KR102104752B1 - An aromatic liquid crystalline polyester resin having low-dielectric properties in a high frequency region - Google Patents

Abstract

The present invention relates to a material containing, based on an LCP resin having low dielectric properties, a laser direct structuring additive, glass bubble, and plate-like filler, and has low dielectric properties in a high frequency region, enables the laser direct structuring, and has excellent mechanical strength and high heat resistance.

Description

Aromatic liquid crystal polyester resins with low dielectric properties in the high frequency range {AN AROMATIC LIQUID CRYSTALLINE POLYESTER RESIN HAVING LOW-DIELECTRIC PROPERTIES IN A HIGH FREQUENCY REGION}

In a changing environment in which a system that connects all things called the Internet of Things (IoT) to the Internet is expanded, each information is collected and indirectly sends and receives large amounts of information at high speed, such as prompt feedback based on the information obtained. Opportunities to do it are also increasing. Information and communication devices, such as smartphones and tablet PCs, which have led this development in the past, have been further improved in the direction of smaller, lighter, and more versatile. In addition, the application of high-speed transmission parts to rapidly acquire and control sensor and camera information obtained during driving through the expansion of EV and autonomous driving technologies is expected to increase in the automotive sector in the future.

Due to the increase in the amount of transmission information, a high-frequency wideband shift of a transmission signal progresses, and according to these changes, there is an increasing demand for high-performance and highly reliable electronic components capable of adapting to high-frequency regions such as microwaves and millimeter waves.

LCP (Liquid Crystal Polymer) is one of the materials with low dielectric constant and low dielectric loss. 5G communication materials are emerging as the market needs change, which requires low permittivity and dielectric loss in the high frequency range. In particular, in the case of sensors and antennas that receive high-frequency signals, there is a need for materials capable of laser direct processing that can simplify complex circuits.

In the case of existing smart phones, laser / direct processing of PC / ABS resin was applied to sensors and antennas, but high dielectric loss in the high-frequency region required low dielectric loss materials.

LCP is a generic term for thermoplastic aromatic polyesters that exhibit liquid crystallinity upon melting. It has a rigid and unbreakable molecular structure, which is characterized by very little entanglement of molecules specific to polymer materials. Due to its high fluidity, high heat resistance, and high dimensional accuracy, it is widely used in the connector market. Moreover, the high heat resistance comes from a structure in which the molecular skeleton is highly symmetrical and the mobility of liquid crystal is limited. The DK of the conventional LCP has a value of 3.7 to 4.5.

Direct laser structuring is to design a desired pattern on a polymer composition using a laser, and to plate copper and nickel on it to realize electrical properties. The design is free because it is possible to design a fine pattern at a desired location through a laser and a dedicated program. In addition, even if there is an error in the designed pattern, it can be easily corrected by correcting the program. With the miniaturization and complexity of electronic components, the need for materials that can be directly structured by lasers is increasing.

With the proliferation of 5G communication and V2X communication by automatic operation, materials that can be applied to high-speed transmission parts and high-frequency transmission parts are needed. It is not necessary to simply provide a material with low dielectric constant and low dielectric loss in the high-frequency region, and at the same time, laser direct processing is possible to cope with miniaturization and complexity, and heat resistance, fluidity, dimensional stability, and mechanical strength must all be provided.

The present invention secures an optimal LCP resin having low dielectric properties, and thus has a low dielectric property polymer capable of directly structuring a complex antenna and sensor design so that laser signals can be rapidly exchanged in a high-frequency region through a proprietary filler design. To develop a composition.

The present invention provides a polymer composition comprising a laser direct structuring additive, filler, and glass bubble based on LCP resin with low dielectric properties.

According to the present invention, it is possible to provide a polymer composition having low dielectric properties in a high frequency region and capable of direct laser structuring. This material is suitable for electronic components for 5G communication.

Figure 1 shows that the content of the LDS additive among the components of the present invention is plated when composed of 6% by weight per 100 parts by weight of the polymer composition.
FIG. 2 shows that the plating property is poor when the content of the LDS additive among the components of the present invention is composed of 5% by weight per 100 parts by weight of the polymer composition.
3 is a graph comparing the dielectric properties of the aromatic liquid crystal polyester resin according to the embodiment of the present invention and the aromatic liquid crystal polyester resin according to the comparative example for each frequency domain.
4 is a graph showing LCP dielectric properties according to a comparative example.
Figure 5 is a graph showing the dielectric properties of the polymer composition according to the type of additives added to the LCP resin of the present invention, that is, each content of talc and glass fiber.
Figure 6 is a graph showing the dielectric properties of the polymer composition according to the size of the additive, that is, Glass Bubble added to the LCP resin of the present invention.

In order to fully understand the configuration and effect of the present invention, preferred embodiments of the present invention will be described. However, the present invention is not limited to the embodiments disclosed below, and can be implemented in various forms and various changes can be made. However, the description of the embodiments is provided to make the disclosure of the present invention complete, and to fully inform the scope of the invention to those skilled in the art.

In general, the present invention relates to a polymer composition comprising a laser direct structuring additive, filler, glass bubble in the LCP resin having the low dielectric properties and optionally comprising glass fibers and / or other additives. In the present invention, the properties of the components and / or their concentrations are selectively controlled, while still enabling laser activation, while maintaining low dielectric properties, good mechanical strength and high heat resistance. Thus, the material can be readily processed into a substrate, and then one or more conductive elements can be applied using a laser direct structuring process. If necessary, the conductive element can be an antenna, so that the final component is an antenna structure that can be used for a wide variety of different electronic components such as mobile phones.

For example, Talc, glass bubble, and copper chromite are used in the LCP resin to have a Dk of less than 3k and a low Df in the high-frequency region that can be used for 5G communication repeaters and antennas. .

Securing LCP resin composition with low dielectric properties

The inventors have designed monomer types and composition ratios of LCP resins having low dielectric properties suitable for the present invention through many studies.

There are two types of LCP. One is a lyotropic liquid crystal, and when dissolved in a solvent, has liquid crystal properties. The other is a thermoplastic liquid crystal having liquid crystal properties when melted. Thermoplastic liquid crystals are mainly used in the electronics industry because they have excellent properties in small electronic devices and are suitable for mass production of injection molding. Among commercial engineering plastics, LCP is suitable for small products with high fluidity, and has high thermal stability and excellent flame retardancy, hygroscopicity and shrinkage in the reflow process.

The polymer composition of the present invention uses one or more LCP resins. The amount of such LCP resin is typically from about 20% to about 80% by weight of the polymer composition, from about 30% to about 75% by weight in some embodiments and from about 40% to about 70% by weight in some embodiments. Suitable LCP resins can include aromatic liquid crystal polyesters, aromatic poly (esteramides), aromatic poly (estercarbonates), aromatic polyamides, and the like, similarly one or more aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, Repeating units formed from aromatic aminocarboxylic acids, aromatic amines, aromatic diamines, and the like, and combinations thereof.

For example, the aromatic liquid crystal polyester may include (1) two or more aromatic hydroxycarboxylic acids; (2) one or more aromatic hydroxycarboxylic acids, one or more aromatic dicarboxylic acids and one or more aromatic diols; And / or (3) one or more aromatic dicarboxylic acids and one or more aromatic diols. Examples of suitable aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2-hydroxy-6-naphthoic acid; 2-hydroxy-5-naphthoic acid; 3-hydroxy-2-naphthoic acid; 2-hydroxy-3-naphthoic acid; 4'-hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl-4-benzoic acid; 4'-hydroxyphenyl-3-benzoic acid and the like, and alkyl, alkoxy, aryl and halogen substituents thereof. Examples of suitable aromatic dicarboxylic acids include terephthalic acid; Isopic acid; 2,6-naphthalenedicarboxylic acid; Diphenyl ether-4,4'-dicarboxylic acid; 1,6-naphthalenedicarboxylic acid; 2,7-naphthalenedicarboxylic acid; 4,4'-dicarboxy biphenyl; Bis (4-carboxyphenyl) ether; Bis (4-carboxyphenyl) butane; Bis (4-carboxyphenyl) ethane; Bis (3-carboxyphenyl) ether; Bis (3-carboxyphenyl) ethane and the like, and alkyl, alkoxy, aryl, and halogen substituents thereof. Examples of suitable aromatic diols include hydroquinone; Resorcinol; 2,6-dihydroxynaphthalene; 2,7-dihydroxy hydroxynaphthalene; 1,6-dihydroxynaphthalene; 4,4'-dihydroxybiphenyl; 3,3'-dihydroxybiphenyl; 3,4'-dihydroxybiphenyl; 4,4'-dihydroxybiphenyl ether; Bis (4-hydroxyphenyl) ethane and the like, and alkyl, alkoxy, aryl, and halogen substituents thereof.

In certain embodiments, the aromatic liquid crystal polyesters include 4-hydroxybenzoic acid (HBA) and other optional repeating units such as high purity terephthalic acid (PTA) and / or high purity isophthalic acid (PIA); Hydroquinone (HQ), 4,4-biphenol (BP) and / or acetaminophen (APAP), and combinations thereof. The monomer unit derived from HBA may constitute 40 to 80% by weight of the LCP resin, preferably 50 to 70% by weight, more preferably 60% by weight.

The monomer unit derived from PTA and / or PIA may constitute 0.1 to 30% by weight of the LCP resin, and preferably 5 to 20% by weight.

Similarly, the monomer units derived from BP can make up about 5 to 35% by weight of the LCP resin, preferably 10 to 30% by weight, more preferably 20% by weight.

The aromatic polyester may be an LCP resin further containing repeat units derived from terephthalic acid, isophthalic acid, hydroquinone, 4,4-biphenol or a combination thereof.

The preparation of the LCP resin used in the present invention can be carried out by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers), usually melt polymerization, slurry polymerization, etc. Is used. The compounds having an ester-forming ability can be used for polymerization in an intact form, and may also be modified with a derivative having the ester-forming ability from a precursor before polymerization. When polymerizing these, various catalysts can be used. Representative examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali and alkaline earth metal salts of carboxylic acids, BF3, and the like. And the same Lewis acid salt. The amount of the catalyst used is generally about 0.001 to 1% by mass, particularly about 0.01 to 0.2% by mass, relative to the total mass of the monomer. When further required by these polymerization methods, the molecular weight can be increased by reduced pressure or solid phase polymerization heated in an inert gas.

In certain embodiments, in the production of aromatic liquid crystalline polyesters in the present invention, acylated compounds of 2-hydroxy-6-naphic acid and aromatic diols can be used. The acylated compound can be obtained by acylating the phenolic hydroxyl group of 2-hydroxy-6-naphic acid and aromatic diol with fatty acid anhydride.

Examples of fatty acid anhydrides are acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoate anhydride, monochloroacetyl anhydride, dichloroacetyl anhydride, trichloroacetyl anhydride, monobro Moacetyl dianhydride, dibromoacetyl anhydride, tribromoacetyl anhydride, mono fluoroacetyl anhydride, difluoroacetyl anhydride, trifluoroacetyl anhydride, glutaric anhydride, maleic anhydride, succinic anhydride and βbromopropionic acid Contains anhydride. The anhydrides may be used alone or as a mixture of two or more thereof.

Acetic anhydride, propionic anhydride, butyric anhydride and isobutyric anhydride are preferably used from the viewpoint of their cost and handling performance, and acetic anhydride is more preferably used.

LCP resin has low dielectric constant and dielectric loss characteristics in the high frequency region. For example, it has a Dk value of 3.67 or less in the 1 kHz frequency region, and preferably has a Dk value of 3.10 or less. In addition, it has a Dk value of 3.46 or less in the 10 kHz frequency region, and preferably a Dk value of 3.08 or less. For example, it has a Df value of less than 4.37 (10-3) at 1 kPa, preferably a Df value of less than 0.73 (10-3). In addition, it has a Df value of 0.81 (10-3) or less at 10 Hz, and preferably has a Df value of 0.40 (10-3) or less.

The Df and Dk values show a characteristic in which the value decreases as it goes from 1 kHz to 10 kHz (ie, toward the high-frequency region).

A resin composition that can be directly laser processed using a resin having excellent dielectric properties.

The inventors have prepared compounds with additives and composition ratios suitable for the present invention through many studies.

The LCP resin relative to 100 parts by weight of the polymer composition is composed of 20 to 80% by weight, preferably 50 to 70% by weight, more preferably 64% by weight. The type of the LCP resin is not particularly limited, and suitable examples may include aromatic liquid crystal polyester, aromatic poly (esteramide), aromatic poly (estercarbonate), aromatic polyamide, and the like, and similarly one or more aromatic hydroxy And repeat units formed from carboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic amines, aromatic diamines, and combinations thereof.

The polymer composition has low dielectric properties in the high frequency region. For example, it is characterized by low DK (dielectric constant) and DF (dielectric loss) values. Permittivity (ε) is a dielectric (Dielectric Material), that is, an important characteristic value representing the electrical properties of a non-conductor.

For example, the polymer composition has a DK value of 3.78 or less at 1 GHz, more preferably 3.0 or less, and more preferably 2.68 or less. Further, the DK value at 10 GHz is 3.78 or less, more preferably 3.08 or less, and more preferably 2.67 or less.

For example, the polymer composition has a DF value of 5.00 (10 ^-3 ) or less at 1 GHz, preferably 0.73 (10 ^-3 ) or less, and more preferably 0.18 (10 ^-3 ) or less. Further, at 10 GHz, the DK value is 0.8 (10 ^-3 ) or less, preferably 0.50 (10 ^-3 ) or less, and more preferably 0.10 (10 ^-3 ) or less.

In view of the fact that the polymer composition contains a laser direct structuring (LDS) additive, the polymer composition is capable of a laser direct structuring process. In this process, the LDS additive is exposed to the laser, causing the release of metal. Thus, the laser draws a pattern of conductive elements on the part and leaves a rough surface containing incorporated metal particles. These particles then act as nuclei for crystal growth during the plating process (eg, copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, etc.).

The polymer composition may be composed of 100 parts by weight of a laser direct structuring additive 0.1 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 5 to 7% by weight.

The polymer composition may include that the laser activatable additive is a spinel crystal. Spinel crystals may have the formula AB ₂ O ₄ . A is a metal cation having a valence of 2, and B is a metal cation having a valence of 3. The spinel crystals are MgAl ₂ O ₄ , ZnAl ₂ O ₄ , FeAl ₂ O ₄ , CuFe ₂ O ₄ , CuCr ₂ O ₄ , MnFe ₂ O ₄ , NiFe ₂ O ₄ , TiFe ₂ O ₄ , FeCr ₂ O ₄ , MgCr ₂ O ₄ or a combination thereof.

The laser direct structuring additive included in the present invention is preferably Copper Chromite.

The LDS additive is 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 6% by weight based on the total weight of the thermoplastic resin composition. If this content is low, laser direct processing is difficult, and the plating part is peeled off at high temperature and high humidity, so it is desirable to maintain more than 6wt%.

When the content of the LDS additive is less than 6%, plating is poor due to peeling during the cross cut test after plating, and if it exceeds 6%, the expensive additive content increases, so there is no economical efficiency, so 6% by weight compared to the total weight of the polymer composition Most preferred.

100 parts by weight of the polymer composition, 0.1 to 20% by weight of glass bubbles, preferably 0.1 to 15% by weight, more preferably 5 to 10% by weight. When glass bubbles are contained, dielectric loss is reduced in a high-frequency region. Generally, glass bubbles are processed during the processing of a polymer compound, such as high pressure spraying, kneading, extrusion, pultrusion, sintering, or molding (e.g., compression molding, injection molding, blow molding, rotational molding ( roto-molding), thermoforming, and injection-compression molding) are preferred to be strong enough to avoid breaking or breaking.

In general, glass bubbles lower the weight of the polymer composition and improve its processability, dimensional stability and flow properties. In addition, due to its heat resistance, heat insulation properties, pressure resistance, impact resistance, and hollow particle structure, it can have a low dielectric constant, which can be imparted as bulk properties to the compositions containing them.

In certain embodiments, the polymer composition may use talc as a filler, and when talc is used, the polymer composition has a DK value of about 3.5. Therefore, a glass bubble can be used to lower the DK value to 3.0 or less.

When the glass bubble additive is contained, dielectric loss is reduced in the high-frequency region. The average particle diameter of the glass bubbles is preferably 5 μm or more from the viewpoint of moldability, more preferably 10 μm or more, and preferably from 200 μm or less from the viewpoint of suppression of breakage of the glass bubbles and formability. It is more preferably 100 µm or less, and even more preferably 50 µm or less. The size of the glass bubble added in the present invention is not limited, but is preferably 10 to 20 μm.

Table 1 below shows the DK and DF values for each frequency according to the size of the glass bubble.

MHz 20㎛, Dk 20㎛, Df 15㎛, Dk 15㎛, Df 1000 2.92782 0.031184 3.03833 0.033511 2000 2.85429 0.000042 2.95022 0.000038 3000 2.81965 0.000030 2.91052 0.000075 4000 2.83192 0.000058 2.92629 0.000095 5000 2.86226 0.001432 2.96252 0.001374 6000 2.88055 0.003763 2.98366 0.004090 7000 2.86191 0.004690 2.9604 0.005217 8000 2.78831 0.004919 2.87187 0.005619
The polymer composition of the present invention may include 5 to 50% by weight, preferably 15 to 40% by weight of filler, based on the total weight. The type of the filler is not particularly limited, and examples thereof include mica, Talc, Glass Fiber, graphite, and various metal foils (for example, aluminum foil, iron foil, copper foil). In the present invention, it is most preferable to use Talc. In the case of using glass fiber, plating smearing occurs when laser is directly processed. Therefore, it is more preferable to use Talc having no plating smear and having a low DK value.

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Table 2 below shows that Talc is more preferable than Glass Fiber as a filler for improving physical properties such as durability of the polymer composition. Talc is preferred as a filler of the present invention because it has low dielectric properties.

MHz Talc 40%
Dk Talc 40%
Df Glass Fiber 30%
Dk Glass Fiber 30%
Df 1000 3.45811 0.000046 3.5515 0.000026 2000 3.50351 0.000079 3.64119 0.000058 3000 3.52559 0.000102 3.68521 0.000153 4000 3.52644 0.000136 3.68013 0.000198 5000 3.51339 0.000191 3.64876 0.000170 6000 3.49308 0.001142 3.61376 0.003087 7000 3.47104 0.004500 3.59237 0.006071 8000 3.45094 0.007303 3.59784 0.007847
The polymer composition of the present invention may contain other fillers depending on the selection. The filler is composed of 100 parts by weight of 0 to 40% by weight of the polymer composition, more preferably 0.1 to 20% by weight. When the content of the additive is more than 0% by mass, the required mechanical strength is easily secured, and the curvature suppression effect of the molded body is likely to increase. Moreover, when content is 20 mass% or less, fluidity at the time of melting of a material tends to improve.

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Examples of the filler include glass fibers such as milled glass fibers and split glass fibers; Inorganic fillers such as glass beads, hollow glass spheres, glass powder, mica, talc, clay, silica, alumina, potassium titanate, wollastonite, calcium carbonate (weight, lightweight, gelatinous), magnesium carbonate, basic magnesium carb Bonate, sodium sulfate, calcium sulfate, barium sulfate, calcium sulfite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium silicate, silica sand, silica stone, quartz titanium oxide, zinc jade Seed, iron oxide graphite, molybdenum asbestos, silica alumina fiber, alumina fiber, gypsum fiber, carbon fiber, carbon black, white carbon, diatomaceous earth, bentonite, sericite, sand bar and graphite; And metallic or non-metallic whiskers such as potassium titanate whiskers, alumina whiskers, aluminum borate whiskers, silicon carbide whiskers and silicon nitride whiskers. Glass fibers, glass powder, mica, talc, and carbon fibers are preferably used among them. Two or more kinds of the above fillers can be used in the aromatic liquid crystal polyester resin composition of the present invention.

In the polymer composition according to the present invention, other additives, for example, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, dyes or pigments, coloring agents, lubricants, mold release agents, to the extent that does not impair the effects of the present invention, Crystallization accelerators, crystal nucleating agents, etc. can also be appropriately added depending on the required performance.

The preparation of the polymer composition according to the present invention is not particularly limited. For example, preparation of a polymer composition is achieved by blending LCP resins, LDS additives, glass bubbles, fillers and any other components, and melt kneading them using a single-screw or twin-screw extruder.

A molded article can be obtained by molding the polymer composition of the present invention. Once the polymer composition is prepared, the thermoplastic composition can be molded into a substrate of a desired shape. Typically, the formed part is molded using a one-component injection molding process in which dried and preheated plastic granules are injected into a mold. As disclosed above, a conductive element is then formed on the substrate using a laser direct structure process (LDS). Activation with a laser causes a physicochemical reaction in which the spinel crystals open and release metal atoms. These metal atoms serve as nuclei for metallization (eg, reducing copper coating). The laser also creates microscopically irregular surfaces and removes polymer metrics, while creating numerous fine pits and undercuts that copper can settle during metallization. The final component can be, for example, a molded circuit component (MID) or a component containing an integrated electronic circuit conductive element. Examples of such components include conductive elements such as patch antenna structures, inverse-F antenna structures, closed and open slot antenna structures, loop antenna structures, monopole, dipole, planar inverse-F antenna structures, hybrids of this design, etc. It is to form a variety of different types of antennas, such as an antenna having a resonant element formed by. Due to the high dielectric constant of the thermoplastic composition of the present invention, the size of the antenna structure can be relatively small.

The present polymer composition (eg, antenna structure) is very versatile and can be used for different electronic components. By way of example, the molded part may be formed of an electronic part, such as a desktop computer, portable computer, small electronic device, or the like. In one suitable configuration, the component is available as a relatively small, portable electronic component with as little internal space as possible. In addition, examples of suitable portable electronic components include mobile phones, laptop computers, small portable computers (eg, ultraportable computers, netbook computers and tablet computers), wrist watch devices, pendant devices, headphones and earphone devices, wireless communication capabilities. Media players, portable computers (sometimes also called personal digital assistants), remote controls, satellite positioning system (GPS) devices, portable gaming devices, and the like. The component may also be integrated with other components, such as a camera module, speaker or battery cover of a portable device.

The melt viscosity of the polymer composition may be, for example, about 30 to 50 Pa.s, preferably 45 Pa.s or less, more preferably 40 Pa.s or less. This material has very good fluidity, so high-speed fine injection molding is possible and it can be applied to various fields as electrical / electronic component materials.

The thermoplastic resin composition has excellent mechanical properties. For example, tensile strength of 92 to 129 MPa tensile strength; Flexural strength between about 115 and 198 kPa; About 8.2 to 19.6 ㎬ flexural modulus. The flexural properties can be measured according to ASTM D790.

HDT of the thermoplastic resin composition is characterized in that, for example, about 227 ° C or higher.

The preparation of the liquid crystal resin composition according to the present invention is not particularly limited. For example, a thermoplastic material is prepared by blending a liquid crystal resin, a laser direct structuring additive, a glass bubble, a plate-like filler, and other additives and melt-kneading them using a single-screw or twin-screw extruder.

Example

The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

Melt viscosity : Melt viscosity (Pa · s) was measured according to ISO Test No. 11443 at 350 ° C. and a shear rate of 1000 s-1 using a GOTTFERT RG20 capillary rheometer.

Tensile Strength, Strain at Break : Tensile properties were tested according to ASTM D638.

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Flexural Strength, Flexural Moduls : Flexural properties were tested according to ASTM D790.

HDT : As the thermal property of plastic, it means the maximum limit temperature at which plastic can be used for a specific purpose, and tested according to ASTM D648.

Plating property : The degree of peeling was measured through a cross cut test.

Dielectric constant and loss factor : Dielectric constant (or relative static permittivity) and loss factor were measured using a ROHDE & SCHWARZ ZNB8 or ZNB20 network analyzer and using a coaxial probe type DAK-TL -P. More specifically, it was measured with a flat plate specimen having a size of 60 mm x 60 mm x 2 mm. Ten specimens were tested and the average values reported.

Example

LCP resin 1 polymerization (Example)

15,000 g (146.9 moles) of acetic anhydride was added to a batch reactor of 200 L capacity and 20,000 g (144.8 moles) of monomeric p-hydroxy benzoic acid (HBA) and 9,000 g (48.3 moles) of high purity terephthalic acid were rotated while the stirrer was rotated. (PTA) 6,000 g (36.2 moles), high purity isophthalic acid (PIA) 2,000 g (12.1 moles) were added, and then 12,100 g (118.6 moles) of acetic anhydride was further added to ensure good mixing in a batch reactor. Thereafter, 2.8 g of potassium acetate catalyst and 11.1 g of magnesium acetate catalyst were added. Thereafter, the inner space of the reactor is made inactive, and then the reactor temperature is raised to a temperature at which the acetic anhydride inside the batch reactor is refluxed over 1 hour, and while refluxing at that temperature, acetic anhydride is acetylated with acetylating agent for 2 hours Upset. While increasing the amount of acetic acid produced in the acetylation reaction and removing unreacted anhydrous acetic acid to a temperature of 0.5 ° C./min to 325 ° C. to produce an all-aromatic liquid crystal polyester, cooling and solidifying while discharging through the lower valve 1 Tea pulverization yielded 32,000 g. Subsequently, the mixture was secondly crushed using a fine pulverizer, placed in a rotary furnace, and heated at a flow rate of 25 L / min for 1 hour to 200 ° C while maintaining at this temperature for 2 hours, and then 0.2 ° C / min to 285 ° C. After the temperature was raised to 3 hours, an aromatic aromatic polyester resin was prepared.

LCP resin 2 polymerization (comparative example)

15,000 g (146.9 moles) of acetic anhydride was added to a batch reactor having a capacity of 200 L, and 26,000 g (188.2 moles) of monomer p-hydroxy benzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA) 2,952 were rotated while the stirrer was rotated. g (15.7 mol), biphenol (BP) 7,303 g (39.2 mol), high-purity terephthalic acid (PTA) 9,122 g (54.9 mol), p-acetaminophen (APAP) 2,371 g (15.7 mol), and then acetic anhydride 18,470 More g (181 mol) is added to ensure good mixing in a batch reactor. Thereafter, 3.6 g of potassium acetate catalyst and 14.5 g of magnesium acetate catalyst were added. Thereafter, the inner space of the reactor is made inactive, and then the reactor temperature is raised to a temperature at which the acetic anhydride inside the batch reactor is refluxed over 1 hour, and while refluxing at that temperature, acetic anhydride is acetylated with acetylating agent for 2 hours. Upset. While increasing the amount of acetic acid produced in the acetylation reaction and removing unreacted anhydrous acetic acid to a temperature of 0.5 ° C./min to 325 ° C. to produce an all-aromatic liquid crystal polyester, cooling and solidifying while discharging through the lower valve 1 Tea was ground to obtain 46,000 g. Subsequently, the mixture was secondly crushed using a fine pulverizer, placed in a rotary furnace, and heated at a flow rate of 25 L / min for 1 hour to 200 ° C while maintaining at this temperature for 2 hours, and then 0.2 ° C / min to 288 ° C After the temperature was raised to 3 hours, an aromatic aromatic polyester resin was prepared.

Table 3 below shows the dielectric properties by frequency by polymerizing two resins having different monomer types and compositions. (Composition is 100% by weight of resin)

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No. Monomer composition 1 GHz 5 GHz 8 GHz HBA HNA BP TPA IPA APAP Dk Df Dk Df Dk Df Example 60 - 20 15 5 - 3.11 8.7 * 10 ^-3 3.10 7.7 * 10 ^-4 3.04 8.1 * 10 ^-3 Comparative example 60 5 12.5 17.5 - 5 3.13 8.2 * 10 ^-3 3.17 3.1 * 10 ^-3 3.17 1.2 * 10 ^-2

* Dk: dielectric constant * Df: dielectric dissipation factor

(Example) In the case of HBA / BP / TPA / IPA = 60/20/15/5 composition resin, it shows the characteristic that the Dk value decreases toward the high frequency region.

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(Comparative example) In the case of HBA / HNA / BP / TPA / APAP-60 / 5 / 12.5 / 17.5 / 5 composition resin, the dielectric constant and dielectric loss increase as it goes to the high frequency region.

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Table 4 below shows specific DK and DF values for LCP resin 2 (comparative example).

MHz LCP Resin 2 Dk LCP Resin 2 Df 1000 3.13531 0.009958 1500 3.15816 0.007721 2000 3.17638 0.005392 2500 3.18202 0.004611 3000 3.19769 0.00317 3500 3.19737 0.00253 4000 3.19149 0.002371 4500 3.18199 0.002649 5000 3.17077 0.003311 5500 3.15953 0.0043 6000 3.14979 0.005556 6500 3.14287 0.007017 7000 3.13994 0.008615 7500 3.14206 0.01028 8000 3.15019 0.011934

Examples 3 to 12

Preparation of Compound: Using the twin-screw extruder, the additives in the following table were added to the following LCP resin in a weight ratio, followed by melt kneading.

Table 5 below shows the types of substances and additives and their composition. (100% by weight of the present invention.)

3 4 5 6 7 8 9 10 11 12 LCP Resin 1 (wt%) 54 55 53 54 64 64 64 64 64 - LCP Resin 2 (wt%) - - - - - - - - - 54 Copper Chromite (wt%) 6 5 7 6 6 6 6 6 6 6 Talc (wt%) 40 40 40 30 - 20 15 20 15 40 Glass Fiber (wt%) - - - 10 30 - - - - - Glass Bubble 1 (20㎛, wt%) - - - - - 5 10 - - - Glass Bubble 2 (15㎛, wt%) - - - - - - - 5 10 -

Table 6 is a result of the material composition of Table 2.

3 4 5 6 7 8 9 10 11 12 Melt Viscosity
(Pa.s) 49 46 43 47 39 48 36 50 108 56 Tensile Strength (MPa) 88 92 93 100 129 99 90 104 98 97 Strain at Break (%) 4.0 4.1 4.1 3.3 1.9 4.2 4.7 4.3 5.1 3.64 Flexural Strength (MPa) 128 131 134 145 198 138 115 143 123 132 Flexural Modulus (GPa) 12.1 12.8 13.0 14.7 19.6 12.3 8.2 12.6 8.5 12.0 HDT (℃) 233 235 236 257 267 254 234 254 235 238 Plating property ○ X ○ ○ ○ ○ ○ ○ ○ ○ 1 GHz Dk 3.46 3.45 3.45 3.53 3.94 3.10 2.68 3.08 2.67 3.67 Df (10 ^-3 ) 4.37 4.28 4.36 7.81 9.59 0.73 0.18 0.71 0.10 5.48 10 GHz Dk 3.46 3.46 3.47 3.45 3.92 3.08 2.67 3.07 2.65 3.75 Df (10 ^-3 ) 0.64 0.65 0.60 0.73 0.79 0.22 0.07 0.40 0.06 0.81

* Plating property O: No peeling during cross cut test after plating

 Plating property X: Peeling occurs during cross cut test after plating

 The content of copper chromite that affects the plating property is more than 6%

If the content of copper chromite is less than 6%, plating is poor due to peeling during the cross cut test after plating, and if it exceeds 6%, the expensive additive content increases, so there is no economical efficiency. Fit

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 When using glass bubble, it can be confirmed that the dielectric properties are reduced at high frequencies.

 In particular, it can be seen that the lower the dielectric properties, the higher the frequency range.

When glass bubble is used, the Dk value that can be used in the 5G repeater is less than 3, and the Df value is close to 0, so it can be used. In particular, the performance of a large glass bubble is better. When the size of the glass bubble is 15㎛ at 1GHz, the Dk value becomes 3 or more, so the size of the glass bubble is also better than 15㎛.

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Claims (7)

Oil field obtained by polymerizing the monomer mixture obtained by mixing p-hydroxybenzoic acid, biphenol, terephthalic acid, and isophthalic acid in acetic anhydride under reflux temperature of acetic anhydride. An aromatic liquid crystal polyester resin having a low dielectric constant in a high frequency region, showing a constant (Dk) and a dielectric loss coefficient (Df) in the range of 0.0087 to 0.00077 in the frequency range of 1 GHz to 8 GHz,
The p-hydroxy benzoic acid ranges from 50 to 70% by weight based on the weight of the monomer mixture;
The biphenol ranges from 10 to 30% by weight based on the weight of the monomer mixture;
An aromatic liquid crystal polyester resin having low dielectric properties in a high frequency region, wherein the terephthalic acid and isophthalic acid range from 10 to 40% by weight based on the weight of the monomer mixture. delete delete delete delete delete A material for 5G communication comprising an aromatic liquid crystal polyester resin having low dielectric properties in the high frequency region according to claim 1.

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