CN109735060A - A kind of thermoplastic composite and preparation method thereof for laser direct structuring technique - Google Patents
A kind of thermoplastic composite and preparation method thereof for laser direct structuring technique Download PDFInfo
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- CN109735060A CN109735060A CN201811652792.5A CN201811652792A CN109735060A CN 109735060 A CN109735060 A CN 109735060A CN 201811652792 A CN201811652792 A CN 201811652792A CN 109735060 A CN109735060 A CN 109735060A
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Abstract
The thermoplastic composite and preparation method thereof that the invention discloses a kind of for laser direct structuring technique is made of the raw material of following weight percent meter: liquid crystal polyester 59%-98.9%, laser-sensitive additive 1%-10%, compatilizer 0.1%-1%, filler 0%-30%.Laser-sensitive additive and compatilizer are modified with other supplementary material blending extrusions after being pre-mixed latter vacuum heat treatment 2-6 hours.The characteristics of thermoplastic composite of the invention improves the dispersibility and activation capacity of laser-sensitive additive, reduces dosage, while maintaining liquid crystal polyester high temperature resistant and high tenacity, thus the composite material has excellent comprehensive performance.
Description
Technical field
The present invention relates to a kind of thermoplastic composite, specially a kind of polymerizable mesogenic for laser direct structuring technique
The preparation method of object composite material and this composite material belongs to liquid crystal polymer technical field of composite materials.
Background technique
Laser direct forming (LDS, Laser Direct Structuring) technology is a kind of laser processing and chemical plating
The production technology of processing procedure, to make three dimensional mold interconnection element (3D-MID, Three-dimensional Moulded
Interconnect Device).Its principle be by laser irradiation to the plastic cement product containing laser-sensitive additive on, activation
Circuit pattern out, the region being activated on the product can deposit the metals such as copper, nickel, gold in no electrochemical plating, to assign
Three-dimensional plastic cement product conducting function.
Nowadays, electronic component becomes increased popularity and usually provides wireless communication ability.For example, electronic component can make
It is communicated with the mobile phone frequency range (2G/3G/4G standard) under 815MHz~3600MHz.Electronic component also can be used
The wireless network of 2.4GHz and 5GHz frequency band (802.11a/b/g/n/ac) is communicated.Such electronic component structure body, i.e.,
3D-MID, usually plastic rubber substrate and the conducting element formed thereon or channel are constituted, be it is a kind of have integrated printed conductor or
The three-dimensional part of circuit layout.Using LDS method, 150 μm or smaller conducting element width and spacing can be obtained, to use
Space and loss of weight are saved in lesser electronic device.Another advantage of LDS method is its flexibility.It is conductive logical to change
Road design, only need to reprogram control laser, without redesigning mold.Which reduce processing costs, save the time.
Currently, the material science for being applied to LDS technology has also obtained quick development.Resin matrix covers general plastic
Material, engineering plastics and special engineering plastics.It is wherein polycarbonate (PC), polycarbonate and polypropylene than more typical application
Nitrile/Butadiene/Styrene alloy (PC/ABS), polybutylene terephthalate (PBT) (PBT), poly(p-phenylene terephthalamide)
(PPA) etc..However, these materials be both needed to addition fire retardant, this will be unfavorable for the mechanical performance of material, which makes it unsuitable in
It is required that surface mount process (SMT) resistant to high temperature.In addition, the dielectric loss angle tangent value of these materials is higher, this makes its hardly possible
In application for high-frequency communication device.
Thermotropic liquid crystal polymer (TLCP) is a kind of high-performance polyester material, the component that can be used for manufacturing include it is electrical and
Electric power connector, circuit board, motor insulation shell fast, for various purposes, motor vehicle assembly, cooker/baking tray, substitution ceramics are used as
High temperature light socket and light-emitting diode housing and/or mounting.It is usually with its excellent melt-processed shaping characteristic, solid
Some anti-flammabilitys, low loss tangent value and all multipurposes at high temperature and it is famous.
Existing TLCP is used for the application (such as CN 104961922A, CN 103906803B) of LDS material now, still, existing
There is the coat of metal adhesive force on the LCP mouldings being prepared in technology not strong, and the LDS material of the prior art can not expire
The foot requirement, and required laser-sensitive additive is more, influences the toughness of moulding material.
Summary of the invention
The purpose of the invention is to provide the thermoplastic composite for laser direct structuring technique, swashed with less
Photaesthesia additive amount, to obtain preferable metallic film adhesive force, and the composite material obtained has preferable toughness.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of thermoplastic composite is made of the raw material of following weight percent meter:
Liquid crystal polyester in the present invention is the liquid crystal polyester for showing liquid crystal liquid crystal property in the molten state, liquid used in the present invention
The fusing point of brilliant polyester is at 250~350 DEG C, and preferably 300~340 DEG C.The melt viscosity of liquid crystal polyester used in the present invention is logical
Often in 10~100Pas, preferably 25~45Pas.
Liquid crystal polyester is to use aromatic compound as liquid crystal polyester made of starting monomer, and fragrance is preferably used only
Compounds of group is as Wholly aromatic liquid crystal polyester made of starting monomer.
The laser-sensitive additive is the mixed metal oxides of tin and antimony, additive amount 1%-10%.Use phase
After holding agent, its usage amount can be reduced and do not influence the activation effect of laser-sensitive additive, additive amount is preferably 1%-3%.
The compatilizer is that can mix with liquid crystal polyester, and the stearates of metal oxide dispersion is promoted to disperse
Agent, the combination including one or more of odium stearate, calcium stearate, lithium stearate.
Filler described in the filler is milled glass fiber, talcum, mica, titanium dioxide, silica, wollastonite
One or more of combination.If will affect the toughness of material containing a large amount of inorganic fillers, and it will affect laser-sensitive
The activation effect of additive, therefore additive amount is preferably 0%-30%.
Above-mentioned thermoplastic composite can use well known melt molding method (and relevant device), including be injected into
Type, extrusion (when especially forming sheet material, film or pipe), blow molding and sinter molding.
The preparation method of above-mentioned thermoplastic composite, its step are as follows:
(1) liquid crystal polyester is dried in vacuo at 105 DEG C~200 DEG C 2~15 hours, it is true preferably at 120 DEG C~180 DEG C
Sky is 4~8 hours dry；
(2) laser-sensitive additive is pre-mixed with compatilizer, and vacuum heat treatment 2~6 is small at 55 DEG C~150 DEG C
When, vacuum heat treatment 2~3 hours preferably at 60 DEG C~120 DEG C；
(3) double screw extruder extrusion is added using Weightlessness balance according to a certain percentage with other auxiliary materials in (1), (2), made
Grain.Double screw extruder from spout to extrusion die temperature be 280~350 DEG C respectively, 300~360 DEG C, 320~380 DEG C,
300~380 DEG C, 300~350 DEG C, 240~300 DEG C, engine speed is 300 revs/min.Performance test test specimen is infused with injection molding machine
Penetrate molding.
Later, conducting element is formed on injection molding molded item using LDS method.Use laser activation laser-sensitive
Additive, wherein physical-chemical reaction release metallic atom occurs for metal oxide.These metallic atoms are in molded part surface,
To serve as the nuclearing centre of other metals of electroless deposition.Other metals of deposition, such as copper, so that it may solid in this plating process
It is scheduled on molded part surface, forms conductive component.Gained molded item is MID component, wherein containing integrated electronic circuit conduction
Element.100 test pieces are prepared with this method, hundred lattice tests is carried out, the area that averagely falls off is calculated.
The invention has the following advantages: the present invention improves laser-sensitive additive using stearic acid compatilizer
Dispersibility reduces its usage amount, makes it that can also have preferable laser activation effect and chemical plating effect under lower content.
Specific embodiment
The present invention is further illustrated below by embodiment and comparative example, in the case where not violating spirit of the invention, the present invention
It should be not limited to the content that following embodiment is specifically expressed.
Properties of product test method:
In the present invention, Izod notch impact strength (IS) is tested with ASTM D256 method, sample thickness 3.2mm.Thermal deformation
Temperature (HDT) is measured by ASTM D648 method, applies load 1.82MPa.
In the present invention, the adhesive force of the coat of metal is assessed using being averaged of testing of the hundred lattice area that falls off.
Embodiment 1-8 and comparative example 1-3
Liquid crystal polyester: KG300, Shanghai Pret Chemical New Material Co., Ltd.
Laser-sensitive additive:8850, Merck groups；
Odium stearate: Licomont Nav 101, Clariant company.
Talcum powder: HM 4, IMI Fabi company.
Liquid crystal polyester is dried in vacuo 4 hours at 140 DEG C；Laser-sensitive additive is pre-mixed with compatilizer, and
Vacuum heat treatment 2 hours at 60 DEG C.Material after drying is claimed material twin-screw extrusion is added by weightlessness by the proportion of table 1
Extruding pelletization in machine.Extruder includes transfer element, kneading member, low-pressure area (to make that may be present in polyester be volatilized into
Divide and be discharged under vacuum) and mouth mold.Extruder from spout to extrusion die temperature be 240 DEG C respectively, 290 DEG C, 300 DEG C,
310 DEG C, 315 DEG C, 325 DEG C, 345 DEG C, engine speed is 300 revs/min.Thermoplastic composite leaves mouth mold, through water-carrying groove
Cooling, pelletizing.
Thermoplastic composite particle prepares test performance with injection moulding method after 150 DEG C dry 3~5 hours
Batten.350 DEG C of injection temperature, injection pressure 20MPa, 5~10sec of injection time, cooling time 5~10sec, mould temperature 90~
110℃.The batten of injection formed is tested for the property after 50% relative humidity, 23 DEG C are placed at least 24 hours, is tested
Performance is listed in table 2.
Table 1
Table 2
"/": chemical plating can not carry out under the comparative example.
From Examples 1 to 8 and comparative example 1~3 it can be seen that
After thermoplastic composite chemical plating obtained in Examples 1 to 8 have coat of metal strong adsorption force, high tenacity,
The advantages that heat resistance is good.Compared with comparative example it can be found that after having used compatilizer, laser-sensitive additive amount is significantly
It reduces, while the adsorption capacity of the coat of metal can be increased.And when filer content is excessively high, the toughness of composite material is rapidly deteriorated.
Thermoplastic composite for LDS of the invention can be gathered around in the case where laser-sensitive additive lower usage amount
The characteristics of having preferable laser activation effect and chemical plating effect, while maintaining liquid crystal polyester high temperature resistant, high tenacity, has excellent
Comprehensive performance.
Claims (6)
1. a kind of thermoplastic composite for laser direct structuring technique, it is characterised in that: by following weight percent meter
Raw material composition:
2. a kind of thermoplastic composite for laser direct structuring technique according to claim 1, it is characterised in that:
The thermotropic liquid crystalline polyester is the liquid crystal polyester for using aromatic compound to be prepared as starting monomer.
3. a kind of thermoplastic composite for laser direct structuring technique according to claim 1, it is characterised in that:
The laser-sensitive additive is the mixed metal oxides of tin and antimony.
4. a kind of thermoplastic composite for laser direct structuring technique according to claim 1, it is characterised in that:
The compatilizer is stearates, the combination including one or more of odium stearate, calcium stearate, lithium stearate.
5. a kind of thermoplastic composite for laser direct structuring technique according to claim 1, it is characterised in that:
The filler is the group of one or more of milled glass fiber, talcum, mica, titanium dioxide, silica, wollastonite
It closes.
The preparation method of thermoplastic composite described in 6. claim 1-5 is one of any, it is characterised in that: its step are as follows:
(1) liquid crystal polyester is dried in vacuo at 105 DEG C~200 DEG C 2~15 hours, vacuum is dry preferably at 120 DEG C~180 DEG C
Dry 4~8 hours；
(2) laser-sensitive additive is pre-mixed with compatilizer, and vacuum heat treatment 2~6 hours at 55 DEG C~150 DEG C,
It is preferred that vacuum heat treatment 2~3 hours at 60 DEG C~120 DEG C；
(3) it uses Weightlessness balance that double screw extruder extrusion is added according to a certain percentage (1), (2) and other auxiliary materials, be granulated.It is double
Screw extruder from spout to extrusion die temperature be 280~350 DEG C respectively, 300~360 DEG C, 320~380 DEG C, 300~
380 DEG C, 300~350 DEG C, 240~300 DEG C, engine speed is 300 revs/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| CN114381093A (en) * | 2021-12-28 | 2022-04-22 | 上海普利特化工新材料有限公司 | Thermoplastic composite material with high dielectric constant and low dielectric loss and preparation method thereof |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| WO2023103273A1 (en) * | 2021-12-07 | 2023-06-15 | 富海(东营)新材料科技有限公司 | Liquid crystalline polymer composite material for rapid injection molding and preparation method therefor, and injection molding screw for rapid injection molding |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11705641B2 (en) | 2019-08-21 | 2023-07-18 | Ticoan Llc | Antenna system including a polymer composition having a low dissipation factor |
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| US12136762B2 (en) | 2019-08-21 | 2024-11-05 | Ticona Llc | Polymer composition for use in an antenna system |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US12107617B2 (en) | 2019-09-23 | 2024-10-01 | Ticona Llc | RF filter for use at 5G frequencies |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
| US12035467B2 (en) | 2020-02-26 | 2024-07-09 | Ticona Llc | Circuit structure |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
| US12230865B2 (en) | 2021-02-18 | 2025-02-18 | Ticona Llc | Polymer composition for use in an antenna system |
| WO2023103273A1 (en) * | 2021-12-07 | 2023-06-15 | 富海(东营)新材料科技有限公司 | Liquid crystalline polymer composite material for rapid injection molding and preparation method therefor, and injection molding screw for rapid injection molding |
| CN114381093A (en) * | 2021-12-28 | 2022-04-22 | 上海普利特化工新材料有限公司 | Thermoplastic composite material with high dielectric constant and low dielectric loss and preparation method thereof |
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Effective date of registration: 20240125 Address after: No.230, Xiasheng Road, Jinshan District, Shanghai, 201502 Patentee after: SHANGHAI PRET NEW CHEMICAL MATERIAL Co.,Ltd. Country or region after: China Patentee after: Shanghai Pret Composites Co.,Ltd. Patentee after: ZHEJIANG PRET NEW MATERIALS Co.,Ltd. Patentee after: CHONGQNG PULITE NEW MATERIAL Co.,Ltd. Address before: No.230, Xiasheng Road, Jinshan District, Shanghai, 201502 Patentee before: SHANGHAI PRET NEW CHEMICAL MATERIAL Co.,Ltd. Country or region before: China Patentee before: Shanghai Pret Composites Co.,Ltd. Patentee before: ZHEJIANG PRET NEW MATERIALS Co.,Ltd. Patentee before: CHONGQNG PULITE NEW MATERIAL Co.,Ltd. Patentee before: SHANGHAI PRET MATERIAL TECHNOLOGY Co.,Ltd. |
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