酰亚胺、马来酸酐和N-苯基马来酰亚胺)的至少一种单体(其用量为组分A重量的15～35％，优选为20～30％)。
组分B提供弹性体接枝基础。该接枝基础优选具有<0℃，更优选<-20℃，特别优选<-60℃的玻璃化转变温度。
具体地，组分B可为如下物质中的一种或几种：二烯橡胶、二烯-乙烯基嵌段共聚物橡胶、EP(D)M橡胶、聚氨酯橡胶、硅酮橡胶、氯丁二烯橡胶、乙烯/乙酸乙烯酯橡胶等。
具体地，所述增韧剂为HR-181或M722中的一种或两种。
优选地，所述抗氧剂为受阻酚类抗氧剂(例如1010、176等)、亚磷酸酯类 抗氧剂(例如168、626、9228等)或受阻胺类抗氧剂(例如1098等)中的一种或几种。
优选地，所述润滑剂为PETS、、GTS、GMS、硅油或白油中的一种或几种。
本发明的PCABS组合物还可以包括一些其它的功能助剂以实现更多样化的性能。
例如阻燃剂(如BDP、RDP、苯氧磷腈等，重量百分数为1～20％)；抗静电剂(如导电炭黑、导电石墨、聚酰胺聚醚嵌段共聚物、离子液体等，重量百分数为1～30％)；抗菌剂(如具有一定载体的银离子抗菌剂等，重量百分数为0.01～5％)；填料(如碳酸钙、滑石粉、硅灰石、二氧化钛、硫酸钡、玻璃纤维等，重量百分数为0.1～90％)；色粉(如炭黑、硫化锌等无机类颜料、蒽醌等有机类染料，重量百分数为0.001～20％)。
优选地，所述PCABS组合物的ASTM缺口冲击大于600J/m；注塑光泽度小于15；挤出光泽度小于20；260℃/2.16kg的熔融指数大于20。
本发明提供的PCABS组合物既可挤出得到，也可注塑得到。
利用挤出工艺制备得到PCABS组合物的过程如下：
上述PCABS组合物的制备方法，包括如下步骤：将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，挤出，造粒，即得所述PCABS组合物。
具体地，将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、增韧剂、抗氧剂和润滑剂混合通过高混机混合后从主喂料口加入，聚氨酯组分单独通过侧喂料口加入，挤出，造粒，即得所述PCABS组合物。
相较于聚碳酸酯，聚氨酯组分的耐热性较差，通过侧喂料口加入可以更好地保证聚氨酯的性能。
利用注塑工艺制备得到PCABS组合物的过程如下：
上述PCABS组合物的制备方法，包括如下步骤：将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，注塑，即得所述PCABS组合物。
本发明的制备方法工艺简单，适用性强，易于推广应用。
上述PCABS组合物在制备工程塑料中的应用也在本发明的保护范围内。
优选地，PCABS组合物在电子电器、交通运输、建筑材料领域中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明提供的PCABS组合物通过添加ABS、丙烯酸壳类硅橡胶和聚氨酯来改善光泽，赋予PCABS组合物较好的哑光效果，可满足多种工艺对光泽度的需求；另外，ABS和聚氨酯的添加还可大幅度提高PCABS的加工流动性，同时保持较高的强度和韧性。
本发明的制备方法工艺简单，适用性强，易于推广应用。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
PC树脂，S-2000F，上海三菱，重均分子量为48000，端羟基含量为10ppm；
PC树脂，E-1000F，上海三菱，重均分子量为50000，端羟基含量为25ppm；
ABS树脂：PA747S，奇美，橡胶含量18％，粒径285nm；
ABS树脂：8391，上海高桥，橡胶含量11％，粒径385nm；
丙烯酸壳类硅橡胶：S-2130，日本三菱丽阳，硅胶含量为30％，橡胶粒径D50为800nm；
丙烯酸壳类硅橡胶：S-2100，日本三菱丽阳，硅胶含量为10％，橡胶粒径D50为850nm；
丙烯酸壳类硅橡胶：Sx-006，日本三菱丽阳，硅胶含量为10％，橡胶粒径D50为100nm；
聚氨酯：PC-8创新化工，Tg为-48℃，折射率为1.52，吸油值为80，D50为5μm；
聚氨酯：PC-5创新化工，Tg为-35℃，折射率为1.52，吸油值为52，D50为38μm；
聚氨酯：PC-3创新化工，Tg为-35℃，折射率为1.52，吸油值为40，D50 为38μm；
抗氧剂：1076和168，BASF；
润滑剂：PETS，发基；
增韧剂：HR-181台湾奇美；
其它功能助剂：色粉，炭黑BP800，卡博特。
各实施例和对比例的PCABS组合物通过如下方法制备得到。
挤出工艺：将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、增韧剂、抗氧剂、润滑剂和其它功能助剂(如有)混合通过高混机混合后从主喂料口加入，聚氨酯组分单独通过侧喂料口加入，挤出，造粒，即得所述PCABS组合物。
注塑工艺：将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂、润滑剂和其它功能助剂(如有)混合，注塑，即得所述PCABS组合物。
本发明各实施例及对比例的PCABS组合物的各项性能的测试方法如下：
冲击强度：根据ASTM D256-2010标准下测试3.0mmIZOD缺口冲击强度；缺口类型为注塑缺口，其中注塑温度为260℃；其中冲击强度越高，材料韧性越好。
注塑光泽度：根据ASTM-D523-2014标准下测试3.0mm厚度直径不小于60mm的注塑板，注塑温度为260℃，用光泽度仪测试60°光泽度大小，光泽度越小，哑光效果越好，当注塑光泽度小于20°，挤出光泽度小于25°的情况下，综合哑光效果最佳。
挤出光泽度：在挤出温度为240℃下成型膜厚为3.0mm的板材，经过室温冷却48h后，按照ASTM-D523-2014标准下用光泽度仪测试60°光泽度大小，光泽度越小，哑光效果越好。
熔融指数：在设定温度为260℃的熔指仪上，按照ISO1133-2011标准，选择2.16kg负荷的测试条件，称量设定的待测粒子的重量，在停留时间240s进行熔融指数测试；熔融指数控制在22～30之间最佳，过小会出现注塑缺陷，过大会引起挤出破裂。
实施例1～13
本实施例提供一系列的PCABS组合物，其组分如表1。
表1实施例1～13提供的PCABS组合物的组分(份)
Figure PCTCN2021090751-appb-000003
Figure PCTCN2021090751-appb-000004
实施例14～19
本实施例提供一系列的PCABS组合物，其组分如表2。
表2实施例14～19提供的PCABS组合物的组分(份)
Figure PCTCN2021090751-appb-000005
Figure PCTCN2021090751-appb-000006
对比例1～7
本对比例提供一系列的PCABS组合物，其组分如表3。
表3对比例1～7提供的PCABS组合物的组分(份)
Figure PCTCN2021090751-appb-000007
按上述提及的测试方法对各实施例和对比例的PCABS组合物的性能进行测定，测试结果如表4。
其中，对比例5由于聚氨酯的添加量过大，无法挤出/注塑成型，故无法进行性能测试。对比例4挤出/注塑成型后出现了严重的外观缺陷。
表4各实施例和对比例的PCABS组合物的性能测试结果
Figure PCTCN2021090751-appb-000008
从表4可知，本发明各实施例提供的PCABS组合物具有较好的加工流动性、较高的强度和韧性及优异的哑光性能；其中，在一定范围内(实施例1、6～9)，丙烯酸壳类硅橡胶的添加量增大时，冲击强度逐渐改善，而且哑光效果越来越明显；当丙烯酸壳类硅橡胶的添加量为5份，聚氨酯的添加量为10份时，两者协同作用最佳(实施例1)，具有最为优异的哑光效果；丙烯酸壳类硅橡胶的添加量继续增大时，加工流动性能将变差，而哑光效果也由于丙烯酸壳类硅橡胶和聚氨酯的协同作用减弱也略有降低；如丙烯酸壳类硅橡胶的添加量过大(如对比例4)，会引起材料的严重分层外观缺陷，并且丙烯酸壳类硅橡胶中的橡胶粒子将析出至组合物的表面导致相分离，韧性较差，且使得哑光效果相对于不添加(对比 例1)仅略有提升。在一定范围内(实施例1、10～13)，聚氨酯的添加量增大时，哑光效果越来越好，尤其是挤出哑光改善，同时体系的流动性逐渐改善；但聚氨酯的添加量较大时，体系的热稳定性降低将导致韧性的下降；如聚氨酯的添加量过大(如对比例5)，会严重降低体系的热稳定性导致韧性的下降；当丙烯酸壳类硅橡胶的添加量为5～10，聚氨酯的添加量为5～10时，具有更佳的综合性能。而对比例1由于未对PCABS组合物进行改性处理，和传统的PCABS材料都为高光泽，无法实现哑光的表面质感，通过单一的增韧剂的加入不能实现哑光效果，却带来加工缺陷和相分离的风险；对比例3由于仅添加丙烯酸壳类硅橡胶，虽然可以实现较好的韧性，但也无法通过添加量实现哑光效果的呈现；对比例2由于仅添加聚氨酯，虽然可以降低光泽度但是不满足均匀的哑光要求，同时单独加入聚氨酯会导致PCABS基体不具备足够的韧性导致应用局限，且流动性过大易引起挤出不稳定；对比例6由于添加的丙烯酸壳类硅橡胶的橡胶粒径(D50)过小，流动性得到进一步提升易引起挤出不稳定；在受到外力作用时，橡胶粒间的树脂层厚度不足以有效阻止裂纹扩展，因此韧性不佳；同时PCABS组合物无法形成足够的表面质量的橡胶粒子来达到一定的漫反射效果，对光泽的改善效果不佳。对比例7由于未添加ABS，加工流动性差，韧性不佳；且组合物的熔体粘度高，流动性差，不能让聚氨酯和丙烯酸酯实现良好的分散进而影响表面质量，通过聚氨酯和丙烯酸壳类硅橡胶的协同作用无法实现哑光效果。
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。

Claims (10)

  1. 一种PCABS组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯 10～90份，
    ABS      10～90份，
    丙烯酸壳类硅橡胶 0.5～20份，
    聚氨酯 0.5～20份，
    增韧剂 0.1～20份，
    抗氧剂 0.001～5份，
    润滑剂 0.001～5份，
    所述丙烯酸壳类硅橡胶的橡胶D50不小于350nm。
  2. 根据权利要求1所述PCABS组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯 50～70份，
    ABS 30～50份，
    丙烯酸壳类硅橡胶 5～10份，
    聚氨酯 5～10份，
    增韧剂 1～15份，
    抗氧剂 0.01～2份，
    润滑剂 0.1～3份。
  3. 根据权利要求1所述PCABS组合物，其特征在于，所述聚碳酸酯的重均分子量为40000～52000，端羟基含量不大于100ppm。
  4. 根据权利要求1所述PCABS组合物，其特征在于，丙烯酸壳类硅橡胶的硅胶含量不小于10％。
  5. 根据权利要求1所述PCABS组合物，其特征在于，所述丙烯酸壳类硅橡胶的橡胶D50为800～1000nm。
  6. 根据权利要求1所述PCABS组合物，其特征在于，所述聚氨酯的Tg温度小于-30℃，折射率为1.52，且吸油值在50～150，D50为3～40μm。
  7. 根据权利要求1所述PCABS组合物，其特征在于，所述增韧剂为含橡胶的接枝聚合物；所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂或受阻胺类抗氧剂中的一种或几种；所述润滑剂为PETS、GTS、GMS、硅油或白油中 的一种或几种。
  8. 根据权利要求1所述PCABS组合物，其特征在于，所述PCABS组合物的ASTM缺口冲击大于600J/m；注塑光泽度小于15；挤出光泽度小于20；260℃/2.16kg的熔融指数大于20。
  9. 权利要求1～8任一所述PCABS组合物的制备方法，其特征在于，包括如下步骤：将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、增韧剂、抗氧剂和润滑剂挤出，造粒，即得所述PCABS组合物；或将聚碳酸酯、ABS、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，注塑，即得所述PCABS组合物。
  10. 权利要求1～8任一所述PCABS组合物在制备工程塑料中的应用。
PCT/CN2021/090751 2020-11-06 2021-04-28 一种pcabs组合物及其制备方法和应用 WO2022095362A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011228457.XA CN112375362B (zh) 2020-11-06 2020-11-06 一种pc/abs组合物及其制备方法和应用
CN202011228457.X 2020-11-06

Publications (1)

Publication Number Publication Date
WO2022095362A1 true WO2022095362A1 (zh) 2022-05-12

Family

ID=74578786

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/090751 WO2022095362A1 (zh) 2020-11-06 2021-04-28 一种pcabs组合物及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN112375362B (zh)
WO (1) WO2022095362A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112375362B (zh) * 2020-11-06 2022-03-22 金发科技股份有限公司 一种pc/abs组合物及其制备方法和应用
CN114806124B (zh) * 2022-03-31 2024-05-14 金发科技股份有限公司 一种耐候pc/聚酯合金材料及其制备方法与应用

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4526926A (en) * 1983-04-22 1985-07-02 The Dow Chemical Company Low gloss carbonate polymer blends
CN101535407A (zh) * 2006-11-03 2009-09-16 拜尔材料科学有限公司 具有低光泽和低温抗冲性的热塑性组合物
CN104927337A (zh) * 2015-07-15 2015-09-23 上海锦湖日丽塑料有限公司 一种耐湿热老化、高pu泡沫结合强度pc/abs材料
CN106674962A (zh) * 2016-12-21 2017-05-17 上海嘉远拜力投资管理有限公司 一种热老化性能优异的pc/abs合金及其制备方法
KR20170063123A (ko) * 2015-11-30 2017-06-08 주식회사 엘지화학 저광택 및 내광성이 우수한 폴리카보네이트-abs계 얼로이 수지 조성물 및 이를 포함하는 성형품
CN107674396A (zh) * 2017-09-25 2018-02-09 上海长伟锦磁工程塑料有限公司 一种超低光泽、高耐候、耐刮擦性pc/abs合金及其制备方法
KR20190079384A (ko) * 2017-12-27 2019-07-05 주식회사 엘지화학 저광택 및 내광성이 우수한 폴리카보네이트-abs계 얼로이 수지 조성물 및 이를 포함하는 성형품
CN112375363A (zh) * 2020-11-06 2021-02-19 金发科技股份有限公司 一种玻纤增强的聚碳酸酯组合物及其制备方法和应用
CN112375362A (zh) * 2020-11-06 2021-02-19 金发科技股份有限公司 一种pcabs组合物及其制备方法和应用
CN112457645A (zh) * 2020-11-06 2021-03-09 金发科技股份有限公司 一种聚碳酸酯合金组合物及其制备方法和应用
CN112480625A (zh) * 2020-11-06 2021-03-12 金发科技股份有限公司 一种聚酯合金组合物及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10213431A1 (de) * 2002-03-26 2003-10-09 Bayer Ag Schlagzähmodifizierte Polymer-Zusammensetzung
RU2467038C2 (ru) * 2008-03-31 2012-11-20 Тейдзин Кемикалз Лтд. Композиция ароматической поликарбонатной смолы и формованное из нее изделие
CN102115583A (zh) * 2009-12-30 2011-07-06 上海金发科技发展有限公司 一种耐候、低光泽、高流动的聚碳酸酯组合物
CN102070894B (zh) * 2011-01-19 2012-12-26 烟台万华聚氨酯股份有限公司 一种高流动高抗冲耐刮擦聚碳酸酯组合物及其制备方法
MX2014007863A (es) * 2011-12-29 2014-09-22 Bayer Ip Gmbh Composiciones polimericas con adhesion mejorada.
CN106810842B (zh) * 2017-02-08 2018-09-14 厦门市天宇塑料工业有限公司 一种耐候阻燃可用于室外灯罩的光扩散pc及其制备方法
CN111500042B (zh) * 2020-03-25 2022-11-15 上海金发科技发展有限公司 一种哑光pc/abs合金材料及其制备方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4526926A (en) * 1983-04-22 1985-07-02 The Dow Chemical Company Low gloss carbonate polymer blends
CN101535407A (zh) * 2006-11-03 2009-09-16 拜尔材料科学有限公司 具有低光泽和低温抗冲性的热塑性组合物
CN104927337A (zh) * 2015-07-15 2015-09-23 上海锦湖日丽塑料有限公司 一种耐湿热老化、高pu泡沫结合强度pc/abs材料
KR20170063123A (ko) * 2015-11-30 2017-06-08 주식회사 엘지화학 저광택 및 내광성이 우수한 폴리카보네이트-abs계 얼로이 수지 조성물 및 이를 포함하는 성형품
CN106674962A (zh) * 2016-12-21 2017-05-17 上海嘉远拜力投资管理有限公司 一种热老化性能优异的pc/abs合金及其制备方法
CN107674396A (zh) * 2017-09-25 2018-02-09 上海长伟锦磁工程塑料有限公司 一种超低光泽、高耐候、耐刮擦性pc/abs合金及其制备方法
KR20190079384A (ko) * 2017-12-27 2019-07-05 주식회사 엘지화학 저광택 및 내광성이 우수한 폴리카보네이트-abs계 얼로이 수지 조성물 및 이를 포함하는 성형품
CN112375363A (zh) * 2020-11-06 2021-02-19 金发科技股份有限公司 一种玻纤增强的聚碳酸酯组合物及其制备方法和应用
CN112375362A (zh) * 2020-11-06 2021-02-19 金发科技股份有限公司 一种pcabs组合物及其制备方法和应用
CN112457645A (zh) * 2020-11-06 2021-03-09 金发科技股份有限公司 一种聚碳酸酯合金组合物及其制备方法和应用
CN112480625A (zh) * 2020-11-06 2021-03-12 金发科技股份有限公司 一种聚酯合金组合物及其制备方法和应用

Also Published As

Publication number Publication date
CN112375362A (zh) 2021-02-19
CN112375362B (zh) 2022-03-22

Similar Documents

Publication Publication Date Title
WO2022095365A1 (zh) 一种玻纤增强的聚碳酸酯组合物及其制备方法和应用
KR100836572B1 (ko) 기계적 물성이 우수한 광확산성 수지 조성물
WO2022095362A1 (zh) 一种pcabs组合物及其制备方法和应用
CN112457645B (zh) 一种聚碳酸酯合金组合物及其制备方法和应用
KR20130057795A (ko) 열가소성 수지 조성물 및 이를 이용한 성형품
KR102165697B1 (ko) 그라프트 공중합체, 이를 포함하는 열가소성 수지 조성물 및 이의 제조방법
CN110218432A (zh) 一种高韧性pc/pmma合金材料及其制备方法
CN114957874B (zh) 一种高硬度耐划伤聚苯乙烯复合材料及其制备方法与应用
KR100983872B1 (ko) 고광택, 고경도 투명 열가소성 수지 조성물
KR101132143B1 (ko) 기계적 물성 및 내후성이 우수한 광확산 수지 조성물
CN112480626B (zh) 一种玻纤增强聚碳酸酯组合物及其制备方法和应用
JP4852199B2 (ja) レーザーマーキング用ブタジエン系ゴム強化樹脂組成物
KR100988975B1 (ko) 광확산성 열가소성 수지 조성물의 제조방법
KR101931585B1 (ko) 열가소성 수지 조성물 및 이로부터 제조된 성형품
KR102177828B1 (ko) 열가소성 수지 조성물, 이의 제조방법 및 이를 포함하는 사출 성형품
JP2000017170A (ja) 熱可塑性樹脂組成物
KR20130029826A (ko) 고투명 저온 무백화 열가소성 수지 조성물 및 이를 이용한 열가소성 수지의 제조방법
JP2007177229A (ja) 熱可塑性樹脂組成物の製造方法
JP2000204220A (ja) メタクリル系樹脂用改質剤
WO2015008945A1 (ko) 내충격성과 투명성이 우수한 (메트)아크릴레이트계 수지 조성물
JP2013087257A (ja) 透明熱可塑性樹脂組成物およびその成形品
JP2003313393A (ja) 装飾用樹脂および成形品
CN115403886B (zh) 耐刮擦组合物、制备方法以及应用
JP3382661B2 (ja) ガラス繊維配合樹脂組成物
JP2727695B2 (ja) 艶消し剤，その製造法，艶消し熱可塑性樹脂組成物及び成形品

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: 21888066

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 28/09/2023).

122 Ep: pct application non-entry in european phase

Ref document number: 21888066

Country of ref document: EP

Kind code of ref document: A1