KR102507218B1 - Thermotropic liquid crystal polyester resin composition and manufacturing method thereof. - Google Patents

Abstract

The present invention relates to a TLCP resin composition and a method for preparing the same, and specifically, a TLCP resin composition having excellent thermal, mechanical and rheological properties and overcoming the disadvantages of TLCP in which fibrillation occurs quickly by melt-compounding TLCP and PCT, and It relates to a manufacturing method thereof.

Description

TLCP resin composition and its preparation method. {Thermotropic liquid crystal polyester resin composition and manufacturing method thereof.}

The present invention relates to TLCP resin compositions and methods for their preparation.

BACKGROUND ART In recent years, thermoplastic resins having high heat resistance have been required for parts materials for electric/electronic devices, materials for parts for automobile devices, materials for parts for chemical devices, and the like. Liquid crystalline polyester resins are also one of the resins that meet these requirements, and are often applied to precise molded products because of their low shrinkage rate when solidified from a molten state and good fluidity. However, it has problems in that release from the mold is poor during molding, stable continuous molding is difficult, and productivity is poor because the molding speed (molding cycle) is slow. In the prior art, as a method for improving releasability, a method in which a releasability improver is generally added to a resin is used. As the releasability improving agent, the following are known. (1) a method of adding a metal salt of a fatty acid such as zinc stearate or lithium stearate, (2) a method of adding an ester of a fatty acid such as glycerol tristearate, (3) N, N'-alkylene bisalkanamide, etc. A method for adding amides of fatty acids. However, in all of the methods (1), (2), and (3), the thermal decomposition temperature of the release property improving agent is lower than the molding processing temperature of the liquid crystalline polyester resin, and the molded article resulting from the decomposition of the release property improving agent is recognized, although the mold release effect is recognized. It has problems such as discoloration, deterioration of mechanical properties, gas generation during kneading and molding.

In addition, recently, the use environment of the liquid crystalline polyester resin has become more severe, and improved heat resistance has been urgently required. In order to meet the demand, a liquid crystalline polyester resin with a higher melting point has been used, but the problem of a high processing temperature and a decrease in process efficiency has not been easily solved.

In particular, thermotropic liquid crystal polyester is a polymer that exhibits liquid crystal properties in a molten state, and is used in many parts of engineering plastics due to its excellent performance such as high thermal stability, mechanical properties, and molecular orientation. However, there are problems in that fibrillation occurs rapidly, and abrasion resistance is deteriorated, and image defects occur. In order to solve this problem, Japanese Patent Laid-Open No. 2010-106165 discloses a technique for adding additives such as inorganic particles such as silica, but in this case, mechanical and thermal properties are deteriorated.

Therefore, the inventors of the present invention have maintained or improved the physical properties of thermotropic liquid crystal polyester (hereinafter referred to as TLCP) resin having excellent mechanical and rheological properties, heat resistance at high temperature, and a resin capable of significantly suppressing the fibrillation As a result of research to prepare the composition, the composition obtained by melting and compounding polycyclohexylenedimethylterephthalate (hereinafter referred to as PCT) together with TLCP can improve the disadvantages of the conventional TLCP, and at the same time, the existing The present invention was completed by confirming that the thermal and mechanical properties of the TLCP resin were maintained or significantly improved.

Korean Patent Publication No. 10-2012-0010134 (2012.02.02)

The present invention is intended to solve the problems of the prior art as described above, and overcomes the disadvantage of rapid fibrillation of TLCP, has excellent processability, and maintains or improves thermal and mechanical properties compared to TCLP alone polymers. It is intended to provide a TLCP resin composition and a method for preparing the same.

In particular, an object of the present invention is to provide a TLCP resin composition having good surface roughness characteristics due to suppression of fibrillation, remarkably improved wear resistance, and excellent physical properties after processing.

In addition, an object of the present invention is to provide a TLCP resin composition having excellent heat resistance due to its high melting point, high crystallization temperature and high glass transition temperature.

In addition, one aspect of the present invention is to provide a TLCP resin composition that does not cause problems such as deformation of a molded article or deterioration of mechanical properties during molding because the thermal decomposition initiation temperature is not significantly lowered compared to the TCLP single polymer.

In addition, one aspect of the present invention is to provide a TLCP resin composition capable of suppressing a decrease in storage modulus in a wide temperature range and having excellent shape stability.

In order to achieve the above object, one aspect of the present invention is a TLCP resin composition comprising TLCP and PCT, wherein the TLCP is any one or two selected from repeating units represented by Formula 1, Formula 2 and Formula 3 below. Including the above, the PCT provides a TLCP resin composition comprising a repeating unit represented by Formula 5 below.

[Formula 1]

-O-Ar ¹ -CO-

[Formula 2]

-CO-Ar ² -CO-

[Formula 3]

-X-Ar ³ -Y-

(In Formulas 1 to 3, Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylene group;

Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylene group, or a group represented by the following formula (4);

X and Y each independently represent an oxygen element or an imino group;

The hydrogen element contained in the group represented by Ar ¹ , Ar ² or Ar ³ may be independently substituted with a halogen element, an alkyl group of 1 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.)

[Formula 4]

-Ar ⁴ -Z-Ar ⁵ -

(In Formula 4, Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group; Z represents an oxygen element, a sulfur element, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms.)

[Formula 5]

In one embodiment of the present invention, the TLCP may include a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid.

In one embodiment of the present invention, the melting point of the resin composition may be 200 ℃ or more.

In one embodiment of the present invention, the resin composition may have a crystallization temperature of 100°C or higher.

In one embodiment of the present invention, the glass transition temperature of the resin composition may be 60 ℃ or more.

In one embodiment of the present invention, the thermal decomposition initiation temperature of the resin composition may be 400 to 600 ℃.

Another aspect of the present invention is a method for preparing a TLCP resin composition comprising the step of preparing a TLCP resin composition by melt-compounding TLCP and PCT, wherein the TLCP is represented by the following formulas 1, 2 and 3: It includes any one or two or more units selected from among units, and the PCT provides a method for preparing a TLCP resin composition comprising a repeating unit represented by Formula 5 below.

[Formula 1]

-O-Ar ¹ -CO-

[Formula 2]

-CO-Ar ² -CO-

[Formula 3]

-X-Ar ³ -Y-

(In Formulas 1 to 3, Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylene group;

Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylene group, or a group represented by the following formula (4);

X and Y each independently represent an oxygen element or an imino group;

The hydrogen element contained in the group represented by Ar ¹ , Ar ² or Ar ³ may be independently substituted with a halogen element, an alkyl group of 1 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.)

[Formula 4]

-Ar ⁴ -Z-Ar ⁵ -

(In Formula 4, Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group; Z represents an oxygen element, a sulfur element, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms.)

[Formula 5]

In one embodiment of the present invention, the melt compounding may be performed at a stirring speed of 10 to 1000 rpm in a temperature range of 200 to 400 °C.

In one embodiment of the present invention, the TLCP may include a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid.

Another aspect of the present invention provides a molded article formed from the TLCP resin composition described above.

The present invention provides a TLCP resin composition and a method for producing the same, wherein the TLCP resin composition overcomes the disadvantage of rapid fibrillation of TLCP, has excellent processability, and maintains thermal and mechanical properties compared to TCLP alone polymers Or there is an effect that can be improved.

In particular, the TLCP resin composition according to one aspect of the present invention has good surface roughness characteristics due to suppression of fibrillation, remarkably improved abrasion resistance, and excellent physical properties after processing.

In addition, the TLCP resin composition according to one aspect of the present invention has a high melting point, crystallization temperature, and glass transition temperature, and thus has excellent heat resistance.

In addition, the TLCP resin composition according to one aspect of the present invention has the advantage that the thermal decomposition initiation temperature is not significantly lowered compared to the TCLP single polymer, so that problems such as deformation of molded articles or deterioration of mechanical properties during molding do not occur.

In addition, the TLCP resin composition according to one aspect of the present invention can suppress the decrease in storage modulus in a wide temperature range, and thus has excellent shape stability.

1 shows a fracture surface of a TLCP resin composition according to an embodiment of the present invention and a fracture surface of a single TLCP polymer observed by scanning electron microscopy (SEM).

Hereinafter, a TLCP resin composition and a manufacturing method thereof according to the present invention will be described in detail.

Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms used in the description in the present invention are merely to effectively describe specific embodiments and are not intended to limit the present invention. In addition, the unit of additives not specifically described in the specification may be % by weight.

Also, the singular forms used in the specification and appended claims are intended to include the plural forms as well, unless the context dictates otherwise.

In the present invention, by melting compounding TLCP and PCT, the disadvantage of rapid fibrillation of TLCP is overcome, processability is very excellent, and TLCP that can maintain or improve thermal, mechanical and rheological properties compared to TCLP alone polymer A resin composition and a method for preparing the same are provided.

At this time, as mentioned above, TLCP means thermotropic liquid crystal polyester, and PCT means polycyclohexylenedimethyl terephthalate hereinafter.

The present invention will be described in detail as follows.

The TLCP resin composition according to one aspect of the present invention includes TLCP and PCT,

The TLCP may include any one or two or more repeating units represented by Formula 1, Formula 2, and Formula 3 below, and the PCT may include a repeating unit represented by Formula 5 below.

[Formula 1]

-O-Ar ¹ -CO-

[Formula 2]

-CO-Ar ² -CO-

[Formula 3]

-X-Ar ³ -Y-

In this case, in Formulas 1 to 3, Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylene group; Ar ² and Ar ³ are, independently of each other, a phenylene group, a naphthylene group, a biphenylene group, or a represents the group represented by 4; X and Y each independently represent an oxygen element or an imino group; Ar ¹ , Ar ² or Ar ³ represents a hydrogen element contained in the group represented by each other independently of each other, a halogen element, 1 to 10 carbon atoms It may be substituted with an alkyl group of 10 or an aryl group of 6 to 20 carbon atoms.

[Formula 4]

-Ar ⁴ -Z-Ar ⁵ -

In this case, in Formula 4, Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group; Z represents an oxygen element, a sulfur element, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms; The hydrogen element contained in the group represented by Ar ⁴ or Ar ⁵ may be independently substituted with a halogen element, an alkyl group of 1 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.

[Formula 5]

In one aspect of the present invention, examples of the halogen element include, but are not limited to, fluorine, chlorine, bromine and iodine.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, 2 -Ethylhexyl group, n-octyl group, n-decyl group, etc. may be mentioned, but it is not necessarily limited thereto.

Examples of the aryl group having 6 to 20 carbon atoms include, but are not limited to, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group.

When the hydrogen element contained in the group represented by Ar ¹ , Ar ² or Ar ³ is substituted with the halogen element, the alkyl group having 1 to 10 carbon atoms, or the aryl group having 6 to 20 carbon atoms, a group that substitutes the hydrogen element The number of may be independently of each other, preferably two or less, more preferably one, for each group represented by Ar ¹ , Ar ² or Ar ³ , but is not necessarily limited thereto.

Examples of the alkylidene group having 1 to 10 carbon atoms include, but are not limited to, methylene group, ethylidene group, isopropylidene group, n-butylidene group and 2-ethylhexylidene group.

When the hydrogen element contained in the group represented by Ar ⁴ or Ar ⁵ is substituted with the halogen element, the alkyl group having 1 to 10 carbon atoms, or the aryl group having 6 to 20 carbon atoms, the number of groups substituting the hydrogen element is Each group represented by , Ar ⁴ or Ar ⁵ may be independently of each other, preferably two or less, more preferably one, but is not necessarily limited thereto.

In one aspect of the present invention, the repeating unit represented by Formula 1 is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid, and is a repeating unit derived from p-hydroxybenzoic acid (ie, Ar ¹ is p- phenylene group), or a repeating unit derived from 6-hydroxy-2-naphthoic acid (ie, Ar ¹ is a 2,6-naphthylene group), but is not necessarily limited thereto.

In addition, the repeating unit represented by Formula 2 is a repeating unit derived from a predetermined aromatic dicarboxylic acid, a repeating unit derived from terephthalic acid (ie, Ar ² is a p-phenylene group), and a repeating unit derived from isophthalic acid. It is more preferable that it is a unit (ie, Ar ² is a m-phenylene group) or a repeating unit derived from 2,6-naphthalenedicarboxylic acid (ie, Ar ² is a 2,6-naphthylene group), but is necessarily limited thereto. It is not.

In addition, the repeating unit represented by Formula 3 is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine, and is a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine. unit (ie, Ar ³ is a p-phenylene group), or a repeat derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl It is more preferable that it is a unit (ie, Ar ³ is a 4,4'-biphenylene group), but it is not necessarily limited thereto.

When the TLCP according to one aspect of the present invention includes all of the repeating units represented by Formula 1, Formula 2 and Formula 3, the sum of the repeating units represented by Formula 1, Formula 2 and Formula 3 is 100 moles When expressed as %, the content of the repeating unit represented by Formula 1 may be 30 mol% or more, more preferably 40 mol% or more, specifically 30 to 90 mol%, and more preferably 40 to 90 mol%. It may be %, but is not necessarily limited thereto.

More specifically, the TLCP according to one aspect of the present invention may include a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid, more preferably p - It may be a copolymer composed of a repeating unit derived from hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid, but is not necessarily limited thereto.

When the TLCP according to one aspect of the present invention is a copolymer composed of a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid, the repeating unit derived from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, when the sum of the content of repeating units derived from 100 mol% is taken, the content of repeating units derived from p-hydroxybenzoic acid is 90 mol% or less, preferably 80 mol%. It may be % or less, specifically 50 to 90 mol%, preferably 50 to 80 mol%, but is not necessarily limited thereto. In addition, the content of the repeating unit derived from 6-hydroxy-2-naphthoic acid may be 10 mol% or more, preferably 20 mol% or more, specifically 10 to 50 mol%, preferably 20 to 50 mol%. It may be mol%, but is not necessarily limited thereto.

As mentioned above, the TLCP resin composition according to one aspect of the present invention may contain PCT together with the above-described TLCP, and in this case, the PCT may include a repeating unit represented by Formula 5 below.

[Formula 5]

In addition, the TLCP resin composition according to one aspect of the present invention comprises 1 to 99 parts by weight of the PCT, preferably 10 to 50 parts by weight, and more preferably 10 to 30 parts by weight, based on the total weight of the TLCP resin composition. It can, but is not necessarily limited thereto.

PCT is a semi-crystalline polymer obtained by condensation polymerization of terephthalic acid and cyclohexanedimethanol, and has the advantages of high chemical resistance, dimensional stability, and low water absorption. Therefore, by mixing TLCP and PCT, as mentioned above, suppression of fibrillation and processability improvement can be achieved.

More specifically, fibrillation is a phenomenon that occurs due to the fibrous molecular structure unique to liquid crystal polymers, and the TLCP resin composition according to one aspect of the present invention is obtained by blending TLCP with PCT having the above characteristics, Fibrillar molecules in the medium are in a moderately bent state, whereby friction between molecules is suppressed, and therefore fibrillation can be highly suppressed.

Therefore, when the TLCP resin composition according to one aspect of the present invention includes TLCP and PCT according to the above content ratio, the disadvantage of rapid fibrillation of TLCP is overcome, and the surface roughness characteristics are very good, the smoothness of the surface, Abrasion resistance, hygroscopicity, deodorization, etc. are significantly improved, and utilization as a resin composition included in molded articles requiring washing, bonding with other members, etc. can be increased, and there is a surprising effect that can contribute to improving the appearance of products.

Specifically, in the TLCP resin composition according to one aspect of the present invention, the presence of fibrils was not confirmed in both the fibrillation evaluation using an eraser and the fibrillation evaluation using ultrasonic waves, indicating that fibrillation was highly inhibited.

In addition, a ceramic rod guide (material YM-99C) with a diameter of 4 mm is pressed with a contact angle of 2.7 °, and the guide is rubbed in the axial direction at a stroke length of 30 mm and a stroke speed of 600 times / min. Wear resistance measured by measuring the time until occurrence of white powder or fibrils on the rod guide or on the sample surface is confirmed, and obtaining an average value of 5 times excluding the maximum and minimum values among the 7 measurements is not limited thereto, 35 seconds or more, preferably 50 seconds or more, more preferably 80 seconds or more, measured as a significantly longer time compared to the single TLCP polymer, confirming that the wear resistance is very excellent.

In addition, the surface roughness measured by calculating the roughness average from the surface irregularity image of 5㎛×5㎛ area obtained by tapping mode using an atomic force microscope (XE-120 System, PSIA) Although not limited thereto, it was confirmed that the characteristics were very good, showing a lower value than that of a single TLCP polymer at 45 nm or less, more preferably 30 nm or less.

As described above, the TLCP resin composition according to one aspect of the present invention suppresses fibrillation, has excellent abrasion resistance and good surface roughness, does not deteriorate physical properties after processing, and has excellent post-processing properties, so it is industrially useful. There are significant advantages.

In addition, the TLCP resin composition according to one aspect of the present invention does not lower the melting point, crystallization temperature, and glass transition temperature at all compared to the TLCP single polymer, has excellent heat resistance and thermal stability, and the thermal decomposition onset temperature is also not significantly lowered compared to the TLCP single polymer. In addition, problems such as deformation of the molded article or deterioration of mechanical properties during molding do not occur, and there is an effect of excellent shape stability by suppressing the decrease in storage modulus in a wide temperature range.

Looking more specifically, the TLCP resin composition according to one aspect of the present invention may have a melting point of 200 ° C. or higher, preferably 250 ° C. or higher, but is not necessarily limited thereto.

In addition, the TLCP resin composition according to one aspect of the present invention may have a crystallization temperature of 100°C or more, preferably 150°C or more, and more preferably 200°C or more, but is not necessarily limited thereto.

In addition, the TLCP resin composition according to one aspect of the present invention may have a glass transition temperature of 60° C. or higher, preferably 100° C. or higher, but is not necessarily limited thereto.

As described above, the melting point, crystallization temperature and glass transition temperature of the TLCP resin composition according to one aspect of the present invention are not lowered at all compared to the TLCP single polymer, and in some cases have higher values, and its heat resistance and thermal stability are also very It has the advantage of being excellent and can be used for molded products in more diverse technical fields.

In addition, the TLCP resin composition according to one aspect of the present invention may have a thermal decomposition initiation temperature of 400 to 600 ° C, preferably 400 to 500 ° C, but is not necessarily limited thereto.

By having the thermal decomposition initiation temperature in the above range, the TLCP resin composition according to one aspect of the present invention does not significantly decrease the thermal decomposition initiation temperature compared to the TLCP single polymer, and if the thermal decomposition initiation temperature is significantly lowered and lower than the molding processing temperature, at the time of molding However, the TLCP resin composition according to one aspect of the present invention has the advantage that such problems do not occur.

In addition, the molded article formed from the TLCP resin composition according to one aspect of the present invention has a storage modulus of 2.0 to 5.0 GPa at -50 ° C, a storage modulus of 1.0 to 3.0 GPa at 30 ° C, and a storage modulus at 100 ° C. It may be 0.5 to 2.0 GPa, but is not necessarily limited thereto.

In addition, at this time, the molded article formed from the TLCP resin composition according to one aspect of the present invention may have a difference between the storage modulus at -50 ° C and the storage modulus at 100 ° C of 3.0 GPa or less, more preferably 2.0 Gpa or less, but is necessarily limited thereto It is not.

By having the storage modulus in the above range, the TLCP resin composition according to one aspect of the present invention can suppress the decrease of the storage modulus in a wide temperature range, and the deformation against external stress is low, so that high form stability can be realized. there is

As a result, in the case of TLCP, the shear viscosity may be relatively good due to the liquid crystal alignment characteristics in the molten state, but the processability may be relatively good. The resin composition can highly suppress fibrillation by mixing TLCP and PCT, and at the same time, compared to TLCP, heat resistance and mechanical properties are not lowered at all, and melting point, thermal decomposition initiation temperature, etc. are maintained, so that melt processability is not lowered at all. , The range of utilization can be remarkably widened, and the effects of the present invention listed above are very significant.

Another aspect of the present invention relates to a method for preparing the TLCP resin composition.

Specifically, the method for preparing a TLCP resin composition according to one aspect of the present invention includes the step of preparing a TLCP resin composition by melt-compounding TLCP and PCT,

The TLCP may include any one or two or more repeating units represented by Formula 1, Formula 2, and Formula 3 below, and the PCT may include a repeating unit represented by Formula 5 below.

[Formula 1]

-O-Ar ¹ -CO-

[Formula 2]

-CO-Ar ² -CO-

[Formula 3]

-X-Ar ³ -Y-

In this case, in Formulas 1 to 3, Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylene group; Ar ² and Ar ³ are, independently of each other, a phenylene group, a naphthylene group, a biphenylene group, or a represents the group represented by 4; X and Y each independently represent an oxygen element or an imino group; Ar ¹ , Ar ² or Ar ³ represents a hydrogen element contained in the group represented by each other independently of each other, a halogen element, 1 to 10 carbon atoms It may be substituted with an alkyl group of 10 or an aryl group of 6 to 20 carbon atoms.

[Formula 4]

-Ar ⁴ -Z-Ar ⁵ -

In this case, in Formula 4, Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group; Z represents an oxygen element, a sulfur element, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms; The hydrogen element contained in the group represented by Ar ⁴ or Ar ⁵ may be independently substituted with a halogen element, an alkyl group of 1 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.

[Formula 5]

A detailed description of the TLCP resin composition is omitted since it is the same as described above.

In the method for producing a TLCP resin composition according to one aspect of the present invention, the melt compounding may be performed at a stirring speed of 10 to 1000 rpm in a temperature range of 200 to 400 ° C, preferably 200 to 300 ° C, but must be It is not limited to this.

When the above range is satisfied, in the process of preparing the TLCP resin composition through melt compounding, it is possible to smoothly knead the TLCP and PCT while minimizing the decomposition of the polymer due to thermal or mechanical stirring.

At this time, the method for producing the TLCP resin composition according to one aspect of the present invention may be prepared by melt-kneading TLCP, PCT and other components used as necessary using an extruder and extruding them into pellets, but it is necessarily limited to this It is not.

In addition, the extruder preferably has a cylinder, at least one screw disposed in the cylinder, and at least one supply port formed in the cylinder, and more preferably, one that further includes at least one vent portion formed in the cylinder may be used. , but is not necessarily limited thereto.

Another aspect of the present invention relates to a molded article formed from the TLCP resin composition described above.

In one aspect of the present invention, a melt molding method is preferable as the molding method of the TLCP resin composition, and one example thereof is an extrusion molding method such as an injection molding method, a T-die method, or an inflation method, a compression molding method, a blow molding method, a vacuum molding method, and Press molding etc. are mentioned, Among them, although injection molding method is more preferable, it is not necessarily limited to this.

Examples of molded articles formed from the liquid crystal polyester resin composition according to one aspect of the present invention include electric parts, electronic parts, and optical parts. More specifically, connectors such as IMMs, DDRs, CPU sockets, S/Os, DIMMs, board-to-board connectors, FPC connectors, and card connectors, relays such as sockets, relay cases, relay bases, relay spools, and relay armatures. Components, coil bobbins such as optical pick-up bobbins and trans bobbins, oscillators, printed wiring boards, circuit boards, semiconductor packages, computer-related parts, camera barrels, optical sensor casings, compact camera module casings (packages, barrels), projector optical engine components semiconductor manufacturing process-related parts such as members, IC trays, and wafer carriers; home appliance parts such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture parts such as lamp reflectors, LED reflectors, and lamp holders; parts for audio products such as compact discs, laser discs (registered trademark), and speakers; A ferrule for an optical cable, a telephone component, a facsimile component, and a communication device component such as a modem may be mentioned, but this is a non-limiting example and is not necessarily limited thereto.

The present invention will be described in more detail based on the following Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Physical property measurement method]

(1) evaluation of fibrillation

1) Evaluation of fibrillation using an eraser

The surfaces of the samples according to Examples and Comparative Examples were rubbed back and forth 30 times in the MD direction using an eraser specified in JIS S 6050, and the presence or absence of fibrils was visually confirmed.

2) Evaluation of fibrillation using ultrasound

Samples according to Examples and Comparative Examples were immersed in an ultrasonic cleaner (Ultrasonic Cleaning Machine US-102 from SND Corporation Ltd.), and ultrasonic cleaning was performed for 5 minutes at an oscillating frequency of 38 kHz and an output of 100 W. After washing, the presence or absence of fibrils on the resin surface was confirmed visually and under a microscope.

<Evaluation Criteria>

Good: If no fibrils were identified

Bad: If fibrils are identified

(2) Complex shear viscosity

For the samples according to Examples and Comparative Examples, the composite shear viscosity was measured using a rheometer (MCR 102, Anton Paar) in a plate-plate structure (diameter 25 mm, spacing 1 mm) at a temperature of 290 degrees and an angular velocity in the range of 0.1-100 rad / s was measured while dynamically applying shear.

(3) Wear resistance

A ceramic rod guide (material YM-99C) with a diameter of 4 mm was pressed at a contact angle of 2.7 ° so as to be perpendicular to the samples according to Examples and Comparative Examples, and the guide was axially rubbed at a stroke length of 30 mm and a stroke rate of 600 times / min. Observation under a stereo microscope every 15 seconds, measuring the time until the occurrence of white powder or fibrils on the rod guide or on the sample surface is confirmed, and the average value of 5 measurements excluding the maximum and minimum values among the 7 measurements It was obtained and the wear resistance was measured. At this time, it can be said that the longer the average time, the better the wear resistance.

(4) surface roughness

For the samples according to Examples and Comparative Examples, the surface roughness is the arithmetic mean roughness ( Roughness average) was calculated and measured.

(5) melting point and crystallization temperature

Melting points and crystallization temperatures were determined by differential scanning calorimetry (DSC) as known in the art. Under the DSC procedure, the sample was heated and cooled at 20° C. per minute as stated in ISO standard 10350 using DSC measurements performed on an instrument (DSC 6000, PerkinElmer).

(6) Thermal decomposition initiation temperature

The thermal decomposition temperature was measured through a thermogravimetric analyzer (TGA: Thermogravimetric Analyzer, TGA 4000, PerkinElmer) as is known in the art. The 3% weight loss thermal decomposition initiation temperature was confirmed. Thermogravimetric analysis was performed under an air atmosphere, and weight loss was measured while heating from 100 °C to 600 °C.

(7) Storage modulus and glass transition temperature

The storage modulus of elasticity was measured using a DMA (Dynamic Mechanical Analyzer, DMA 8000, PerkinElmer) equipment under conditions of a heating rate of 5°C/min, frequency of 10 Hz, amplitude of 3 μm, and tensile mode. Then, from the obtained results, the storage modulus at -50°C and 100°C and the maximum value of tan δ (glass transition temperature Tg) were determined.

[Examples 1 to 9]

TLCP copolymer (Seyang Polymer Co., Ltd., F600BB) and PCT (SK Chemical, SkyPURA 0302) was dried under vacuum at 100 °C for 24 hours. Thereafter, the dried TLCP copolymer and PCT were mixed in the amounts shown in Table 1, and then melted and compounded at a cylinder set temperature of 290 ° C and a stirring speed of 75 rpm using a 44 mm twin screw extruder (Bautek, BA11), followed by water bath Pellets were formed by cooling at , and then samples prepared by compressing the obtained pellets using a hot press at 290 ° C. were evaluated.

The physical properties of the obtained samples are shown in Tables 1 and 2 below.

[Comparative Example 1]

Except for using the pure TLCP copolymer without mixing PCT in the examples, pellets were prepared as in the examples, and samples prepared by compressing them were evaluated.

The physical properties of the obtained samples are shown in Tables 1 and 2 below.

TLCP content
(wt%) PCT content
(wt%) Fibrillation evaluation complex
shear
viscosity
(Pa s) wear resistance
(sec) surface
asperity
(nm) melting point
(℃) crystallization temperature
(℃) glass
transition
temperature
(℃) Pyrolysis initiation
temperature
(℃) eraser ultrasonic wave Example 1 90 10 Good Good 33142 38 31 282 253 116 429 Example 2 85 15 Good Good 27522 43 39 283 252 116 429 Example 3 80 20 Good Good 21615 34 23 283 253 116 427 Example 4 75 25 Good Good 15564 57 27 283 253 118 424 Example 5 70 30 Good Good 14822 61 24 282 253 119 422 Example 6 60 40 Good Good 6656 45 21 282 253 119 420 Example 7 50 50 Good Good 4163 78 25 282 254 120 420 Example 8 40 60 Good Good 2140 63 13 283 254 118 420 Example 9 30 70 Good Good 1550 85 18 283 254 117 420 Comparative Example 1 100 0 error error 20651 24 57 280 245 115 480

As shown in Table 1, Examples 1 to 9, which are compositions obtained by melt-compounding TLCP and PCT, showed good results in both methods of fibrillation evaluation, especially in comparison with the single TLCP polymer. Compared to Example 1, it was confirmed that very good evaluation results were obtained in terms of surface roughness characteristics, and at the same time, abrasion resistance was also measured for a longer time and significantly improved.

As shown in Table 1, this is considered to be an effect resulting from the difference in composite shear viscosity and the difference in PCT content between Examples and Comparative Examples. Specifically, the composite shear viscosity of Examples 1 to 3 according to one aspect of the present invention is higher than that of the single TLCP polymer of Comparative Example 1, thereby reducing chain orientation of TLCP and reducing fibrillation. On the other hand, in the case of Examples 4 to 9 according to one aspect of the present invention in which a relatively excessive amount of PCT is mixed, the composite shear viscosity is reduced compared to the single TLCP polymer, but in this case, PCT is the matrix as a whole and TLCP is the domain component. Even if the complex shear viscosity is rather low, fibrillation does not occur due to the orientation characteristics of PCT.

In addition, in Examples 1 to 9, the melting point, crystallization temperature, and glass transition temperature are not lowered at all compared to Comparative Example 1, which is a single TLCP polymer, and the thermal decomposition initiation temperature is not significantly lowered, so that post-processability is improved by suppressing fibrillation. At the same time, it was confirmed that physical properties such as heat resistance and thermal stability could also be maintained excellently.

storage modulus
(GPa) temperature -50℃ 30℃ 100℃ Example 1 4.22 2.87 1.46 Example 2 2.98 1.95 0.98 Example 3 2.75 1.79 0.93 Example 4 2.84 1.84 0.99 Example 5 3.03 2.04 1.11 Example 6 2.37 1.61 0.99 Example 7 2.47 1.75 1.10 Example 8 2.10 1.51 0.96 Example 9 1.98 1.48 0.94 Comparative Example 1 4.09 2.43 1.08

As shown in Table 2, Examples 1 to 9, which are compositions obtained by melt compounding TLCP and PCT, are stored as the temperature rises from -50 ° C to 100 ° C, compared to Comparative Example 1, which is a single TLCP polymer. It was confirmed that the degree of decrease in elastic modulus was not large.

As described above, the present invention has been described with specific details and limited examples, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above examples, and the field to which the present invention belongs Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (10)

A TLCP resin composition composed of TLCP and PCT,
The TLCP includes any one or two or more selected from repeating units represented by Formula 1, Formula 2, and Formula 3, and the PCT includes a repeating unit represented by Formula 5 below.
[Formula 1]
-O-Ar ¹ -CO-
[Formula 2]
-CO-Ar ² -CO-
[Formula 3]
-X-Ar ³ -Y-
(In Formulas 1 to 3, Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylene group;
Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylene group, or a group represented by the following formula (4);
X and Y each independently represent an oxygen element or an imino group;
The hydrogen element contained in the group represented by Ar ¹ , Ar ² or Ar ³ may be independently substituted with a halogen element, an alkyl group of 1 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.)
[Formula 4]
-Ar ⁴ -Z-Ar ⁵ -
(In Formula 4, Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group; Z represents an oxygen element, a sulfur element, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms.)
[Formula 5]

According to claim 1,
The TLCP resin composition comprising a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid. According to claim 1,
The TLCP resin composition, wherein the melting point of the resin composition is 200 ° C. or higher. According to claim 1,
The TLCP resin composition, wherein the crystallization temperature of the resin composition is 100 ° C. or higher. According to claim 1,
The TLCP resin composition of which the glass transition temperature of the resin composition is 60 ℃ or more. According to claim 1,
The TLCP resin composition wherein the thermal decomposition initiation temperature of the resin composition is 400 to 600 ° C. A method for producing a TLCP resin composition composed of TLCP and PCT comprising preparing a TLCP resin composition by melt compounding TLCP and PCT,
The TLCP includes any one or two or more selected from repeating units represented by Formula 1, Formula 2, and Formula 3, and the PCT includes repeating units represented by Formula 5 below Preparation of a TLCP resin composition method.
[Formula 1]
-O-Ar ¹ -CO-
[Formula 2]
-CO-Ar ² -CO-
[Formula 3]
-X-Ar ³ -Y-
(In Formulas 1 to 3, Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylene group;
Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylene group, or a group represented by the following formula (4);
X and Y each independently represent an oxygen element or an imino group;
The hydrogen element contained in the group represented by Ar ¹ , Ar ² or Ar ³ may be independently substituted with a halogen element, an alkyl group of 1 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.)
[Formula 4]
-Ar ⁴ -Z-Ar ⁵ -
(In Formula 4, Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group; Z represents an oxygen element, a sulfur element, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms.)
[Formula 5]

According to claim 7,
The melt compounding is a method for producing a TLCP resin composition that is performed at a stirring speed of 10 to 1000 rpm in a temperature range of 200 to 400 ° C. According to claim 7,
Wherein the TLCP comprises a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid. A molded article formed from the TLCP resin composition according to any one of claims 1 to 6.

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