Resin composition as well as preparation method and application thereof

Abstract

The embodiment of the invention provides a resin composition as well as a preparation method and application thereof. The resin composition comprises the following components in percentage by mass: 30-60% of a cycloolefin polymer, 3-15% of an olefin polymer and / or a modified olefin polymer and 35-70% of filler, wherein the filler comprises a titanate filler and a non-titanate filler, the mass percent of the titanate filler is 10%-40%, the mass percent of the non-titanate filler is 0-40%, and the dielectric constant of the non-titanate filler is greater than 20. The resin composition provided by the embodiment of the invention has high dielectric constant, low dielectric loss and relatively high heat resistance and impact resistance, can be used as a dielectric material in the field of communication, and can meet the requirements of mechanical properties and heat resistance while improving the signal transmission efficiency.

Description

Technical Field

[0001] The embodiments of the present application relate to the field of communication technologies, and in particular, to a resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of communication technologies, the demand for high-energy-efficient high-frequency communication is increasing. In high-frequency communication, in order to minimize signal transmission loss, dielectric materials with extremely low dielectric loss Df need to be used. In addition, when the volume of micro-capacitors is limited, to develop capacitor components with high power and high safety factors, dielectric materials with higher dielectric constant Dk and lower dielectric loss Df must be used.

[0003] However, traditional high-dielectric ceramic materials have high production costs, poor toughness, and are not easy to process; while the currently hotly concerned high-dielectric low-loss thermoplastic composites are mainly polyphenylene ether composites. At high frequencies above 10 GHz, their dielectric loss is 0.0015 - 0.003, still unable to meet the requirements of extremely energy-efficient antennas. In addition, higher requirements are currently put forward for properties such as the heat resistance and mechanical strength of dielectric materials. For example, when traffic or data transmission is active, the antenna radio frequency module operates at high power, resulting in excessive heat generation in the module, which requires the dielectric material to have a high heat distortion temperature.

[0004] Therefore, in order to better meet the application requirements of high-frequency communication and miniaturized electronic components, it is necessary to provide a resin material with high dielectric constant, low dielectric loss, as well as high heat resistance and impact resistance. Summary of the Invention

[0005] In view of this, the embodiments of the present application provide a resin composition, which has high dielectric constant, low dielectric loss, as well as high heat resistance and impact resistance. When used as a dielectric material in the communication field, it can improve the signal transmission efficiency while meeting the requirements of mechanical properties and heat resistance, thus better meeting the application requirements of high-frequency communication and miniaturized communication components.

[0006] In the first aspect of the embodiments of the present application, a resin composition is provided. The resin composition includes the following components in mass percentages: 30% - 60% of cycloolefin polymers, 3% - 15% of olefin polymers and / or modified olefin polymers, and 35% - 70% of fillers;

[0007] Among them, the filler includes titanate filler and non-titanate filler. The mass percentage of the titanate filler is 10% - 40%, the mass percentage of the non-titanate filler is 0 - 40%, and the dielectric constant of the non-titanate filler is greater than 20.

[0008] The resin composition provided by the embodiments of the present application is obtained by compounding a cycloolefin polymer with an olefin polymer and / or a modified olefin polymer, and a specific type of filler. It can have both a high dielectric constant, a low dielectric loss, as well as relatively high heat resistance and impact resistance. When used as a dielectric material in the communication field, it can improve the signal transmission efficiency while meeting the requirements of mechanical properties and heat resistance, so as to better meet the application needs of high-frequency communication and miniaturized communication components, and promote the high-frequency and miniaturized development of communication components such as antennas.

[0009] Cycloolefin polymers have excellent dielectric properties, heat resistance, and processing and molding properties, etc. Using them as the main resin of dielectric materials in the communication field can enable the dielectric materials to better meet the application requirements of the communication field. Cycloolefin polymers include two types: cyclic olefin copolymers (COC) and cyclic olefin homopolymers (COP). Among them, cyclic olefin copolymers (COC) are copolymerized from ethylene or α-olefins (monoolefins with double bonds at the ends of the molecular chain) and cycloolefin monomers such as norbornene. Cyclic olefin homopolymers (COP) are homopolymerized from cycloolefin monomers such as norbornene.

[0010] In the embodiments of the present application, the heat distortion temperature of at least part of the cycloolefin polymer is greater than or equal to 140 °C. The cycloolefin polymer having a relatively high heat distortion temperature is beneficial to improving the heat resistance of the resin composition.

[0011] In the embodiments of the present application, the heat distortion temperature of at least part of the cycloolefin polymer is greater than or equal to 150 °C.

[0012] In the embodiments of the present application, the heat distortion temperature of at least part of the cycloolefin polymer is greater than or equal to 160 °C.

[0013] In the embodiments of the present application, at least part of the cycloolefin polymer is a cyclic olefin copolymer. The presence of the cyclic olefin copolymer can better improve the heat resistance of the resin composition.

[0014] In the embodiments of the present application, the mass percentage of the olefin polymer and / or the modified olefin polymer is 5%-10%. The addition of an appropriate amount of the olefin polymer and / or the modified olefin polymer can effectively improve the toughness of the resin composition, enhance the ability of the resin composition to resist impact damage, improve the interfacial bonding force between the inorganic and organic fillers, and enable the resin composition to have sufficient addition of cycloolefin polymers and fillers, thereby facilitating the guarantee of the heat resistance, dielectric properties, and other mechanical properties of the resin composition.

[0015] In some embodiments of the present application, the mass percentage of the olefin polymer in the resin composition is 5%-15%. The main function of the olefin polymer is to improve the toughness of the resin composition and enhance the impact resistance. Controlling it at a relatively high content is beneficial to better enhancing the impact resistance.

[0016] In some embodiments of the present application, the mass percentage of the modified olefin polymer in the resin composition is 1%-5%. The main function of the modified olefin polymer is to improve the interfacial bonding performance of the components. Controlling it at a relatively low content is beneficial to enhancing the interfacial bonding performance while ensuring the improvement of the impact resistance.

[0017] In the embodiments of the present application, the melting temperature of the olefin polymer and / or the modified olefin polymer is greater than 105°C. The melting temperature refers to the temperature required for the substance to change from the high elastic state to the viscous flow state. The olefin polymer and the modified olefin polymer having a relatively high melting temperature are beneficial for the olefin polymer and the modified olefin polymer to play a role in enhancing the toughness of the resin composition while enabling the resin composition to still maintain a relatively high heat resistance.

[0018] In the embodiments of the present application, the olefin polymer includes an olefin block copolymer. The olefin block copolymer is a polymer obtained by block copolymerization of two or more olefin monomers. It has two or more different olefin monomer units and is combined in an orderly manner. The block copolymerization method of the olefin block copolymer can maintain the toughness of the material while ensuring relatively high heat resistance. The olefin block copolymer can be, for example, a propylene-butadiene block copolymer, an ethylene-propylene block copolymer, an ethylene-butadiene block copolymer, etc.

[0019] In the embodiments of the present application, the modified olefin polymer includes a maleic anhydride-grafted olefin polymer.

[0020] In the embodiments of the present application, the mass ratio of the titanate filler to the non-titanate filler is greater than or equal to 0.5:1. Controlling at the above mass ratio is beneficial to enhancing the dielectric properties of the resin composition and better ensuring the dimensional stability of the molded article of the resin composition.

[0021] In the embodiments of the present application, the titanate filler includes one or more of calcium titanate, calcium magnesium titanate, calcium strontium titanate, strontium barium titanate, and barium titanate. These titanate fillers have a relatively high dielectric constant, can also improve the mechanical properties, and are well combined with the resin component. Adding them to the resin composition is beneficial to improving the dielectric properties and impact resistance of the resin composition.

[0022] In the embodiments of the present application, the titanate filler is spherical or quasi-spherical particles, and the average sphericity is greater than 0.85. The titanate filler being spherical or quasi-spherical particles is beneficial to better reducing the dielectric loss Df of the resin composition, reducing interface defects, improving the mechanical properties of the resin composition, increasing the melt index of the composition, and facilitating injection molding. The higher the sphericity, the more beneficial it is. Among them, the sphericity is a parameter characterizing the particle morphology, which is the ratio of the surface area of a sphere with the same volume as the particle to the surface area of the particle. The closer the particle morphology is to a sphere, the closer its sphericity is to 1.

[0023] In the embodiments of the present application, the D50 particle size of the titanate filler is 0.5 μm - 100 μm. D50 is the particle size corresponding to when the cumulative particle size distribution percentage of a sample reaches 50%, and D50 is also called the median diameter or median particle size. The titanate filler having a suitable particle size is beneficial to its uniform dispersion in the resin composition, better exerting the performance advantages of the titanate filler, and improving the compactness, dielectric properties, and mechanical properties of the molded article obtained after the resin composition is molded.

[0024] In the embodiments of the present application, the non-titanate filler includes metal or non-metal oxides, and the metal or non-metal oxides include hafnium dioxide, titanium oxide, lead oxide, tantalum oxide, etc. These metal oxides all have a relatively high dielectric constant and structural stability. Adding them in combination with the titanate filler to the resin composition can effectively improve the dielectric properties and dimensional stability of the resin composition.

[0025] In some embodiments of the present application, the dielectric constant of the non-titanate filler is greater than 50. Selecting a non-titanate filler with a relatively large dielectric constant is beneficial to improving the dielectric properties of the resin composition.

[0026] In the embodiments of the present application, the non-titanate filler is spherical or quasi-spherical particles, and the average sphericity is greater than 0.85. The non-titanate filler being spherical or quasi-spherical particles is beneficial to better reducing the dielectric loss Df of the resin composition, reducing interface defects, and improving the mechanical properties of the resin composition.

[0027] In the embodiments of the present application, the D50 particle size of the non-titanate filler is 0.1 μm - 10 μm. The non-titanate filler having a suitable particle size is beneficial to its uniform dispersion in the resin composition, better exerting the performance advantages of the non-titanate filler, and improving the compactness, dielectric properties, and mechanical properties of the molded article obtained after the resin composition is molded.

[0028] In the embodiments of the present application, the mass percentage of the non-titanate filler is 20%-35%. The addition of an appropriate amount of non-titanate filler in the resin composition can better cooperate with the titanate filler, so that while improving the dielectric properties of the resin composition, the influence of temperature drift is reduced, and at the same time, the coefficient of thermal expansion of the resin composition is better reduced, enabling the resin composition to better have excellent dielectric properties and a low coefficient of thermal expansion.

[0029] In the embodiments of the present application, the resin composition further includes an additive, and the mass percentage of the additive is less than or equal to 2%. The additive can be added according to actual needs to improve the relevant properties of the resin composition.

[0030] In the embodiments of the present application, the additive includes one or more of an antioxidant, a flame retardant, and a lubricant. The antioxidant can improve the antioxidant performance of the resin composition, the flame retardant can improve the flame retardant performance of the resin composition, and the lubricant can improve the lubrication performance of the resin composition.

[0031] In the embodiments of the present application, the dielectric constant Dk of the resin composition is ≥4.5, and the dielectric loss Df at 10 GHz is 0.0004-0.001. Through the design of specific components in the embodiments of the present application, the resin composition has a high dielectric constant and an extremely low dielectric loss at 10 GHz high frequency. When this resin composition is applied to the preparation of communication components, it can effectively improve the signal transmission efficiency and reduce the loss, thereby better meeting the requirements of high-quality and high-efficiency signal transmission of communication components at high frequencies and the requirements for the miniaturization development of communication components. The dielectric constant and dielectric loss can be measured using a network analyzer with a 10 GHz fixture.

[0032] In the embodiments of the present application, the heat deflection temperature of the resin composition is ≥155°C. The heat deflection temperature (HDT) refers to the temperature at which the resin material deforms under an external force, and the heat deflection temperature is an important index for judging the heat resistance performance of the resin composition. The resin composition in the embodiments of the present application has a high heat deflection temperature, indicating its excellent heat resistance performance, and can better meet the requirements of high-temperature application scenarios and improve the reliability of the use of communication components. The heat deflection temperature can be measured using an HDT Vicat test instrument according to the standard ISO75-1 "Plastics - Determination of heat deflection temperature".

[0033] In the embodiments of the present application, the Izod notched impact strength of the resin composition is greater than 5 kJ / m 2The Izod impact strength of the cantilever beam reflects the ability of the material to resist impact. It can be tested using an Izod impact strength testing machine for plastics according to the standard ISO 180: "Determination of Izod impact strength of plastics".

[0034] In the second aspect of the embodiments of the present application, a preparation method of the resin composition described in the first aspect is provided, including:

[0035] Mix the components of the resin composition to obtain a mixture;

[0036] After melting the mixture, extrude and pelletize to obtain the resin composition.

[0037] The preparation method provided by the embodiments of the present application has a simple process and is conducive to mass production.

[0038] In the third aspect of the embodiments of the present application, a molded article is provided, including the molded article of the resin composition described in the first aspect. This molded article can be designed into various regular or irregular shapes and specific sizes according to actual application needs. The molded article is in a solid state. Specifically, the molded article can be obtained by injection molding, calendering molding, or extrusion molding.

[0039] In the fourth aspect of the embodiments of the present application, an electronic component is provided, and the electronic component includes the molded article of the resin composition described in the first aspect. This electronic component can be various electronic components with requirements for dielectric materials, such as communication components, capacitors, etc.

[0040] In the embodiments of the present application, the electronic component includes a communication component. Using the resin composition of the embodiments of the present application as the dielectric material in the communication component can effectively improve the signal transmission efficiency, and at the same time is conducive to improving the thermal stability and impact resistance performance, and enhancing the product reliability.

[0041] In the embodiments of the present application, the communication component includes an antenna, a microwave device, a radio frequency device, a metal strip line assembly, etc. The molded article of the resin composition can specifically be used as a dielectric substrate or a dielectric frame.

[0042] In some embodiments, the resin composition is used in a microwave device in an antenna. For example, it can be used in a phase modulation device of a microwave device. The microwave device can be a microwave modulator, a microwave amplifier, a microwave filter, a microwave switch, a microwave mixer, etc.

[0043] In some embodiments, the resin composition is used in a metal strip line assembly. For example, it can be used to form an isolation device between metal strip lines.

[0044] In some embodiments, the resin composition is used in radio frequency devices, such as radio frequency amplifiers, radio frequency switches, radio frequency filters, radio frequency mixers, radio frequency power amplifiers, combiners, phase shifters, etc.

[0045] An embodiment of the present application further provides a communication system, which includes communication components, and the communication components include a molded product of the resin composition described in the first aspect. The communication system using the above communication components has better signal transmission efficiency, better thermal stability and impact resistance. Description of the Drawings

[0046] Figure 1 It is a flowchart of the preparation method of the resin composition provided by the embodiment of the present application;

[0047] Figure 2 It is a schematic structural diagram of the electronic component 100 provided by the embodiment of the present application. Detailed Embodiments

[0048] The embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.

[0049] Currently, dielectric materials applied to the communication industry are difficult to have both high-frequency low loss, high heat distortion temperature and high impact resistance, which is not conducive to the high-frequency and miniaturization development of communication components such as antennas. In order to better meet the application requirements of communication components such as high-frequency and miniaturized components, an embodiment of the present application provides a resin composition, which has both a high dielectric constant, low dielectric loss, and relatively high heat resistance and impact resistance.

[0050] The resin composition provided by the embodiment of the present application includes the following components in mass percentages: 30%-60% of cycloolefin polymers, 3%-15% of olefin polymers and / or modified olefin polymers, and 35%-70% of fillers;

[0051] Among them, the filler includes titanate filler and non-titanate filler, the mass percentage of the titanate filler is 10%-40%, the mass percentage of the non-titanate filler is 0-40%, and the dielectric constant of the non-titanate filler is greater than 20.

[0052] The resin composition provided by the embodiment of the present application is obtained by compounding cycloolefin polymers with olefin polymers and / or modified olefin polymers, and specific types of fillers. It can have both a high dielectric constant, low dielectric loss, and relatively high heat resistance and impact resistance. Using it as a dielectric material in the communication field can improve signal transmission efficiency while meeting the requirements of mechanical properties and heat resistance, so as to better meet the application requirements of high-frequency communication and miniaturized communication components, and promote the high-frequency and miniaturization development of communication components such as antennas.

[0053] Cyclic olefin polymers have excellent dielectric properties, heat resistance, and processing and molding properties. When used as the main resin of dielectric materials in the communication field, they can enable the dielectric materials to better meet the application requirements of the communication field. Cyclic olefin polymers include two types: cyclic olefin copolymers (COC) and cyclic olefin homopolymers (COP). Among them, cyclic olefin copolymers (COC) are copolymerized from ethylene or α-olefins (monoolefins with double bonds at the ends of the molecular chain) and cyclic olefin monomers such as norbornene. Cyclic olefin homopolymers (COP) are homopolymerized from cyclic olefin monomers such as norbornene.

[0054] In the embodiments of the present application, in order to enable the resin composition to obtain higher heat resistance, in the resin composition, the heat distortion temperature of at least part of the cyclic olefin polymer is greater than or equal to 140 °C, that is, the heat distortion temperature of part or all of the cyclic olefin polymer is greater than or equal to 140 °C. Among them, at least part can be at least 50%, that is, the heat distortion temperature of at least 50% of the cyclic olefin polymer is greater than or equal to 140 °C. In some embodiments, at least part can specifically be, for example, 50%, 55%, 60%, 70%, 80%, 90%, 95%, 100%.

[0055] In some embodiments, in the resin composition, the heat distortion temperature of at least part of the cyclic olefin polymer is greater than or equal to 150 °C, that is, the heat distortion temperature of part or all of the cyclic olefin polymer is greater than or equal to 150 °C. Among them, at least part can be at least 50%, that is, the heat distortion temperature of at least 50% of the cyclic olefin polymer is greater than or equal to 150 °C. In some embodiments, at least part can specifically be, for example, 50%, 55%, 60%, 70%, 80%, 90%, 95%, 100%.

[0056] In some embodiments, in the resin composition, the heat distortion temperature of at least part of the cyclic olefin polymer is greater than or equal to 160 °C, that is, the heat distortion temperature of part or all of the cyclic olefin polymer is greater than or equal to 160 °C. Among them, at least part can be at least 10%, that is, the heat distortion temperature of at least 10% of the cyclic olefin polymer is greater than or equal to 160 °C. In some embodiments, at least part can specifically be, for example, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 70%, 80%, 90%, 95%, 100%.

[0057] In this application, a cycloolefin polymer with a specific heat distortion temperature can be selected according to actual application requirements. In the resin composition, there may be one cycloolefin polymer or multiple cycloolefin polymers. The cycloolefin polymers in the resin composition may have the same heat distortion temperature or different heat distortion temperatures. In some embodiments, the resin composition includes multiple cycloolefin polymers with different heat distortion temperatures.

[0058] In the embodiments of this application, at least part of the cycloolefin polymers are cycloolefin copolymers. The cycloolefin polymers in the resin composition may all be cycloolefin copolymer COC, or part of them may be cycloolefin copolymer COC and the other part may be cycloolefin homopolymer COP. The presence of the cycloolefin copolymer can better improve the heat resistance of the resin composition.

[0059] In the embodiments of this application, the mass percentage of the cycloolefin polymers in the resin composition is 30% - 60%. In some embodiments, the mass percentage of the cycloolefin polymers in the resin composition is 35% - 60%. In some examples, the mass percentage of the cycloolefin polymers in the resin composition is, for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%. Keeping the cycloolefin polymers in the resin composition at an appropriate amount is beneficial to ensuring the basic physical and chemical properties required for the resin composition to be used as a dielectric material, making it more conducive to being formed into the desired shape, applied to various scenarios, and at the same time being able to better achieve insulation and corrosion prevention.

[0060] The resin composition of the present application can effectively improve the toughness of the resin composition and enhance the ability of the resin composition to resist impact damage by adding a small amount of an olefin polymer as a modifier for the cycloolefin polymer. The olefin polymer is a polymer formed by polymerization of one or more olefins, and can be an olefin homopolymer, an olefin random copolymer, or an olefin block copolymer, which is an unmodified olefin polymer. Among them, the olefin homopolymer is a polymer formed by polymerization of one olefin monomer; the olefin random copolymer is a polymer formed by random copolymerization of two or more olefin monomers; the olefin block copolymer is a polymer obtained by block copolymerization of two or more olefin monomers, which has two or more different olefin monomer units and is combined in an orderly manner. Specifically, the olefin polymer can be, but is not limited to, a polymer formed by polymerization of one or more of olefin monomers such as ethylene, propylene, butene, isobutene, pentene, hexene, heptene, octene, nonene, butadiene, pentadiene, hexadiene, heptadiene, octadiene. Examples of the olefin homopolymer can be polyethylene, polypropylene, polybutene, polybutadiene, polyhexadiene. Examples of the olefin block copolymer can be propylene-butadiene block copolymer, ethylene-propylene block copolymer, ethylene-butadiene block copolymer, etc. In some embodiments of the present application, the olefin polymer includes an olefin block copolymer, and the block copolymerization method of the olefin block copolymer can better maintain the toughness of the material while ensuring high heat resistance.

[0061] The resin composition of the present application can improve the interfacial bonding force, improve the toughness of the resin composition to a certain extent, and effectively enhance the ability of the resin composition to resist impact damage by adding a small amount of a modified olefin polymer as a modifier for the cycloolefin polymer. The modified olefin polymer can be a modified product of the above-mentioned olefin polymer. In some embodiments, the modified olefin polymer includes a maleic anhydride-grafted olefin polymer.

[0062] In some embodiments, the resin composition contains only an olefin polymer and does not contain a modified olefin polymer; in some embodiments, the resin composition contains only a modified olefin polymer and does not contain an olefin polymer; in some embodiments, the resin composition contains both an olefin polymer and a modified olefin polymer. The main function of the olefin polymer is toughening, and the main function of the modified olefin polymer is to improve the interfacial bonding force, and the two have good compatibility. The simultaneous presence of these two polymers in the resin composition can better improve the mechanical properties of the resin composition.

[0063] In the embodiments of the present application, the mass percentage of the olefin polymer and / or modified olefin polymer in the resin composition is 3% - 15%. The addition of an appropriate amount of olefin polymer and / or modified olefin polymer can effectively improve the toughness of the resin composition, enhance the ability of the resin composition to resist impact damage, improve the interfacial bonding force between inorganic and organic fillers, and enable the resin composition to have sufficient cycloolefin polymers and fillers added, thus facilitating the guarantee of the heat resistance, dielectric properties and other mechanical properties of the resin composition. In some embodiments of the present application, the mass percentage of the olefin polymer and / or modified olefin polymer is 5% - 10%. In some examples of the present application, the mass percentage of the olefin polymer and / or modified olefin polymer is 3%, 4%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14%, 15%.

[0064] In some embodiments of the present application, the mass percentage of the olefin polymer in the resin composition is 5% - 15%. For example, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14%, 15%. The main function of the olefin polymer is to improve the toughness of the resin composition and enhance the impact resistance. Controlling it at a relatively high content is beneficial to better improving the impact resistance of the resin composition.

[0065] In some embodiments of the present application, the mass percentage of the modified olefin polymer in the resin composition is 1% - 5%. For example, 1%, 2%, 3%, 4%, 5%. The main function of the modified olefin polymer is to improve the interfacial bonding performance of the components. Controlling it at a relatively low content is beneficial to enhancing the interfacial bonding performance while ensuring the improvement of the impact resistance.

[0066] In some examples, the resin composition contains both an olefin polymer and a modified olefin polymer, and the mass percentage of the olefin polymer is greater than that of the modified olefin polymer.

[0067] In the embodiments of the present application, the melting temperature of the olefin polymer and / or modified olefin polymer is greater than 105°C. The melting temperature refers to the temperature required for the substance to change from the high elastic state to the viscous flow state. The olefin polymer and the modified olefin polymer have a relatively high melting temperature, which is beneficial for the olefin polymer and the modified olefin polymer to improve the toughness of the resin composition while enabling the resin composition to still maintain a relatively high heat resistance.

[0068] In the embodiments of the present application, the mass percentage of the filler in the resin composition is 35%-70%. The appropriate addition of the filler can improve the mechanical properties such as the strength and hardness of the resin composition, and can also improve the dielectric properties and heat resistance. In some embodiments, the mass percentage of the filler in the resin composition is 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%.

[0069] In the embodiments of the present application, the filler may include titanate fillers and non-titanate fillers. The mass percentage of the titanate fillers is 10%-40%, and the mass percentage of the non-titanate fillers is 0-40%. In some embodiments, the filler only includes titanate fillers and does not include non-titanate fillers; in some embodiments, the filler includes both titanate fillers and non-titanate fillers.

[0070] The titanate fillers have a relatively high dielectric constant. The inclusion of titanate fillers in the filler is more conducive to improving the dielectric properties and impact resistance of the resin composition. Considering the dielectric properties and the possible temperature drift effects caused by the titanate fillers, etc., in the embodiments of the present application, the mass percentage of the titanate fillers is controlled to be 10%-40%. In some embodiments, the mass percentage of the titanate fillers is controlled to be 15%-35%. In some embodiments, the mass percentage of the titanate fillers is controlled to be 15%-30%. In some embodiments, the mass percentage of the titanate fillers is 10%, 15%, 20%, 25%, 30%, 35%, 40%. In the present application, the temperature drift refers to the change in dielectric constant caused by temperature change.

[0071] In some embodiments of the present application, when the filler only includes titanate fillers, the mass percentage of the titanate fillers is controlled to be 35%-40%, such as 35%, 36%, 37%, 38%, 39%, 40%.

[0072] In the embodiments of the present application, the titanate fillers, i.e., the oxygen-containing acid salts of titanium, may be one or more of calcium titanate, calcium magnesium titanate, calcium strontium titanate, strontium barium titanate, barium titanate. These titanate fillers have a relatively high dielectric constant, can also improve the mechanical properties, and combine well with the resin components. Adding them to the resin composition is conducive to improving the dielectric properties and impact resistance of the resin composition.

[0073] In the embodiments of the present application, the titanate filler is spherical or quasi-spherical particles. The titanate filler being spherical or quasi-spherical particles is beneficial to better reducing the dielectric loss Df of the resin composition, reducing interfacial defects, improving the mechanical properties of the resin composition, increasing the melt index of the composition, and facilitating injection molding. The higher the sphericity, the more beneficial it is. In some embodiments, the average sphericity of the titanate filler is greater than 0.85. Among them, the sphericity is a parameter characterizing the particle morphology, which is the ratio of the surface area of a sphere with the same volume as the particle to the surface area of the particle. The closer the particle morphology is to a sphere, the closer its sphericity is to 1. In some embodiments of the present application, the average sphericity of the titanate filler can be, for example, 0.86, 0.87, 0.88, 0.9, 0.92, 0.93, 0.95, 0.96, 0.98, 0.99, 1.

[0074] In the embodiments of the present application, the D50 particle size of the titanate filler is 0.5 μm - 100 μm. D50 is the particle size corresponding to when the cumulative particle size distribution percentage of a sample reaches 50%, and D50 is also called the median diameter or median particle size. The titanate filler having a suitable particle size is beneficial for its uniform dispersion in the resin composition, better exerting the performance advantages of the titanate filler, and improving the compactness, dielectric properties, and mechanical properties of the molded article obtained after the resin composition is molded. In the embodiments of the present application, the D50 particle size of the titanate filler is 1 μm - 20 μm. In some embodiments, the D50 particle size of the titanate filler can be, for example, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 100 μm.

[0075] In the embodiments of the present application, the mass percentage of the non-titanate filler can be 0 - 40%. The addition of the non-titanate filler in the resin composition can act synergistically with the titanate filler, enabling the resin composition to improve dielectric properties while reducing the influence of temperature drift, and at the same time better reducing the thermal expansion coefficient of the resin composition, so that the resin composition can better possess excellent dielectric properties and low thermal expansion coefficient. In some embodiments of the present application, the mass percentage of the non-titanate filler is 10% - 30%. In some embodiments, the mass percentage of the non-titanate filler is 1%, 3%, 4%, 5%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%.

[0076] In some embodiments of the present application, the mass ratio of the titanate filler to the non-titanate filler is greater than or equal to 0.5:1. Controlling the mass ratio as above is beneficial to improving the dielectric properties of the resin composition and better ensuring the dimensional stability of the molded product of the resin composition. In some embodiments, the mass ratio of the titanate filler to the non-titanate filler is 0.5:1, 0.6:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1. In some embodiments, the mass ratio of the titanate filler to the non-titanate filler is greater than or equal to 1:1.

[0077] In the embodiments of the present application, the non-titanate filler includes metal or non-metal oxides, and the metal or non-metal oxides may include, but are not limited to, hafnium dioxide, titanium oxide, lead oxide, tantalum oxide, and the like. In some embodiments, the non-titanate filler includes one or more of hafnium dioxide, titanium oxide, lead oxide, and tantalum oxide. These metal oxides all have high dielectric constants and structural stabilities. Adding them in combination with the titanate filler to the resin composition can effectively improve the dielectric properties and dimensional stability of the resin composition.

[0078] In the embodiments of the present application, the dielectric constant of the non-titanate filler is greater than 20. Selecting a non-titanate filler with a relatively large dielectric constant is beneficial to improving the dielectric properties of the resin composition. In some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 30; in some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 40; in some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 50; in some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 55; in some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 60; in some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 70; in some embodiments, the dielectric constant of the non-titanate filler is greater than or equal to 80.

[0079] In the embodiments of the present application, the non-titanate filler is spherical or quasi-spherical particles. The non-titanate filler being spherical or quasi-spherical particles is beneficial to better reducing the dielectric loss Df of the resin composition, reducing interfacial defects, and improving the mechanical properties of the resin composition. In some embodiments, the average sphericity of the non-titanate filler is greater than 0.85. In some embodiments of the present application, the average sphericity of the non-titanate filler can be, for example, 0.86, 0.87, 0.88, 0.9, 0.92, 0.93, 0.95, 0.96, 0.98, 0.99, 1.

[0080] In the embodiments of the present application, the D50 particle size of the non-titanate filler is 0.1 μm - 10 μm. The non-titanate filler having a suitable particle size is beneficial to its uniform dispersion in the resin composition, better exerting the performance advantages of the non-titanate filler, and improving the compactness, dielectric properties, mechanical properties, etc. of the molded article obtained after the resin composition is molded. In some embodiments, the D50 particle size of the non-titanate filler can be, for example, 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm.

[0081] To improve certain properties of the resin composition, additives can also be added according to actual needs. In some embodiments of the present application, the resin composition further includes additives, and in the resin composition, the mass percentage of the additives is less than or equal to 2%. The additives can include one or more of antioxidants, flame retardants, and lubricants. Antioxidants can improve the antioxidant performance of the resin composition, flame retardants can improve the flame retardant performance of the resin composition, and lubricants can improve the lubrication performance of the resin composition.

[0082] In the embodiments of the present application, the dielectric constant Dk of the resin composition is ≥ 4.5, and the dielectric loss Df at 10 GHz is 0.0004 - 0.001. Through the design of specific components in the embodiments of the present application, the resin composition has a high dielectric constant and an extremely low dielectric loss at 10 GHz high frequency. When this resin composition is applied to the preparation of communication components, it can effectively improve the signal transmission efficiency and reduce the loss, thereby better meeting the requirements of high-quality and high-efficiency signal transmission at high frequency for communication components and the requirements for the miniaturization development of communication components. The higher the dielectric constant, the more beneficial it is for the miniaturized design of the antenna. In some embodiments, the dielectric constant Dk of the resin composition is, for example, 4.5, 4.6, 4.8, 5.0, 5.2, 5.5, 6.0, 6.2, 6.5, 7.0, 7.1. In some embodiments, the dielectric constant Dk of the resin composition is ≥ 5.0. In some embodiments, the dielectric loss Df of the resin composition at 10 GHz is 0.0004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001. In some embodiments, the dielectric loss Df of the resin composition at 10 GHz is 0.0004 - 0.0008. The dielectric constant and dielectric loss of the resin composition can be tested using a network analyzer with a 10 GHz fixture.

[0083] In the embodiments of the present application, the heat deflection temperature of the resin composition is ≥ 155 °C. The heat deflection temperature (HDT) refers to the temperature at which a resin material deforms under an external force. The heat deflection temperature is an important indicator for judging the heat resistance performance of the resin composition. The resin composition of the embodiments of the present application has a relatively high heat deflection temperature, indicating that it has excellent heat resistance performance and can better meet the requirements of high-temperature application scenarios, improving the reliability of communication components. In some embodiments, the heat deflection temperature of the resin composition is, for example, 155 °C, 160 °C, or 165 °C. The heat deflection temperature can be measured using an HDT Vicat test instrument according to the standard ISO 75-1 Plastics - Determination of heat deflection temperature.

[0084] In the embodiments of the present application, the Izod notched impact strength of the resin composition is greater than 5 kJ / m 2 . The Izod notched impact strength reflects the ability of a material to resist impact and can be measured using an Izod notched impact strength testing machine according to the standard ISO 180 Plastics - Determination of Izod impact strength. In some embodiments, the Izod notched impact strength of the resin composition is greater than or equal to 5.3 kJ / m 2 . In some embodiments, the Izod notched impact strength of the resin composition is greater than or equal to 6 kJ / m 2 . In some embodiments, the Izod notched impact strength of the resin composition is greater than or equal to 6.5 kJ / m 2 . In some embodiments, the Izod notched impact strength of the resin composition is greater than 7 kJ / m 2 .

[0085] The resin composition provided by the embodiments of the present application has both a high dielectric constant, low dielectric loss, as well as relatively high heat resistance and impact resistance. When used as a dielectric material in the communication field, it can improve the signal transmission efficiency while meeting the requirements of mechanical properties and heat resistance, thus being able to better meet the application requirements of high-frequency communication and miniaturized communication components, and promoting the high-frequency and miniaturized development of communication components such as antennas.

[0086] See Figure 1 , the embodiments of the present application also provide a preparation method for the above resin composition, including:

[0087] S101. Mix the components of the resin composition to obtain a mixed material;

[0088] There is no limitation on the way of mixing the cycloolefin polymer, the olefin polymer and / or the modified olefin polymer, and the filler. It can be directly mixed in an extrusion device, for example, mixed in a twin-screw extruder. Specifically, for example: after mixing the resin components, i.e., the cycloolefin polymer, the olefin polymer and / or the modified olefin polymer, add them to the main feeding system of the twin-screw extruder, add the filler to the side feeding system of the twin-screw extruder, and set the feeding flow rate according to the ratio of the resin components and the filler.

[0089] When the components of the resin composition further include additives, the additives can be added to the main feeding system of the twin-screw extruder together with the resin components.

[0090] S102. After melting the mixture obtained in step S101, extrude and pelletize to obtain the resin composition.

[0091] The melting temperature depends on the type of the resin components. During the extrusion and pelletizing process, the extrusion temperature of the twin-screw extruder can be 220°C - 290°C, for example, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C. The screw speed can be 400 rpm - 600 rpm, for example, 400 rpm, 500 rpm, 600 rpm. The screw length-diameter ratio can be 40:1. The resin composition obtained after pelletizing is resin composition particles.

[0092] The preparation method provided by the embodiments of the present application has a simple process and is conducive to mass production.

[0093] The embodiments of the present application further provide a molded article, which includes the molded article of the resin composition in the above embodiments of the present application. The molded article can be designed into various regular or irregular shapes and specific sizes according to actual application needs. The molded article is in a solid state. Specifically, the molded article can be obtained by injection molding, calendering molding, extrusion molding, etc.

[0094] See Figure 2 , the embodiments of the present application further provide an electronic component 100, which includes the molded article of the resin composition in the above embodiments of the present application. In some embodiments, the electronic component includes a functional layer 102 and insulating dielectric layers 101 disposed on opposite sides of the functional layer 102. The insulating dielectric layers 101 include the molded article of the resin composition in the above embodiments of the present application. The electronic component 100 can be various electronic components with application requirements for dielectric materials, such as communication components, capacitors, etc. It should be noted that Figure 2 only schematically shows the possible forms of the insulating dielectric layers 101 of the electronic component 100 to show the existence form of the molded article of the resin composition. This structural schematic diagram does not limit the specific structure of the electronic component 100.

[0095] In some embodiments, the electronic component 100 is a communication component, and the communication component may be various communication components including antennas, microwave devices, radio frequency devices, metal strip line assemblies, etc. that have application requirements for dielectric materials. The molded article of the resin composition may specifically be a dielectric substrate, a dielectric frame, or a dielectric layer. By using the resin composition of the embodiments of the present application as the dielectric material for this communication component, the signal transmission efficiency can be effectively improved, and at the same time, it is also beneficial to improve the thermal stability and impact resistance performance, thereby enhancing the product reliability.

[0096] In some embodiments, the resin composition is used in microwave devices in an antenna, for example, it may be used in a phase control device of a microwave device. These microwave devices may be microwave modulators, microwave amplifiers, microwave filters, microwave switches, microwave mixers, etc.

[0097] In some embodiments, the resin composition is used in radio frequency devices. The radio frequency devices may be, for example, radio frequency amplifiers, radio frequency switches, radio frequency filters, radio frequency mixers, radio frequency power amplifiers, combiners, phase shifters, etc.

[0098] In some embodiments, the resin composition is used in metal strip line assemblies in an antenna, for example, it may be used to form an isolation device between metal strip lines.

[0099] The embodiments of the present application further provide a communication system, which includes the communication component described above in the embodiments of the present application. The communication system using the above communication component has better signal transmission efficiency, better thermal stability and impact resistance performance.

[0100] The embodiments of the present application will be further described below in multiple embodiments.

[0101] Embodiments 1 to 7

[0102] The resin components cycloolefin polymers, olefin polymers, and / or modified olefin polymers, and additives are mixed and then added to the main feeding system of a twin-screw extruder. The filler is added to the side feeding system of the twin-screw extruder. After melting, it is extruded and pelletized to obtain resin composition particles. The ratios of the cycloolefin polymers, olefin polymers, and / or modified olefin polymers, fillers, and additives are shown in Table 1.

[0103] Comparative Examples 1 to 4

[0104] Resin composition particles are prepared using the same preparation method as in Example 1, and its formulation is shown in Table 1.

[0105] In Table 1, spherical or quasi-spherical calcium titanate, quasi-spherical titanium oxide, and silicon dioxide are all fillers.

[0106] The resin compositions and molded articles of Examples 1 to 7 and Comparative Examples 1 to 4 were tested for heat distortion temperature (HDT), Izod notched impact strength, dielectric constant, and dielectric loss. The test results are shown in Table 1.

[0107] Heat distortion temperature (HDT): Tested according to the standard ISO 75-1 "Plastics - Determination of heat distortion temperature", using an HDT Vicat test instrument.

[0108] Izod notched impact strength: Tested according to the standard ISO 180: "Plastics - Determination of Izod impact strength", using an Izod notched impact strength testing machine.

[0109] Dielectric constant and dielectric loss test: Tested using a network analyzer with a 10 GHz fixture.

[0110] Table 1

[0111]

[0112]

[0113] From the test results in Table 1, it can be seen that in Examples 1 to 7 of the present application, by compounding a cycloolefin polymer with a modifier olefin polymer and / or a modified olefin polymer, and a specific type of filler in a suitable ratio to obtain a resin composition, it can have both a high dielectric constant ≥ 4.5, a low dielectric loss ≤ 0.001, a relatively high heat distortion temperature ≥ 155 °C, and an Izod notched impact strength ≥ 5.0 kJ / m 2 .

[0114] The difference between Example 1 and Comparative Example 1 is that the modifier olefin block copolymer was not added in Comparative Example 1. From the results of Example 1 and Comparative Example 1, it can be seen that by compounding the modifier olefin polymer into the cycloolefin polymer system in Example 1, the Izod notched impact strength of the resin composition was significantly improved.

[0115] The difference between Example 1 and Comparative Example 2 is that the mass percentage of the modifier olefin block copolymer added in Comparative Example 2 was greater than 15%. From the results of Example 1 and Comparative Example 2, it can be seen that when using fillers with the same total mass percentage to ensure dielectric properties, the addition of too much modifier olefin block copolymer would cause the heat distortion temperature of the resin composition to not meet the high heat resistance requirements.

[0116] The difference between Example 2 and Comparative Example 3 is that in Comparative Example 3, the amount of calcium titanate filler added is too small, while the amount of titanium oxide filler added is too large. From the results of Example 2 and Comparative Example 3, it can be seen that for fillers with the same total mass ratio, adding too little calcium titanate filler and too much titanium oxide filler is not conducive to improving the dielectric properties and impact resistance. In Example 2, an appropriate amount of calcium titanate filler and titanium oxide filler are compounded, and the dielectric properties and impact resistance of the resin composition are significantly improved.

[0117] Comparing Example 1 and Comparative Example 4, it can be seen that in Example 1 of the present application, the titanium oxide filler with Dk>50 is compounded with the calcium titanate filler, and a relatively high dielectric constant can be obtained. In Comparative Example 4, the non-titanate filler added is silica with Dk<20 of the same mass, resulting in the Dk of the resin composition being much less than 4.5.

[0118] Comparing Example 4 and Example 5, it can be seen that for fillers with the same total mass ratio, a higher proportion of calcium titanate filler than titanium oxide filler is beneficial to improving the dielectric constant of the resin composition.

[0119] It should be understood that the first, second, and various numerical numbers involved herein are only for the convenience of description and are not used to limit the scope of the present application.

[0120] In the present application, "and / or" describes the association relationship of associated objects and indicates that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone, where A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after.

[0121] In the present application, "at least one" means one or more, and "a plurality" means two or more. "At least one of the following items (pieces)" or its similar expression refers to any combination of these items, including any combination of single items (pieces) or plural items (pieces). For example, "at least one of a, b, or c", or, "at least one of a, b, and c" can both represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.

[0122] In the present application, "-" represents a range value, including the endpoint values at both ends. For example, the value of a can be 0.5-15, indicating that the value of a can be between 0.5 and 15, and includes the endpoint values 0.5 and 15.

[0123] It should be understood that in various embodiments of the present application, the sequence numbers of the above processes do not imply the order of execution. Some or all of the steps may be executed in parallel or sequentially. The execution order of each process should be determined according to its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components in mass percentages: 30%-60% of a cycloolefin polymer, 3%-15% of an olefin polymer and / or a modified olefin polymer, and 35%-70% of a filler; Wherein, the filler comprises a titanate filler and a non-titanate filler, the mass percentage of the titanate filler is 10%-40%, the mass percentage of the non-titanate filler is 0-40%, and the dielectric constant of the non-titanate filler is greater than 20.

2. The resin composition according to claim 1, characterized in that, The heat distortion temperature of at least part of the cycloolefin polymer is greater than or equal to 140 °C.

3. The resin composition according to claim 1, wherein The heat distortion temperature of at least part of the cycloolefin polymer is greater than or equal to 150 °C.

4. The resin composition according to any one of claims 1 to 3, characterized in that, The heat distortion temperature of at least part of the cycloolefin polymer is greater than or equal to 160 °C.

5. The resin composition according to any one of claims 1 to 4, characterized in that, At least part of the cycloolefin polymer is a cycloolefin copolymer.

6. The resin composition according to any one of claims 1 to 5, characterized in that The mass percentage of the olefin polymer and / or the modified olefin polymer is 5%-10%.

7. The resin composition according to any one of claims 1 to 6, characterized in that, The melting temperature of the olefin polymer and / or the modified olefin polymer is greater than 105 °C.

8. The resin composition according to any one of claims 1 to 7, characterized in that The olefin polymer comprises an olefin block copolymer.

9. The resin composition according to any one of claims 1 to 8, characterized in that, The modified olefin polymer comprises a maleic anhydride-grafted olefin polymer.

10. The resin composition according to any one of claims 1 to 9, characterized in that, The mass ratio of the titanate filler to the non-titanate filler is greater than or equal to 0.5:

1.

11. The resin composition according to any one of claims 1 to 10, characterized in that, The titanate filler comprises one or more of calcium titanate, calcium magnesium titanate, calcium strontium titanate, strontium barium titanate, and barium titanate.

12. The resin composition according to any one of claims 1 to 11, characterized in that, The titanate filler is spherical or quasi-spherical particles, and the average sphericity is greater than 0.

85.

13. The resin composition according to any one of claims 1 to 12, characterized in that, The D50 particle size of the titanate filler is 0.5 μm-100 μm.

14. The resin composition according to any one of claims 1 to 13, characterized in that, The non-titanate filler comprises a metal or non-metal oxide, and the metal or non-metal oxide comprises titanium oxide.

15. The resin composition according to any one of claims 1 to 14, characterized in that, The dielectric constant of the non-titanate filler is greater than 50, the non-titanate filler is spherical or quasi-spherical particles, and the average sphericity is greater than 0.

85.

16. The resin composition according to any one of claims 1 to 15, characterized in that The D50 particle size of the non-titanate filler is 0.1 μm-10 μm.

17. The resin composition according to any one of claims 1 to 16, characterized in that The mass percentage of the non-titanate filler is 10%-30%.

18. The resin composition according to any one of claims 1 to 17, characterized in that, The resin composition further comprises an additive, and the mass percentage of the additive is less than or equal to 2%.

19. The resin composition according to claim 18, characterized in that, The additive comprises one or more of an antioxidant, a flame retardant, and a lubricant.

20. The resin composition according to any one of claims 1 to 19, characterized in that, The dielectric constant Dk of the resin composition is ≥4.5, and the dielectric loss Df at 10 GHz is 0.0004-0.

001.

21. The resin composition according to any one of claims 1 to 20, characterized in that, The heat distortion temperature of the resin composition is ≥155 °C.

22. The resin composition according to any one of claims 1 to 21, characterized in that, The notched Izod impact strength of the resin composition is greater than 5 kJ / m 2 .

23. The method for preparing the resin composition according to any one of claims 1-22, characterized in that, Comprising: Mixing the components of the resin composition to obtain a mixture; Melting the mixture and then extruding and pelletizing to obtain the resin composition.

24. A molded article, characterized in that, A molded article comprising the resin composition according to any one of claims 1-22.

25. An electronic component, characterized in that, The electronic component comprises a molded article of the resin composition according to any one of claims 1-22.

26. The electronic component according to claim 25, characterized in that, The electronic component comprises a communication component and a capacitor.

27. The electronic component according to claim 26, wherein, The communication component comprises an antenna, a microwave device, a radio frequency device, or a metal strip line assembly.

28. A communication system, characterized in that, The communication system comprises a communication component, and the communication component comprises a molded article of the resin composition according to any one of claims 1-22.

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