CN115948059A - LCP-based LDS material and component and preparation method thereof - Google Patents
LCP-based LDS material and component and preparation method thereof Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application relates to an LCP-based LDS material, a component and a preparation method thereof, belonging to the technical field of high polymer materials, wherein the material comprises the following components: LCP and whiskers; the whiskers comprise poly (butyl acrylate-styrene) whiskers and/or poly (4-hydroxy benzyl ester) whiskers; the whiskers are introduced into the material, so that the strength modulus of the whiskers is high, the shrinkage rate of the whiskers is small, and the characteristics of small diameter and large length-diameter ratio of the whiskers are utilized, so that the shrinkage of the material in different directions can be improved, the transverse shrinkage rate of the material is reduced, the difference between the transverse shrinkage rate and the longitudinal shrinkage rate is reduced, and the precision of a subsequently prepared component can be improved.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to an LCP-based LDS material, an LCP-based LDS component and a preparation method of the LCP-based LDS material.
Background
The laser direct structuring technique is a technique of compounding a metal wiring and a polymer material together by laser. The Liquid Crystal Polymer (LCP) based LDS material is LCP blending modified material. The material is a functional LCP modified material containing metal compounds, and metal conducting circuits can be constructed on the surface of an LCP injection molding part through laser activation and chemical plating processes. The manufacturing process of the LDS functional material product comprises the following steps: (1) designing and preparing a functional material formula; (2) injection molding; (3) laser activation; (4) selective metallization; and (5) spraying and assembling.
The engineering resin base materials of the LDS functional materials commonly used at present comprise: polycarbonate, polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polyimide, liquid crystal polymer, and the like. The LDS functional auxiliary agents which are commonly used are mainly metal organic compounds and inorganic substances, such as basic copper phosphate, tin phosphate, cuprous oxide, antimony oxide and the like. For example, chinese patent application CN110655792a discloses a low dielectric laser direct molding composite material suitable for 5G communication, which comprises the following components: 52-86 parts of base resin, 0-30 parts of glass fiber, 10-30 parts of filler, 1-9 parts of flame retardant, 4-15 parts of toughening agent, 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 rotation speed is 150-300rpm/min. The composite material has low dielectric property and LDS processing capability. In the Chinese invention patent application CN110872436A, the bio-based nylon is modified by introducing the liquid crystal polymer, and the laser direct forming additive is added to obtain the bio-based laser direct forming material which has good strength and toughness and LDS functionality.
The liquid crystal polymer has wide application in the field of 5G communication by virtue of the advantages of low dielectric, low loss, excellent insulating property and the like. Therefore, LCP-based LDS materials are also a focus of research. However, in the injection molding process of the LCP, since the difference between the shrinkage rates in the flow direction and the vertical direction is large, the larger the shrinkage rate of the material is, the lower the dimensional accuracy of the product is. This will have a certain impact on the accuracy of the metallized product behind the LCP based LDS material article. Therefore, it is very important to improve the difference in shrinkage of LCP-based LDS materials.
Disclosure of Invention
The application provides an LCP-based LDS material, an LCP-based LDS component and a preparation method of the LCP-based LDS material and the component, and aims to solve the problem of difference of transverse and longitudinal shrinkage rates of the material.
In a first aspect, the present application provides an LCP-based LDS material, the material comprising: LCP and whiskers; the whiskers include poly (butyl acrylate-styrene) whiskers and/or poly (4-hydroxybenzyl ester) whiskers.
As an alternative embodiment, the composition of the material further comprises: the modified talcum powder is prepared by modifying talcum powder through a silane coupling agent.
As an alternative embodiment, the modified talc powder is in a flake and/or powder form; the particle size of the modified talcum powder is 2000-5000 meshes.
As an alternative embodiment, the material comprises the following components in parts by mass:
60-75 parts of LCP, 5-10 parts of POE-g-MAH, 10-25 parts of crystal whisker, 5-15 parts of modified talcum powder, 10-15 parts of a mixture of basic copper phosphate and copper chromite, 0.1-0.5 part of pentaerythritol stearate, 0.1-0.5 part of antioxidant and 0.5-1 part of ultraviolet absorbent.
As an alternative embodiment, the material comprises the following components in parts by mass:
65-70 parts of LCP, 7-8 parts of POE-g-MAH, 15-20 parts of crystal whisker, 8-12 parts of modified talcum powder, 12-13 parts of a mixture of basic copper phosphate and copper chromite, 0.2-0.4 part of pentaerythritol stearate, 0.2-0.4 part of antioxidant and 0.7-0.8 part of ultraviolet absorbent.
As an alternative embodiment, in the mixture of basic copper phosphate and copper chromite, the mass ratio of basic copper phosphate to copper chromite is 1:1-3:1.
in a second aspect, the present application provides a method for preparing an LCP-based LDS material, the method comprising:
mixing the components of the material provided by the first aspect to obtain a mixture;
and granulating the mixture to obtain the LCP-based LDS material.
In a third aspect, the present application provides a member prepared from the LCP-based LDS material provided in the first aspect.
In a fourth aspect, the present application provides a method for producing a member provided in the third aspect, the method comprising:
obtaining the LCP-based LDS material provided by the first aspect;
and carrying out injection molding and proofing on the material to obtain the component.
As an alternative embodiment, the temperature of the nozzle of the injection molding and proofing cylinder is 320-340 ℃; and/or
The temperature of the front section of the charging barrel for injection molding and proofing is 320-340 ℃; and/or
The interrupted temperature of the charging barrel for injection molding and proofing is 310-320 ℃; and/or
The temperature of the rear section of the charging barrel for injection molding and proofing is 300-310 ℃.
As an alternative embodiment, the temperature of the injection molding proofing mold is 100-150 ℃; and/or
The injection molding pressure of the injection molding proofing is 80-100Mpa; and/or
The pressure maintaining pressure of the injection molding proofing is 20-40Mpa; and/or
The back pressure of the injection molding proofing is 3-5Mpa; and/or
The rotating speed of the screw for injection molding and proofing is 50-100rpm/min.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the applicant finds that the transverse shrinkage rate is larger than the longitudinal shrinkage rate in the injection molding process, and by adopting the material provided by the embodiment of the application, the whisker is introduced into the material, so that the whisker has high strength modulus and small shrinkage rate, and the whisker is introduced into the material to improve the shrinkage of the material in different directions by utilizing the characteristics of small diameter and large length-diameter ratio, so that the transverse shrinkage rate of the material is reduced, the difference between the transverse shrinkage rate and the longitudinal shrinkage rate is further reduced, and the precision of a subsequently prepared component can be improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive labor.
Fig. 1 is a flowchart of a method provided in an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present application are either commercially available or can be prepared by existing methods.
The applicant finds in the course of the invention that: in the injection molding process of LCP, the larger the shrinkage rate of the material is, the larger the shrinkage rate difference between the flow direction and the vertical direction is, and the dimensional accuracy of the product is reduced. This will have a certain impact on the accuracy of the metallized product behind the LCP based LDS material article.
To this end, the applicant intends to solve two aspects, 1, starting from the material formulation: the transverse shrinkage rate of the LCP-based LDS material is reduced to a certain extent by introducing proper organic crystal whiskers and modified talcum powder. 2. Starting from an injection molding process: the temperature of the die is properly reduced, the injection pressure is improved, the injection temperature is reduced, and the proper pressure maintaining pressure, back pressure and screw rotating speed are matched, so that the transverse shrinkage rate of the material can be further reduced, and the difference between the transverse shrinkage rate and the longitudinal shrinkage rate of the material is reduced.
As shown in fig. 1, the present application provides an LCP-based LDS material, which comprises the following components: LCP and whiskers; the whiskers include poly (butyl acrylate-styrene) whiskers and/or poly (4-hydroxybenzene methyl ester) whiskers.
By adopting the design, the whiskers are introduced into the material, so that the strength modulus of the whiskers is high, the shrinkage rate is small, and the characteristics of small diameter and large length-diameter ratio of the whiskers are utilized, so that the shrinkage of the material in different directions can be improved, the transverse shrinkage rate of the material is reduced, and the difference between the transverse shrinkage rate and the longitudinal shrinkage rate is further reduced.
In some embodiments, the composition of the material further comprises: the modified talcum powder is prepared by modifying talcum powder through a silane coupling agent. Specifically, the modified talcum powder is obtained by performing ultrasonic treatment on 15-30 mass parts of KH550 silane coupling agent aqueous solution for 30min.
The talcum powder can reduce the crystallinity of the LCP polymer, and further achieve the purpose of reducing the shrinkage rate.
In some embodiments, the talc powder is in the form of flakes and powder, and the modified talc powder is in the form of flakes and powder, wherein the modified talc powder has a particle size of 2000-5000 mesh, and specifically, the powder has a particle size of 2000 mesh, 3000 mesh, or 5000 mesh.
In some embodiments, the composition of the material comprises, in parts by mass: 60-75 parts of LCP, 5-10 parts of POE-g-MAH, 10-25 parts of whiskers, 5-15 parts of modified talcum powder, 10-15 parts of a mixture of basic copper phosphate and copper chromite, 0.1-0.5 part of pentaerythritol stearate, 0.1-0.5 part of antioxidant and 0.5-1 part of ultraviolet absorbent.
More preferably, the material comprises the following components in parts by mass: 65-70 parts of LCP, 7-8 parts of POE-g-MAH, 15-20 parts of whiskers, 8-12 parts of modified talcum powder, 12-13 parts of a mixture of basic copper phosphate and copper chromite, 0.2-0.4 part of pentaerythritol stearate, 0.2-0.4 part of antioxidant and 0.7-0.8 part of ultraviolet absorbent. Specifically, the antioxidant can be selected from antioxidant 1010, and the ultraviolet absorber can be selected from ultraviolet absorber UV-234.
In some embodiments, the mixture of basic copper phosphate and copper chromite has a mass ratio of basic copper phosphate to copper chromite of 1:1-3:1.
both copper hydroxide phosphate and copper chromite are laser sensitive additives, copper ions can reduce copper atoms under the laser condition, and copper atom metal particles are gathered on the surface of the LCP product, so that metal electroplating is facilitated. On the one hand, the environment is protected by controlling the parameters on the premise of ensuring that the electroplated metal is not influenced, the chromium of the copper chromite pollutes the environment, the use amount is controlled under the condition of meeting the environment-friendly requirement, and the environment-friendly additive of the basic copper phosphate is introduced; on the other hand, the basic copper phosphate is not completely replaced because the basic copper phosphate is high in price, and the cost can be reduced by using a small amount of copper chromite on the premise of ensuring the environmental protection requirement. If the value is too large, the cost continues to increase, and if the value is too small, the risk of environmental pollution is increased.
The embodiment of the application provides a preparation method of an LCP-based LDS material, which comprises the following steps:
s1, mixing the components of the materials to obtain a mixture;
specifically, in this example, 60 to 75 parts of LCP, 5 to 10 parts of POE-g-MAH, 10 to 25 parts of whisker, 5 to 15 parts of talc, 10 to 15 parts of a mixture of basic copper phosphate and copper chromite, 0.1 to 0.5 part of pentaerythritol stearate, 0.1 to 0.5 part of antioxidant, and 0.5 to 1 part of ultraviolet absorber were mixed by a high-speed mixer at 1000rpm/min for 1 hour to obtain a mixture.
And S2, granulating the mixture to obtain the LCP-based LDS material.
Specifically, in this example, the mixture was melt-blended and extruded by a twin-screw extruder to obtain an LCP-based LDS material. The parameters of extrusion granulation are specifically as follows: the extrusion temperature is 280-320 ℃, and the screw rotating speed is 200-300rpm/min.
Embodiments of the present application provide a component prepared from the LCP-based LDS material provided above.
The embodiment of the application provides a preparation method of a component, which comprises the following steps:
s1, mixing the components of the material provided above to obtain a mixture;
specifically, in this example, 60 to 75 parts of LCP, 5 to 10 parts of POE-g-MAH, 10 to 25 parts of whisker, 5 to 15 parts of talc, 10 to 15 parts of a mixture of basic copper phosphate and copper chromite, 0.1 to 0.5 part of pentaerythritol stearate, 0.1 to 0.5 part of antioxidant, and 0.5 to 1 part of ultraviolet absorber were mixed by a high-speed mixer at 1000rpm/min for 1 hour to obtain a mixture.
And S2, granulating the mixture to obtain the LCP-based LDS material.
Specifically, in this example, the mixture was melt-blended by a twin-screw extruder and extruded to obtain an LCP-based LDS material. The parameters of extrusion granulation are specifically as follows: the extrusion temperature is 280-320 ℃, and the screw rotating speed is 200-300rpm/min.
And S3, carrying out injection molding and proofing on the material to obtain the component.
In some embodiments, the injection proofing barrel nozzle temperature is 320-340 ℃; the temperature of the front section of the charging barrel for injection molding and proofing is 320-340 ℃; the interrupted temperature of the charging barrel for injection molding and proofing is 310-320 ℃; the rear section temperature of the charging barrel for injection molding and proofing is 300-310 ℃.
In some embodiments, the mold temperature for the injection proofing is 100-150 ℃; the injection molding pressure of the injection molding proofing is 80-100Mpa; the pressure maintaining pressure of the injection molding and proofing is 20-40Mpa; the back pressure of the injection molding proofing is 3-5Mpa; the rotating speed of the screw for injection molding and proofing is 50-100rpm/min.
Under the condition of ensuring injection molding, the crystallinity of the product can be properly adjusted and reduced by controlling the temperature, the pressure and the time. And if the values of part of parameters are too small, the product cannot be subjected to normal injection molding, and if the values of part of parameters are too large, the crystallinity of the material is too large. For example, the temperature of the die is higher, the melt is cooled slowly, the relaxation time is long, the orientation level is low, the crystallinity of the polymer is high, and the actual shrinkage rate of the product is large.
Specifically, in the present example, the LCP-based LDS material was dried in an oven at 150 ℃ for 3-5 hours. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the nozzle temperature of the charging barrel is 320-340 ℃, the front section temperature of the charging barrel is 320-340 ℃, the middle section temperature of the charging barrel is 310-320 ℃, the rear section temperature of the charging barrel is 300-310 ℃, the mold temperature is 100-150 ℃, the injection pressure is 80-100Mpa, the pressure maintaining pressure is 20-40Mpa, the back pressure is 3-5Mpa, and the screw rotating speed is 50-100rpm/min.
The present application is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. The experimental methods without specifying specific conditions in the following examples were generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
Example 1
A method of making a component, the method comprising:
step 1: extrusion granulation according to material system formula
And (3) carrying out ultrasonic treatment on the flaky talcum powder for 30min by using 15 mass parts of KH550 silane coupling agent aqueous solution. 65 parts of LCP, 5 parts of POE-g-MAH, 14 parts of poly (butyl acrylate-styrene) whisker, 5 parts of flaky talcum powder, 10 parts of mixture of basic copper phosphate and copper chromite (the mass ratio of the basic copper phosphate to the copper chromite is 1:1), 0.2 part of pentaerythritol stearate, 0.3 part of antioxidant 1010 and 0.5 part of ultraviolet absorbent UV-234 are mixed by a high-speed mixer at 1000rpm/min for 1 hour and uniformly mixed to obtain the LCP composite material for laser direct molding. The extrusion temperature was 300 ℃ and the screw speed was 200rpm/min.
And 2, step: LCP modified granular material injection molding
The modified LCP material from step 1 was dried in an oven at 150 ℃ for 3h. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the temperature of a nozzle of the charging barrel is 340 ℃, the front section temperature of the charging barrel is 340 ℃, the middle section temperature of the charging barrel is 320 ℃, and the rear section temperature of the charging barrel is 310 ℃; the mold temperature is 150 ℃, the injection pressure is 80Mpa, the pressure maintaining pressure is 20Mpa, the back pressure is 3Mpa, and the screw rotating speed is 50rpm/min.
Example 2
A method of making a component, the method comprising:
step 1: extruding and granulating according to the formula of the material system
And (3) carrying out ultrasonic treatment on the talcum powder with the particle size of 3000 meshes for 30min by using 20 mass percent of KH550 silane coupling agent aqueous solution. 65 parts of LCP, 5 parts of POE-g-MAH, 14 parts of poly (4-hydroxy-benzyl ester) whisker, 5 parts of 3000-mesh-size talcum powder, 10 parts of a mixture of basic copper phosphate and copper chromite (the mass ratio of the basic copper phosphate to the copper chromite is 1:1), 0.2 part of pentaerythritol stearate, 0.3 part of antioxidant and 0.5 part of ultraviolet absorbent UV-234 are mixed for 1 hour and uniformly mixed by a high-speed mixer at 1000rpm/min to obtain the LCP composite material for laser direct forming. The extrusion temperature was 300 ℃ and the screw speed was 200rpm/min.
Step 2: LCP modified granular material injection molding
The modified LCP material in step 1 was dried in an oven at 150 ℃ for 3h. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the temperature of a nozzle of the charging barrel is 340 ℃, the temperature of the front section of the charging barrel is 340 ℃, the temperature of the middle section of the charging barrel is 320 ℃, and the temperature of the rear section of the charging barrel is 310 ℃; the temperature of the mold is 150 ℃, the injection pressure is 80Mpa, the pressure maintaining pressure is 20Mpa, the back pressure is 3Mpa, and the rotating speed of the screw is 50rpm/min.
Example 3
A method of making a component, the method comprising:
step 1: extrusion granulation according to material system formula
And (3) performing ultrasonic treatment on the talc powder with the granularity of 5000 meshes for 30min by using 20 mass percent of KH550 silane coupling agent aqueous solution. 60 parts of LCP, 7 parts of POE-g-MAH, 17 parts of poly (4-hydroxy-benzyl ester) whisker, 5 parts of talcum powder with 5000 meshes of granularity, 10 parts of mixture of basic copper phosphate and copper chromite (the mass ratio of the basic copper phosphate to the copper chromite is 2:1), 0.2 part of pentaerythritol stearate, 0.3 part of antioxidant and 0.5 part of ultraviolet absorbent UV-234 are mixed for 1 hour and uniformly mixed by a high-speed mixer at 1000rpm/min to obtain the LCP composite material for laser direct forming. The extrusion temperature was 310 ℃ and the screw speed was 200rpm/min.
And 2, step: LCP modified granular material injection molding
The modified LCP material in step 1 was dried in an oven at 150 ℃ for 3h. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the temperature of a nozzle of the charging barrel is 340 ℃, the temperature of the front section of the charging barrel is 340 ℃, the temperature of the middle section of the charging barrel is 320 ℃, and the temperature of the rear section of the charging barrel is 310 ℃; the mold temperature is 150 ℃, the injection pressure is 80Mpa, the pressure maintaining pressure is 20Mpa, the back pressure is 3Mpa, and the screw rotating speed is 60rpm/min.
Example 4
A method of making a component, the method comprising:
step 1: extrusion granulation according to material system formula
And (3) carrying out ultrasonic treatment on the talc powder with the granularity of 5000 meshes for 30min by using 20 mass percent of KH550 silane coupling agent aqueous solution. 60 parts of LCP, 7 parts of POE-g-MAH, 17 parts of poly (4-hydroxy-benzyl-ester) whisker, 5 parts of talcum powder with 5000-mesh granularity, 10 parts of mixture of basic copper phosphate and copper chromite (the mass ratio of the basic copper phosphate to the copper chromite is 2:1) pentaerythritol stearate, 0.3 part of antioxidant 1010 and 0.5 part of ultraviolet absorbent UV-234 are mixed by a high-speed mixer at 1000rpm/min for 1 hour and uniformly mixed to obtain the LCP composite material for laser direct forming. The extrusion temperature was 310 ℃ and the screw speed was 250rpm/min.
Step 2: LCP modified granular material injection moulding
The modified LCP material from step 1 was dried in an oven at 150 ℃ for 5h. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the temperature of a nozzle of the charging barrel is 330 ℃, the temperature of the front section of the charging barrel is 330 ℃, the temperature of the middle section of the charging barrel is 310 ℃, and the temperature of the rear section of the charging barrel is 300 ℃; the temperature of the mold is 130 ℃, the injection pressure is 80Mpa, the pressure maintaining pressure is 20Mpa, the back pressure is 3Mpa, and the rotating speed of the screw is 70rpm/min.
Example 5
A method of making a component, the method comprising:
step 1: extrusion granulation according to material system formula
And (3) carrying out ultrasonic treatment on the talc powder with the granularity of 5000 meshes for 30min by using 20 mass percent of KH550 silane coupling agent aqueous solution. 60 parts of LCP, 7 parts of POE-g-MAH, 17 parts of poly (4-hydroxy-benzyl ester) whisker, 5 parts of talcum powder with 5000 meshes of granularity, 10 parts of mixture of basic copper phosphate and copper chromite (the mass ratio of the basic copper phosphate to the copper chromite is 2:1), 0.2 part of pentaerythritol stearate, 0.3 part of antioxidant and 0.5 part of ultraviolet absorbent UV-234 are mixed for 1 hour and uniformly mixed by a high-speed mixer at 1000rpm/min to obtain the LCP composite material for laser direct forming. The extrusion temperature was 310 ℃ and the screw speed was 250rpm/min.
And 2, step: LCP modified granular material injection moulding
The modified LCP material in step 1 was dried in an oven at 150 ℃ for 5h. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the temperature of a nozzle of the charging barrel is 330 ℃, the front section temperature of the charging barrel is 320 ℃, the middle section temperature of the charging barrel is 310 ℃, and the rear section temperature of the charging barrel is 300 ℃; the temperature of the mold is 130 ℃, the injection pressure is 90Mpa, the pressure maintaining pressure is 30Mpa, the back pressure is 4Mpa, and the rotating speed of the screw is 80rpm/min.
Comparative example 1
A method of making a component, the method comprising:
step 1: extrusion granulation according to material system formula
And (3) carrying out ultrasonic treatment on the flaky talcum powder for 30min by using 15 mass percent of KH550 silane coupling agent aqueous solution. 65 parts of LCP, 5 parts of POE-g-MAH, 14 parts of glass fiber, 5 parts of flaky talcum powder, 10 parts of mixture of basic copper phosphate and copper chromite (the mass ratio of the basic copper phosphate to the copper chromite is 1:1), 0.2 part of pentaerythritol stearate, 0.3 part of antioxidant 1010 and 0.5 part of ultraviolet absorbent UV-234 are mixed for 1 hour and uniformly mixed by a high-speed mixer at 1000 rpm/min.
Step 2: LCP modified granular material injection molding
The modified LCP material in step 1 was dried in an oven at 150 ℃ for 3h. And then carrying out injection molding and proofing on the dried material by an injection molding machine. The injection molding process comprises the following specific steps: the temperature of a nozzle of the charging barrel is 340 ℃, the temperature of the front section of the charging barrel is 340 ℃, the temperature of the middle section of the charging barrel is 320 ℃, and the temperature of the rear section of the charging barrel is 310 ℃; the mold temperature is 150 ℃, the injection pressure is 80Mpa, the pressure maintaining pressure is 20Mpa, the back pressure is 3Mpa, and the screw rotating speed is 50rpm/min.
Relevant experiments and effect data:
the injection molded articles of the LCP based LDS materials prepared in examples 1 to 5 were subjected to shrinkage test in the transverse and longitudinal directions, and the results are shown in the following table:
from the above table, by using the method provided in the embodiment of the present application, the transverse shrinkage rate of the material can be reduced to a certain extent by introducing an appropriate amount of whiskers and performing silane modification on the surface of the talc powder. Then the temperature of the die is reduced, the injection pressure is increased, the injection temperature is reduced in a reasonable range, and the operations of maintaining pressure, back pressure, screw rotating speed and the like are matched; the transverse shrinkage rate of the material can be further reduced, and the difference between the transverse shrinkage rate and the longitudinal shrinkage rate of the material is further reduced. So that the shrinkage difference between the transverse direction and the longitudinal direction of the LCP-based LDS product can be reduced from 0.5 percent to 0.1 percent.
Various embodiments of the present application may exist in a range of forms; it is to be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the stated range, such as 1, 2, 3, 4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
In this application, where the context requires no explicit explanation, the use of directional words such as "upper" and "lower" in particular refers to the direction of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "including" and the like mean "including but not limited to". In this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. As used herein, "at least one" means one or more, and "a plurality" means two or more. "at least one," "at least one item(s) below," or similar expressions, refer to any combination of these items, including any combination of item(s) alone or item(s) in plurality. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An LCP-based LDS material, wherein the composition of said material comprises: LCP and whiskers; the whiskers include poly (butyl acrylate-styrene) whiskers and/or poly (4-hydroxybenzene methyl ester) whiskers.
2. The LCP-based LDS material of claim 1, wherein the composition of the material further comprises: the modified talcum powder is prepared by modifying talcum powder through a silane coupling agent.
3. The LCP-based LDS material of claim 2, wherein the modified talc powder is in the form of flakes and/or powder; the particle size of the modified talcum powder is 2000-5000 meshes.
4. The LCP-based LDS material according to any one of claims 1 to 3, wherein the composition of said material comprises in parts by mass:
60-75 parts of LCP, 5-10 parts of POE-g-MAH, 10-25 parts of crystal whisker, 5-15 parts of modified talcum powder, 10-15 parts of a mixture of basic copper phosphate and copper chromite, 0.1-0.5 part of pentaerythritol stearate, 0.1-0.5 part of antioxidant and 0.5-1 part of ultraviolet absorbent.
5. The LCP-based LDS material of claim 4, wherein the composition of said material comprises, in parts by mass:
65-70 parts of LCP, 7-8 parts of POE-g-MAH, 15-20 parts of crystal whisker, 8-12 parts of modified talcum powder, 12-13 parts of a mixture of basic copper phosphate and copper chromite, 0.2-0.4 part of pentaerythritol stearate, 0.2-0.4 part of antioxidant and 0.7-0.8 part of ultraviolet absorbent.
6. The LCP-based LDS material of claim 5, wherein the mixture of copper hydroxide phosphate and copper chromite has a copper hydroxide phosphate to copper chromite mass ratio of 1:1-3:1.
7. a component prepared from the LCP-based LDS material as claimed in any one of claims 1 to 6.
8. A method of making a component, wherein the component is the component of claim 7, the method comprising:
obtaining the LCP-based LDS material of any one of claims 1 to 6;
and carrying out injection molding and proofing on the material to obtain the component.
9. The method for manufacturing a component according to claim 8, wherein the injection proofing barrel nozzle temperature is 320-340 ℃; and/or
The temperature of the front section of the charging barrel for injection molding and proofing is 320-340 ℃; and/or
The interrupted temperature of the charging barrel for injection molding and proofing is 310-320 ℃; and/or
The rear section temperature of the charging barrel for injection molding and proofing is 300-310 ℃.
10. The method for manufacturing a component according to claim 8, wherein the temperature of the injection molding and proofing mold is 100-150 ℃; and/or
The injection molding pressure of the injection molding proofing is 80-100Mpa; and/or
The pressure maintaining pressure of the injection molding proofing is 20-40Mpa; and/or
The back pressure of the injection molding proofing is 3-5Mpa; and/or
The rotating speed of the screw for injection molding and proofing is 50-100rpm/min.
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| CN101942193A (en) * | 2009-07-10 | 2011-01-12 | 合肥杰事杰新材料有限公司 | Whisker-enhanced nylon composite |
| CN106633363A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Polypropylene composition for 3D printing, and preparation method thereof |
| CN110655792A (en) * | 2019-10-29 | 2020-01-07 | 中广核高新核材科技（苏州）有限公司 | Low-dielectric-laser direct-forming composite material suitable for 5G communication and preparation method thereof |
| CN111961352A (en) * | 2020-08-25 | 2020-11-20 | 中广核高新核材科技（苏州）有限公司 | Laser direct-forming low-warpage LDS composite high polymer material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101942193A (en) * | 2009-07-10 | 2011-01-12 | 合肥杰事杰新材料有限公司 | Whisker-enhanced nylon composite |
| CN106633363A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Polypropylene composition for 3D printing, and preparation method thereof |
| CN110655792A (en) * | 2019-10-29 | 2020-01-07 | 中广核高新核材科技（苏州）有限公司 | Low-dielectric-laser direct-forming composite material suitable for 5G communication and preparation method thereof |
| CN111961352A (en) * | 2020-08-25 | 2020-11-20 | 中广核高新核材科技（苏州）有限公司 | Laser direct-forming low-warpage LDS composite high polymer material and preparation method thereof |
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