PCT/TLCP resin composition for 5G antenna oscillator substrate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of novel engineering plastics, and relates to a PCT/TLCP resin composition for a 5G antenna oscillator substrate, and a preparation method and application thereof.
Background
The antenna oscillator is a component and a functional part in the communication base station, has the main functions of guiding and amplifying electromagnetic waves, enables electromagnetic signals received by the antenna to be stronger, is an important component of the antenna, has larger consumption in the communication base station and the antenna, and has more complex general structural design. The traditional production and manufacturing process of the antenna oscillator adopts a metal material (aluminum alloy or zinc alloy) for die-casting molding, however, the antenna oscillator is often complex in structure, multiple in machining and molding procedures by adopting the metal material, high in difficulty and difficult to ensure in precision, so that the production cost of the product is high; and the metal material density is big, collects numerous antenna elements inside the antenna and makes the antenna quality big, brings inconvenience for installation, transportation, and high accuracy, low weight and low cost's plastic antenna element is expected to become market mainstream gradually.
The integrated plastic vibrator has the advantages of high precision, high integration, low weight, low cost and the like, but how to realize the antenna circuit on the common plastic substrate with high reliability is a core technical difficulty. The integrated plastic vibrator needs to take dielectric property, mechanical property, processing property and electroplating property of the material into consideration.
At present, the mass production of plastic oscillators in the antenna industry is conducted by an LDS (laser direct structuring) process, and the main process comprises the following steps: injection molding, laser radium carving, ultrasonic cleaning, quick copper, chemical copper, acid cleaning, chemical nickel, chemical gold and the like. However, the LDS process still has the defects, the LDS process adopts an LDS-TLCP material at present, the weight is larger, the material cost is high, the source of TLCP raw materials is less, the processing process requirement is high, and the equipment requirement is high; the LDS-TLCP material has very high requirements on the mold temperature, the charging barrel temperature, the injection pressure, the injection speed, the molding cycle and the like of the injection molding process, the yield is generally 85 percent, and the injection molding process has higher cost; all the coating surfaces need to be subjected to laser etching treatment by adopting an LDS process, and the laser etching cost is high; the coating requirement of the LDS process is high, the time of the integrated plating production process is long, the efficiency is low, and the process cost is high.
CN110655792A discloses a low-dielectric-constant laser direct-molding composite material suitable for 5G communication and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 52-86 parts of base resin (one or more of polyphenyl ether, polyimide, liquid crystal polymer and polyphenylene sulfide), 0-30 parts of glass fiber, 10-30 parts of filler, 1-9 parts of flame retardant, 4-15 parts of flexibilizer, 0.1-1 part of lubricant, 0.2-1 part of antioxidant and 10-30 parts of laser sensitive additive; the preparation method of the composite material comprises the following steps: processing by using a double-screw extruder, wherein the melt extrusion temperature is 250-380 ℃, and the screw rotating speed is 150-300 rpm/min; the composite material provided by the patent application has a low dielectric constant, but the base resin of the composite material adopts a few sources such as polyphenyl ether and liquid crystal polymer, the processing technology requirement is high, and the composite material adopts a laser direct forming technology, so that the production cost is high and the yield is low.
The intrinsic defects of the antenna oscillator formed by combining the LDS functional plastic and the metal material seriously obstruct the large-scale application market demand of the antenna oscillator in the age of 5G communication, and related markets and researchers quickly develop a second research and development direction and an integrated selective electroplating plastic antenna oscillator direction.
CN110982297A discloses a 5G low dielectric strength LCP composite material and a preparation method thereof, wherein the 5G low dielectric strength LCP composite material comprises the following components in parts by weight: 700 parts of LCP resin 650-; the preparation method comprises the following steps: s1, mixing main materials, S2, extruding a brace, and S3, cooling and granulating; the composite material provided by the patent application has lower dielectric constant and dielectric loss, but still has the defects of less sources, high price, low impact strength, obvious anisotropy, lower weld mark strength and the like of liquid crystal polymers and the like, and has the disadvantages of great damage to processing equipment, rough surface and difficult electroplating.
Therefore, it is necessary to develop a new resin composition for a substrate of a 5G antenna element to meet the application requirements.
Disclosure of Invention
The invention aims to provide a PCT/TLCP resin composition for a 5G antenna oscillator substrate and a preparation method and application thereof, the resin composition provided by the invention has excellent dielectric property, mechanical property and electroplating property, the formed product has high bonding strength with an electroplated layer, and the electroplated layer has good stability; meanwhile, the PCT/TLCP resin composition has extremely low hygroscopicity and creep property, good processability and high cost performance, and can meet the application requirements of a 5G antenna oscillator base material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a PCT/TLCP resin composition for a 5G antenna element substrate, which comprises the following components in parts by weight based on 100 parts of the total weight of the PCT/TLCP resin composition:
the TLCP resin in the resin composition provided by the invention has the reinforcing function of orienting the composition into microfibers in situ, so that the modulus and strength of the material can be improved; meanwhile, the TLCP resin has lower melt viscosity in a molten state, and is matched with the PCT resin and the compatible toughening agent for use, so that the compatibility, uniformity and stability of the resin composition are improved, and the processability of the resin composition is improved, and therefore, the TLCP resin is favorable for preparing devices with thin walls or larger molding areas and more complex product shapes; further, the combination of the TLCP resin, the PCT resin, the compatible toughening agent, and the other components can provide the resulting composition with good dimensional stability and creep resistance, as well as good chemical and dielectric properties.
The content of TLCP resin is less, so that the defects of low anisotropy and low welding strength of the TLCP pure resin modified material can be reduced, and the cost can be greatly reduced.
The PCT resin is polymerized by 1, 4-cyclohexanedimethanol (CHDM for short) and dimethyl terephthalate (DMT for short), and has a molecular structural formula as follows:
TLCP is a thermotropic liquid crystal polymer, and can be roughly classified into three types according to the degree of heat resistance, as shown in fig. 1: form I, form II and form III.
In the present invention, the PCT resin is 20 to 65 parts by weight, for example, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, and the like.
In the present invention, the TLCP resin is 5 to 30 parts by weight, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, etc.
In the present invention, the glass fiber is 20 to 60 parts by weight, for example, 30 parts by weight, 40 parts by weight, 50 parts by weight, 55 parts by weight, and the like.
In the present invention, the compatible toughening agent is 1 to 15 parts by weight, for example, 2 parts by weight, 5 parts by weight, 10 parts by weight, 12 parts by weight, and the like.
In the present invention, the other auxiliary is 0.5 to 7 parts by weight, for example, 1 part by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, or the like.
Preferably, the mass of the TLCP resin is 20-100%, such as 22%, 25%, 28%, 30%, 32%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, etc., of the mass of the PCT resin, more preferably 20-50%, still more preferably 20-35%.
In the present invention, when the mass of the TLCP resin is 20-35% of the mass of the PCT resin, the resulting composition has more excellent uniformity, stability, and weld strength, etc.
In the invention, the compatible toughening agent is selected from any one or a combination of at least two of MBS resin (methyl methacrylate-butadiene-styrene copolymer), ABS resin and high rubber powder thereof, ASA resin and high rubber powder thereof, styrene elastomer grafted maleic anhydride copolymer or thermoplastic polyester elastomer (TPEE), further preferably from any one or a combination of at least two of MBS resin, ABS resin and high rubber powder thereof or thermoplastic polyester elastomer, and further preferably from thermoplastic polyester elastomer (TPEE).
According to the invention, a thermoplastic polyester elastomer (TPEE) is preferably selected as a compatible toughening agent, the TPEE has higher similarity with the structures of PCT resin and TLCP, can be compatible with PCT and LCP at the same time, and has high impact strength at high and low temperatures and good chemical resistance.
Preferably, the amount of the compatible toughening agent added is less than 25% of the total mass of the TLCP resin and PCT resin, such as 20%, 18%, 16%, 15%, 14%, 12%, 10%, 5%, etc., and more preferably 10-20%.
The glass fiber can be long fiber or short glass fiber which is continuously wound, the cross section of the fiber is round, flat, rhombic and the like, and the glass fiber also comprises a compound of round glass fiber and special-shaped glass fiber.
Preferably, the glass fibers have an average diameter of 4 to 15 μm, such as 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, etc., preferably 6 to 11 μm, such as 7 μm, 9 μm, etc.
Preferably, the glass fibers comprise round cross-section glass fibers and/or shaped glass fibers.
Preferably, the profiled glass fiber is a glass fiber with an oval, cocoon or quadrilateral cross section, and the aspect ratio of the cross section of the profiled glass fiber is preferably 1 (2-4), such as 1:2.5, 1:3, 1:3.5 and the like.
Preferably, the glass fiber is preferably a round section glass fiber with a diameter of 7-11 μm (e.g. 8 μm, 9 μm, 10 μm, etc.) and/or a profiled glass fiber with a cross-section aspect ratio of 1 (2-4).
When the invention applies the round section glass fiber with the diameter of 7-11 μm and/or the profiled glass fiber with the cross section short length-diameter ratio of 1 (2-4), the finally obtained resin composition has more excellent rigidity and high and low temperature impact toughness.
In the invention, the PCT resin is semi-crystalline PCT resin with the intrinsic viscosity of 0.65-0.80dL/g, such as 0.66dL/g, 0.68dL/g, 0.70dL/g, 0.72dL/g, 0.75dL/g, 0.78dL/g and the like, and the melting point of 280-300 ℃, such as 285 ℃, 290 ℃, 295 ℃ and the like; more preferably, the intrinsic viscosity is 0.65 to 0.75dL/g, and still more preferably, the melting point is 285 ℃ to 297 ℃.
The preferable PCT resin of the invention can lead the finally obtained resin composition to have better mechanical property and can improve the high-low temperature toughness of the resin composition.
Preferably, the melting point of the TLCP resin is 280-350 ℃, such as 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ and the like.
Preferably, the other auxiliaries include dispersants, nucleating agents and antioxidants.
Preferably, the other auxiliary agents comprise the following components in parts by weight based on 100 parts of the total weight of the resin composition:
0.1-3 parts of a dispersant;
0.1-2 parts of nucleating agent;
0.3 to 2 weight portions of antioxidant.
In the present invention, the dispersant is 0.1 to 3 parts by weight, for example, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, and the like.
In the present invention, the nucleating agent is 0.1 to 2 parts by weight, for example, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.5 parts by weight, 1.8 parts by weight, and the like.
In the present invention, the antioxidant is used in an amount of 0.3 to 2 parts by weight, for example, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.5 parts by weight, 1.8 parts by weight, etc.
Preferably, the dispersant comprises any one or a combination of at least two of silicone, ionomer, hyperbranched polymer or macrocyclic oligoester (CBT), further preferably silicone and/or hyperbranched polymer.
The hyperbranched polymer can be selected from Hyper 100, Hyper181, CYD701 series, CYD816, CYD818 and the like.
Preferably, the nucleating agent is selected from any one of or a combination of at least two of a linear saturated carboxylic acid sodium salt, talc or a vinyl ionomer such as Honeywell's Aclyn series, Dupont's surlyn series.
Preferably, the antioxidant is selected from a composition of hindered phenol and phosphite ester, further preferably a composition of hindered phenol and phosphite ester in a mass ratio of 2: 1-1: 4, wherein the 2: 1-1: 4 can be 1:1, 1:2, 1:3 and the like.
Preferably, the hindered phenol is selected from any one or a combination of at least two of polyhydric hindered phenolic antioxidants, thio-hindered phenolic antioxidants or asymmetric hindered phenolic antioxidants, such as BASF corporation 1010, 245, 1098, CA, and the like; CYTEC, 3114, 3125, 1790, 330, etc.; GA-80, BBMC, AO-80 series of SUMITOMO/ADK, etc.
The phosphites include, but are not limited to 168, 618, 619, P-EPQ, 626, 627, PEP 36, 9228, and the like.
In a second aspect, the invention provides a preparation method of the PCT/TLCP resin composition for the 5G antenna element substrate according to the first aspect, wherein the preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with other auxiliary agents;
(2) and (2) melting, extruding and granulating the mixture obtained in the step (1) and glass fibers to obtain the PCT/TLCP resin composition for the 5G antenna oscillator substrate.
Preferably, the melt extrusion is carried out in a twin screw extruder.
Preferably, the glass fibers are added at a 5-7 stage (e.g., 6 stage, etc.) side feed port of the twin screw extruder.
Preferably, the operating parameters of the twin-screw extruder are: a first region 180-, 270 ℃, 280 ℃, etc.) and a head temperature of 270 ℃ and 290 ℃ (e.g., 275 ℃, 280 ℃, 285 ℃, etc.).
In a third aspect, the invention provides an application of the PCT/TLCP resin composition for the 5G antenna element substrate according to the first aspect as the 5G antenna element substrate.
Compared with the prior art, the invention has the following beneficial effects:
the resin composition provided by the invention can enable the finally obtained composition to have a lower dielectric constant and higher dielectric strength through the matching of TLCP resin, PCT resin, a compatible toughening agent and other components, and has higher electroplating performance and electroplating layer stability, so that the resin composition can meet the application requirements of 5G antenna oscillator substrates, and the performances are as follows:
(1) the rigidity and toughness are balanced in a wider temperature range. The normal temperature impact strength is 8.2KJ/m2Above, low temperature impact strength of 8.1KJ/m2The flexural modulus is 7890MPa or more.
(2) Excellent dielectric properties. The resin composition of the present invention has a dielectric constant of 3.6(1GHz) or less and a dielectric strength of 32kV/mm or more. The lower dielectric constant and the higher dielectric strength enable the signal transmission speed to be faster and the signal loss degree to be smaller in the 5G electromagnetic field.
(3) Excellent electroplating performance and electroplating layer stability. The stability of the electroplated layer of the resin composition provided by the invention can reach 1-2 levels. The integrated antenna oscillator transmits and receives electromagnetic wave signals by forming an electroplating circuit on the surface of the resin base material, and has good electroplating performance and higher stability of an electroplating layer, which is important for the application performance of the antenna oscillator.
Drawings
FIG. 1 is a classification diagram of TLCP resin of the present invention.
FIG. 2 is a flow chart of a preparation process of the PCT-TLCP resin composition for the 5G antenna element substrate.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A PCT/TLCP resin composition for a 5G antenna element substrate comprises the following components in parts by weight based on 100 parts of the total resin composition:
wherein the PCT resin has the intrinsic viscosity of 0.75dL/g and the melting point of 282 +/-2 ℃; the melting point of the TLCP resin is 330-340 ℃ (T3300, Nantong Haidi); the glass fiber is a glass fiber with a circular section (the diameter is 9 μm); the compatible toughening agents are G1652(SEBS) and 1901GT (SEBS-G-MAH) in a mass ratio of 1: 1; the dispersing agent is silicone powder; the nucleating agent is Nav 101; the antioxidant is 1010 and 619 (mass ratio is 2: 3).
The preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with a dispersing agent, a nucleating agent and an antioxidant;
(2) carrying out melt extrusion and granulation on the mixture obtained in the step (1) and glass fibers in a double-screw extruder to obtain a PCT/TLCP resin composition for the 5G antenna oscillator substrate;
wherein, the glass fiber is added into a feeding port at 7 sections of the double-screw extruder;
wherein, the working parameters of the double-screw extruder are as follows: one interval is 200 deg.C, two intervals is 260 deg.C, three intervals is 260 deg.C, four intervals is 260 deg.C, five intervals is 260 deg.C, six intervals is 260 deg.C, seven intervals is 260 deg.C, eight intervals is 270 deg.C, nine intervals is 270 deg.C and head temperature is 280 deg.C.
Example 2
A PCT/TLCP resin composition for a 5G antenna element substrate comprises the following components in parts by weight based on 100 parts of the total resin composition:
wherein the PCT resin has the intrinsic viscosity of 0.75dL/g and the melting point of 285 +/-2 ℃; the melting point of the TLCP resin is 330-340 ℃ (T3300, Nantong Haidi); the glass fiber is a glass fiber with a circular section (the diameter is 11 μm); the compatible toughening agent is KH-R172(TPEE) and G1702(SEBS) in a mass ratio of 4: 3; the dispersant is Hyper 100; the nucleating agent is Nav 101; the antioxidant is 1010 and 619 (mass ratio is 2: 3).
The preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with a dispersing agent, a nucleating agent and an antioxidant;
(2) carrying out melt extrusion and granulation on the mixture obtained in the step (1) and glass fibers in a double-screw extruder to obtain a PCT/TLCP resin composition for the 5G antenna oscillator substrate;
wherein, the glass fiber is added into a feeding port at the side of 6 sections of the double-screw extruder;
wherein, the working parameters of the double-screw extruder are as follows: one zone at 180 deg.C, two zones at 240 deg.C, three zones at 240 deg.C, four zones at 240 deg.C, five zones at 240 deg.C, six zones at 240 deg.C, seven zones at 240 deg.C, eight zones at 245 deg.C, nine zones at 245 deg.C, and head temperature at 270 deg.C.
Example 3
A PCT/TLCP resin composition for a 5G antenna element substrate comprises the following components in parts by weight based on 100 parts of the total resin composition:
wherein the PCT resin has the intrinsic viscosity of 0.75dL/g and the melting point of 285 +/-2 ℃; the melting point of the TLCP resin is 330-340 ℃ (T3300, Nantong Haidi); the glass fiber is flat glass fiber ECS301 HFPA; the compatible toughening agent is E920(MBS) and KH-R163(TPEE), and the mass ratio is 1: 1; the dispersant is CBT 100100; the nucleating agent is Nav 101; the antioxidant is 1010 and 619 (mass ratio is 2: 3).
The preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with a dispersing agent, a nucleating agent and an antioxidant;
(2) carrying out melt extrusion and granulation on the mixture obtained in the step (1) and glass fibers in a double-screw extruder to obtain a PCT/TLCP resin composition for the 5G antenna oscillator substrate;
wherein, the glass fiber is added into a feeding port at the 5-section side of the double-screw extruder;
wherein, the working parameters of the double-screw extruder are as follows: one interval of 220 deg.C, two intervals of 310 deg.C, three intervals of 310 deg.C, four intervals of 310 deg.C, five intervals of 310 deg.C, six intervals of 310 deg.C, seven intervals of 290 deg.C, eight intervals of 290 deg.C, nine intervals of 290 deg.C and head temperature of 290 deg.C.
Example 4
A PCT/TLCP resin composition for a 5G antenna element substrate comprises the following components in parts by weight based on 100 parts of the total resin composition:
wherein the PCT resin has the characteristic viscosity number of 0.65dL/g and the melting point of 288 +/-2 ℃; the melting point of the TLCP resin is 330-340 ℃ (T3300, Nantong Haidi); the glass fiber is round section glass fiber (diameter is 11 μm) and flat glass fiber TFG-3.0-T4355, the mass ratio of the two is 3: 1; the compatible toughening agent is GP33(BASF) and KH-R182(TPEE) in a mass ratio of 4: 3; the dispersant is ionomer Aclyn 295A; the nucleating agent is Nav 101; the antioxidant is 1010 and 619 (mass ratio is 2: 3).
The preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with a dispersing agent, a nucleating agent and an antioxidant;
(2) carrying out melt extrusion and granulation on the mixture obtained in the step (1) and glass fibers in a double-screw extruder to obtain a PCT/TLCP resin composition for the 5G antenna oscillator substrate;
wherein, the glass fiber is added into a feeding port at the side of 6 sections of the double-screw extruder;
wherein, the working parameters of the double-screw extruder are as follows: one zone at 180 deg.C, two zones at 255 deg.C, three zones at 255 deg.C, four zones at 255 deg.C, five zones at 255 deg.C, six zones at 260 deg.C, seven zones at 260 deg.C, eight zones at 270 deg.C, nine zones at 270 deg.C, and head temperature at 290 deg.C.
Example 5
The difference from example 2 is that in this example, the compatible toughening agent is 7 parts by weight of KH-R172 (TPEE).
Example 6
The difference from example 2 is that in this example, the glass fiber is a circular cross-section glass fiber having a diameter of 13 μm.
Example 7
The difference from example 3 is that in this example, the glass fiber is a flat glass fiber TFG-3.0-T436 (cross-sectional aspect ratio of short to long is about 1: 6).
Example 8
The difference from example 1 is that in this example, the amount of the TLCP resin was 14.7 parts by weight and the amount of the PCT resin was 50 parts by weight, while the total amount of the TLCP resin and the PCT resin was kept constant.
Example 9
The difference from example 1 is that in this example, the total addition amount of the TLCP resin, the PCT resin and the compatible toughening agent is 9 parts by weight, and the total addition amount of the TLCP resin and the PCT resin is 59.7 parts by weight, and then the proportions are as in example 1.
Example 10
A PCT/TLCP resin composition for a 5G antenna element substrate comprises the following components in parts by weight based on 100 parts of the total resin composition:
wherein the PCT resin has the intrinsic viscosity of 0.75dL/g and the melting point of 285 +/-2 ℃; the melting point of the TLCP resin is 330-340 ℃ (T3300, Nantong Haidi); the glass fiber is flat glass fiber ECS301 HFPA; the compatible toughening agent is KH-R172 (TPEE); the dispersant is CBT 100100; the nucleating agent is 8000 meshes of talcum powder; the antioxidant is 1010 and 619 (mass ratio is 2: 3).
The preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with a dispersing agent, a nucleating agent and an antioxidant;
(2) carrying out melt extrusion and granulation on the mixture obtained in the step (1) and glass fibers in a double-screw extruder to obtain a PCT/TLCP resin composition for the 5G antenna oscillator substrate;
wherein, the glass fiber is added into a feeding port at the side of 6 sections of the double-screw extruder;
wherein, the working parameters of the double-screw extruder are as follows: one interval of 220 deg.C, two intervals of 310 deg.C, three intervals of 310 deg.C, four intervals of 310 deg.C, five intervals of 310 deg.C, six intervals of 310 deg.C, seven intervals of 290 deg.C, eight intervals of 290 deg.C, nine intervals of 290 deg.C and head temperature of 290 deg.C.
Example 11
A PCT/TLCP resin composition for a 5G antenna element substrate comprises the following components in parts by weight based on 100 parts of the total resin composition:
wherein the PCT resin has the characteristic viscosity number of 0.65dL/g and the melting point of 288 +/-2 ℃; the melting point of the TLCP resin is 330-340 ℃ (T3300, Nantong Haidi); the glass fiber is flat glass fiber TFG-3.0-T4355; the compatible toughening agent is KH-R172 (TPEE); the dispersant is ionomer Aclyn 295A; the nucleating agent is Nav 101; the antioxidant is phosphite 619.
The preparation method comprises the following steps:
(1) mixing the PCT resin, the TLCP resin and the compatible toughening agent, and then premixing with a dispersing agent, a nucleating agent and an antioxidant;
(2) carrying out melt extrusion and granulation on the mixture obtained in the step (1) and glass fibers in a double-screw extruder to obtain a PCT/TLCP resin composition for the 5G antenna oscillator substrate;
wherein, the glass fiber is added into a feeding port at the 5-section side of the double-screw extruder;
wherein, the working parameters of the double-screw extruder are as follows: one zone at 180 deg.C, two zones at 255 deg.C, three zones at 255 deg.C, four zones at 255 deg.C, five zones at 255 deg.C, six zones at 260 deg.C, seven zones at 260 deg.C, eight zones at 270 deg.C, nine zones at 270 deg.C, and head temperature at 290 deg.C.
Comparative example 1
The difference from example 1 is that the comparative example does not include the TLCP resin, and the corresponding increase is in parts by weight of the PCT resin.
Comparative example 2
The difference from example 4 is that no TLCP resin was added in this comparative example.
Comparative example 3
The difference from example 1 is that the weight part of the TLCP resin in this comparative example is 40 weight parts, and the corresponding adjusted PCT resin is 24.7 weight parts.
Comparative example 4
The difference from example 1 is that in this comparative example the compatible toughening agent was replaced with toughening agent Elvaloy AC1125 (ethylene-acrylate copolymer).
Performance testing
The resin compositions provided in examples 1 to 11 and comparative examples 1 to 4 were subjected to a performance test by the following method:
(1) dielectric constant: the dielectric constant of the prepared samples was tested using a united states Keysight network analyzer (E5063A) -japan AET coaxial resonant cavity combination apparatus. Taking not less than 5 points of each sample plate under each test condition, and removing residual data of the obvious abnormal data to obtain an average value;
(2) dielectric strength: referring to standard IEC60249-1-2013, taking not less than 5 points of each sample plate under each test condition, and removing the residual average values of the obvious abnormal data;
(3) tensile strength: testing with reference to the test standards provided by ISO 527.1-2012;
(4) impact strength: the test is carried out according to the test standard provided by ISO 180-2013;
(5) flexural modulus: testing is carried out according to the test standard provided by ISO 178-2010;
(6) vicat softening point: the test is carried out according to the test standard provided by ISO 306 and 2013;
(7) stability of an electroplated layer: carrying out a Baige experiment according to the standard GBT9286-1998, taking points of not less than 5 tests under each test condition of each sample plate, recording the minimum value and the maximum value, wherein the higher the number is, the lower the adhesion force of the electroplated layer and the base material is;
(8) low-temperature impact strength: the test is carried out according to the test standard provided by ISO 180-;
the test properties are shown in tables 1-2:
TABLE 1
TABLE 2
The PC provided by the inventionThe T/TLCP resin composition has excellent high temperature resistance and electrical performance, and simultaneously has lower hygroscopicity and creep performance; the PCT/TLCP resin composition provided by the invention has good processability and durability, and simultaneously gives consideration to dielectric property, mechanical property, electroplating property and electroplating stability. Wherein the resin composition has a dielectric constant of less than 3.6(1GHz), a dielectric strength of more than 32kV/mm, a plating layer stability of 1-2 grade, a flexural modulus of more than 7890MPa, a tensile strength of more than 116MPa, and a normal-temperature impact strength of 8.2KJ/m2Above, low temperature impact strength of 8.1KJ/m2The above can be used for the 5G antenna element substrate.
As can be seen from the comparison between example 2 and example 5, the compatible toughening agent of the present invention, preferably the thermoplastic polyester elastomer, can make the resulting resin composition have more excellent dimensional stability, chemical resistance, high and low temperature impact toughness, etc.; as is clear from the comparison between examples 2 and 3 and examples 6 to 7, the glass fiber of the present invention is preferably a round-section glass fiber having a diameter of 7 to 11 μm and/or a shaped glass fiber having a cross-sectional aspect ratio of 1 (2 to 4); as can be seen from the comparison of example 1 and example 8, the TLCP resin of the present invention has a better effect when the mass is 20-35% of the mass of the PCT resin; as can be seen from the comparison between example 1 and example 9, the compatible toughening agent of the present invention is added in an amount of 10 to 20% by mass based on the total mass of the TLCP resin and the PCT resin, and the effect is better.
As can be seen from examples 1 and 4 and comparative examples 1 to 3, the addition of the TLCP resin and the selection of the addition amount of the TLCP resin in the invention need to be within the limited range of the invention, and if the addition amount of the TLCP is too large, the processing temperature is high, the equipment requirement is high, so that the TLCP resin is difficult to be directly applied to general extrusion equipment; as can be seen from the comparison between example 1 and comparative example 4, the selection of the compatible toughening agent in the present invention is required to be within the range defined in the present invention so that the resulting resin composition has superior overall properties.
The applicant states that the PCT/TLCP resin composition for a 5G antenna element substrate and the preparation method and application thereof are described in the above embodiments, but the invention is not limited to the above process steps, i.e. the invention is not meant to be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.