Composition for synthesizing liquid crystal polymer, liquid crystal polymer for electric and electronic products using the same, polymer resin composition and molded article

Abstract

The present invention relates to a composition for synthesizing a liquid crystal polymer, which can synthesize a liquid crystal polymer having excellent insulating properties, heat resistance and processability, and to a liquid crystal polymer for electric and electronic products, a polymer resin composition and a molded article using the same.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0070919, filed June 7, 2017, and Korean Patent Application No. 10-2017-0166961, filed December 6, 2017, and all contents disclosed in the documents of said Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a composition for synthesizing a liquid crystal polymer, a liquid crystal polymer for electrical and electronic products, a polymer resin composition, and a molded article using the same. More specifically, the present invention relates to a composition for synthesizing a liquid crystal polymer that can synthesize a liquid crystal polymer having excellent insulating properties, heat resistance, and processability, and a liquid crystal polymer for electrical and electronic products, a polymer resin composition, and a molded article using the same. [Background technology]

[0003] In general, liquid crystal polymers are polymers that maintain a crystalline state even in a molten state and have liquid crystallinity, and have excellent properties such as heat resistance, flowability, flame retardancy, and moldability.

[0004] There are various types of liquid crystal polymers with these properties, but in most cases, only aromatic molecules are used as monomers, and the basic physical properties of the liquid crystal polymers vary depending on the content ratio of the monomers.

[0005] Recently, the need for high-voltage components has emerged due to the specifications of electrical and electronic products. For example, to be used in components such as USB 3.1 connectors, materials that have excellent insulation properties as well as heat resistance are required.

[0006] Currently, there are no commercially available polymer materials that simultaneously have excellent heat resistance, flowability, moldability, and insulating properties, so there is a demand for polymer materials that combine all of these physical properties.For example, the currently used fully aromatic liquid crystal polymer resin in the connector market has a low Comparative Tracking Index (CTI) of 3 to 4, which can lead to current leakage and damage to parts.

[0007] Due to these limitations, there is a need for plastic products that have excellent comparative tracking index properties for application in high voltage electrical and electronic connector applications.

[0008] Therefore, there is a demand for the development of liquid crystal polymers that have excellent insulating properties and heat resistance at a level that makes them suitable for use in high-voltage components, properties that are difficult to achieve with conventional polymer materials. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention provides a composition for synthesizing a liquid crystal polymer, which can synthesize a liquid crystal polymer having excellent insulating properties, heat resistance and processability.

[0010] The present invention also provides a liquid crystal polymer for electrical and electronic products that has excellent insulating properties, heat resistance and processability.

[0011] Furthermore, the present invention provides a polymer resin composition and a molded article using the liquid crystal polymer. [Means for solving the problem]

[0012] The present specification provides a composition for synthesizing a liquid crystal polymer, comprising: an alicyclic dicarboxylic acid or a derivative thereof; an aromatic diol; an aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group; and an aromatic monocarboxylic acid having 11 to 20 carbon atoms and a hydroxy group, wherein the molar ratio of the alicyclic dicarboxylic acid or a derivative thereof to 1 mole of the aromatic diol is 0.9 to 1.1, and the total molar content of the alicyclic dicarboxylic acid or a derivative thereof and the aromatic diol is 20 mol % to 80 mol % based on the total composition.

[0013] The present specification also provides a liquid crystal polymer for electrical and electronic products, which comprises a repeating unit represented by the following chemical formula 5; and a repeating unit represented by the following chemical formula 6; and the sum of the molar content of the repeating unit represented by the chemical formula 5 and the molar content of the repeating unit represented by the chemical formula 6 is 90 mol % to 99 mol %.

[0014] [ka]

[0015] In the above formula 5, R 31 is a cycloalkylene group having 3 to 10 carbon atoms, and R 32 is an arylene group having 6 to 20 carbon atoms,

[0016] [ka]

[0017] In the above formula 6, R 33 is an arylene group having 6 to 9 carbon atoms.

[0018] The present specification further provides a polymer resin composition and a molded article using the liquid crystal polymer for electrical and electronic products.

[0019] Hereinafter, a composition for synthesizing a liquid crystal polymer according to a specific embodiment of the present invention, a liquid crystal polymer for electric and electronic products using the same, a polymer resin composition, and a molded article will be described in more detail.

[0020] In this specification, when a part "comprises" a certain component, this means that it can further include other components, rather than excluding other components, unless otherwise specified.

[0021] In this specification, a derivative means a compound obtained by changing a parent compound by introducing a functional group, oxidation, reduction, atomic substitution, or the like, to the extent that the structure and properties of the parent compound are not significantly changed. Specific examples of derivatives of dicarboxylic acid compounds such as aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, or aromatic dicarboxylic acids include dicarboxylic acid ester compounds such as aliphatic dicarboxylic acid esters, alicyclic dicarboxylic acid esters, or aromatic dicarboxylic acid esters.

[0022] In this specification, a monocarboxylic acid refers to a compound having one carboxy group (-COOH) in the molecule, and a dicarboxylic acid refers to a compound having two carboxy groups (-COOH) in the molecule.

[0023] As used herein, an alkyl group may be linear or branched and has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms.

[0024] In this specification, the aryl group is not particularly limited, but preferably has 6 to 20 carbon atoms and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. As the monocyclic aryl group, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited to these. As the polycyclic aryl group, the aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc., but is not limited to these.

[0025] In this specification, a cycloalkylene group is a divalent group derived from a cycloalkane and has 3 to 30, or 3 to 20, or 3 to 10 carbon atoms. Examples of cycloalkylene groups include, but are not limited to, cyclopropylene, cyclobutylene, cyclopentylene, 3-methylcyclopentylene, 2,3-dimethylcyclopentylene, cyclohexylene, 3-methylcyclohexylene, 4-methylcyclohexylene, 2,3-dimethylcyclohexylene, 3,4,5-trimethylcyclohexylene, 4-tert-butylcyclohexylene, cycloheptylene, and cyclooctylene.

[0026] In this specification, an arylene group refers to an aryl group having two bonding positions, i.e., a divalent group. The above description of the aryl group is applicable to these groups, except that they are both divalent groups.

[0027] According to one embodiment of the present invention, there is provided a composition for synthesizing a liquid crystal polymer, comprising: an alicyclic dicarboxylic acid or a derivative thereof; an aromatic diol; an aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group; and an aromatic monocarboxylic acid having 11 to 20 carbon atoms and a hydroxy group, wherein the molar ratio of the alicyclic dicarboxylic acid or a derivative thereof to 1 mole of the aromatic diol is 0.9 to 1.1, and the total molar content of the alicyclic dicarboxylic acid or a derivative thereof and the aromatic diol is 20 mol % to 80 mol % based on the total composition.

[0028] Specifically, in the composition for synthesizing a liquid crystal polymer of the embodiment, the molar ratio of the alicyclic dicarboxylic acid or its derivative to 1 mole of aromatic diol is 0.9 to 1.1, preferably 1, and the total molar content of the alicyclic dicarboxylic acid or its derivative and the aromatic diol may be 20 mol% to 80 mol%, or 20 mol% to 36 mol%, or 66 mol% to 80 mol% based on the total composition.

[0029] The present inventors have confirmed through experiments that the liquid crystal polymer produced by adjusting the molar ratio of the alicyclic dicarboxylic acid or its derivative to 1 mole of the aromatic diol in the composition for synthesizing the liquid crystal polymer to 0.9 to 1.1, preferably 1, and adjusting the total molar content of the alicyclic dicarboxylic acid or its derivative and the aromatic diol to 20 mol% to 80 mol% based on the total composition, and completing the acetylation reaction of the monomer at an initial reaction temperature of 100°C to 200°C and atmospheric pressure, followed by heating to 300°C to 400°C, and finally reducing the pressure from atmospheric pressure to less than 1 Torr in a stepwise manner, mainly contains repeating units between the alicyclic dicarboxylic acid or its derivative and the aromatic diol, thereby ensuring both heat resistance and insulating properties, and thus completing the invention.

[0030] In particular, the composition for synthesizing a liquid crystalline polymer according to one embodiment may further contain, in addition to the alicyclic dicarboxylic acid or its derivative and the aromatic diol, an aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group and an aromatic monocarboxylic acid having 11 to 20 carbon atoms, in order to adjust the heat resistance of the liquid crystalline polymer to be produced.

[0031] In this case, the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is added so that the total molar content of the alicyclic dicarboxylic acid or its derivative, the aromatic diol, and the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is 90 mol% or more, or 90 mol% to 99 mol%, based on the total composition. In the step of reacting at an initial reaction temperature of 100°C to 200°C and atmospheric pressure, an acetylation reaction of the monomer occurs, and after a final temperature increase to 300°C to 400°C, the pressure is gradually reduced from atmospheric pressure to less than 1 torr, whereby an esterification reaction of the alicyclic dicarboxylic acid or its derivative, the aromatic diol, and the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group occurs, thereby inducing an alicyclic-aromatic mesogen to form the main repeating unit in the final liquid crystal polymer.

[0032] In addition, aromatic monocarboxylic acids having 11 to 20 carbon atoms and containing a hydroxyl group have relatively strong aromatic properties per unit compound, and even a small amount can significantly reduce the insulating properties of the entire polymer. Therefore, by using a content of the aromatic monocarboxylic acid below a certain amount, the insulating properties of the mesogen formed by the alicyclic dicarboxylic acid or its derivative and the aromatic diol can be fully realized.

[0033] More specifically, the content of each component contained in the composition for synthesizing a liquid crystal polymer according to the embodiment may be 10 mol % to 40 mol % of the alicyclic dicarboxylic acid or its derivative, 10 mol % to 40 mol % of the aromatic diol, 15 mol % to 75 mol % of the aromatic monocarboxylic acid having 7 to 10 carbon atoms and containing a hydroxy group, and 1 mol % to 6 mol % of the aromatic monocarboxylic acid having 11 to 20 carbon atoms and containing a hydroxy group, based on 100 mol % of the entire composition.

[0034] In particular, when the alicyclic dicarboxylic acid or its derivative is added in an amount of 10 mol% to 18 mol%, or 33 to 40 mol%, and the aromatic diol is added in an amount of 10 mol% to 18 mol%, or 33 to 40 mol%, and the total amount of the alicyclic dicarboxylic acid or its derivative and the aromatic diol is added in an amount of 20 mol% to 36 mol%, or 66 to 80 mol%, better heat resistance and insulating properties are ensured. When the molar content is outside the above range, the insulating properties or heat resistance may be reduced, or it may be difficult to fully realize the liquid crystal properties.

[0035] The alicyclic dicarboxylic acid or its derivative is a compound for introducing an alicyclic moiety into the liquid crystal polymer, thereby improving the insulating properties of the liquid crystal polymer. The alicyclic dicarboxylic acid or its derivative may include a cycloalkane dicarboxylic acid having 5 to 20 carbon atoms or an ester compound thereof.

[0036] Specific examples of the cycloalkanedicarboxylic acid having 5 to 20 carbon atoms or its ester compound include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-dimethylcyclohexane dicarboxylate, 1,3-dimethylcyclohexane dicarboxylate, and 1,2-dimethylcyclohexane dicarboxylate, and preferably, 1,4-cyclohexanedicarboxylic acid can be used.

[0037] Meanwhile, the aromatic diol is used as a reactive monomer for esterification with the alicyclic dicarboxylic acid or its derivative, thereby improving the heat resistance and mechanical properties of the liquid crystal polymer. An example of the aromatic diol is a benzenediol having 6 to 10 carbon atoms. If the carbon number of the benzenediol increases to 10 or more, the insulating properties may decrease due to the increase in the aromatic moieties introduced into the liquid crystal polymer.

[0038] Examples of the benzenediol having 6 to 10 carbon atoms include hydroquinone and resorcinol, and preferably, hydroquinone can be used.

[0039] Meanwhile, the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is added to adjust the heat resistance of the liquid crystal polymer to be produced, and specifically, the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is represented by the following chemical formula 1.

[0040] [ka]

[0041] In the above Chemical Formula 1, at least one of R1 to R5 is a hydroxy group, and the rest are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0042] Preferably, 4-hydroxybenzoic acid can be used, in which R3 is a hydroxy group and R1, R2, R4, and R5 are hydrogen in Chemical Formula 1.

[0043] The aromatic monocarboxylic acid having 11 to 20 carbon atoms and containing a hydroxy group is represented by the following chemical formula 2 as an aromatic monocarboxylic acid having 11 to 20 carbon atoms and containing a hydroxy group.

[0044] [ka]

[0045] In the above Chemical Formula 2, R6 to R 12 At least one of these is a hydroxy group, and the rest are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0046] Preferably, in the above Chemical Formula 2, R9 is a hydroxy group, and R6 to R8, R 10 ~R 12 can be used, where R is hydrogen, 6-hydroxy-2-naphthalenecarboxylic acid.

[0047] Meanwhile, the composition for synthesizing a liquid crystal polymer may further contain a cycloalkane monocarboxylic acid having 5 to 20 carbon atoms and containing a hydroxy group; a bicycloalkane monocarboxylic acid having 5 to 30 carbon atoms and containing a hydroxy group; or an ester compound thereof.

[0048] Specific examples of the cycloalkane monocarboxylic acid having 5 to 20 carbon atoms and containing a hydroxy group include the compound represented by the following chemical formula 3.

[0049] [ka]

[0050] In the above formula 3, R 13 ~R 17 At least one of R is a hydroxy group, and the rest are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 15 is a hydroxy group, and R 13 ~R 14 , R 16 ~R 17 4-hydroxycyclohexanecarboxylic acid, where is hydrogen, can be used.

[0051] Specific examples of the bicycloalkane monocarboxylic acid having 5 to 30 carbon atoms and containing a hydroxy group include the compound represented by the following chemical formula 4.

[0052] [ka]

[0053] In the above formula 4, R 18 ~R 24 At least one of R is a hydroxy group, and the remaining R are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 21 is a hydroxy group, and R 18 ~R 20 , R 22 ~R 24 Decahydro-6-hydroxy-2-naphthalenecarboxylic acid, where is hydrogen, can be used.

[0054] Additionally, the liquid crystal polymer synthesis composition may further contain, as necessary, an alicyclic diol having 5 to 20 carbon atoms, or a derivative compound of an aromatic diol, or an aromatic dicarboxylic acid.

[0055] Examples of the alicyclic diol having 5 to 20 carbon atoms include 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 4,4'-bicyclohexanol, 3,3'-bicyclohexanol, and 2,2'-bicyclohexanol.

[0056] An example of the aromatic diol derivative compound is acetaminophen, and an example of the aromatic dicarboxylic acid is terephthalic acid, isophthalic acid, etc.

[0057] The composition for synthesizing the liquid crystal polymer may contain various additives to improve physical properties, etc. The type, method, and timing of addition of the additives are not particularly limited, and various known additives may be used without limitation. Specific examples of the additives include impact modifiers, antioxidants, compatibilizers, hydrolysis stabilizers, ultraviolet light stabilizers, heat stabilizers, color additives, fixatives, flame retardants, electrically conductive materials for dissipating static electricity, and mixtures of two or more of these.

[0058] The liquid crystalline polymer produced from the composition for synthesizing a liquid crystalline polymer can be used for components of electrical and electronic products, more preferably components of high-voltage electrical and electronic products or components of electronic devices for large-capacity transmission. The liquid crystalline polymer produced from the composition for synthesizing a liquid crystalline polymer has excellent heat resistance while satisfying the comparative tracking index required for high-voltage component materials and has the excellent flowability unique to liquid crystalline polymers, making it possible to provide a material that meets all the physical properties required for high-voltage component materials.

[0059] Meanwhile, according to another embodiment of the present invention, there is provided a liquid crystalline polymer including a polymerization reaction result of the composition for synthesizing a liquid crystalline polymer of the above embodiment. Specifically, there is provided a liquid crystalline polymer for electrical and electronic products, which includes a repeating unit represented by Chemical Formula 5 and a repeating unit represented by Chemical Formula 6, and the sum of the molar content of the repeating unit represented by Chemical Formula 5 and the molar content of the repeating unit represented by Chemical Formula 6 is 90 mol % to 99 mol %.

[0060] The present inventors have confirmed through experiments that liquid crystal polymers for electrical and electronic products mainly contain a repeating unit represented by Chemical Formula 5 (a repeating unit formed by an esterification reaction between an alicyclic dicarboxylic acid or its derivative and an aromatic diol) and a repeating unit represented by Chemical Formula 6 (a repeating unit formed by an esterification reaction of an aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group), thereby ensuring both heat resistance and insulating properties, and have completed the invention.

[0061] In the liquid crystal polymer for electrical and electronic products, the repeating unit represented by Chemical Formula 5 and the repeating unit represented by Chemical Formula 6 may be bonded to form a block copolymer or may be bonded randomly to form a random copolymer, and the specific polymerization form is not particularly limited.

[0062] Specifically, in the liquid crystal polymer for electrical and electronic products, the sum of the molar content of the repeating unit represented by Chemical Formula 5 and the molar content of the repeating unit represented by Chemical Formula 6 may be 90 mol% to 99 mol%, or 93 mol% to 99 mol%, or 96 mol% to 99 mol%, based on the molar content of all repeating units contained in the entire liquid crystal polymer.

[0063] The sum of the molar content of the repeating unit represented by Chemical Formula 5 and the molar content of the repeating unit represented by Chemical Formula 6 means the sum of the molar content of the repeating unit represented by Chemical Formula 5 and the molar content of the repeating unit represented by Chemical Formula 6, when the molar content of all repeating units contained in the entire liquid crystal polymer is 100 mol%.

[0064] That is, in the liquid crystal polymer for electrical and electronic products, the repeating unit represented by Chemical Formula 5 and the repeating unit represented by Chemical Formula 6 occupy the majority as main repeating units, and the physical properties of the liquid crystal polymer can be realized by the repeating unit represented by Chemical Formula 5 and the repeating unit represented by Chemical Formula 6.

[0065] In the above formula 5, R 31 is a cycloalkylene group having 3 to 10 carbon atoms, and R 32 is an arylene group having 6 to 20 carbon atoms, or R 31 is a cycloalkylene group having 4 to 8 carbon atoms, and R 32 may be an arylene group having 6 to 10 carbon atoms.

[0066] In the above formula 6, R 33 may be an arylene group having 6 to 9 carbon atoms or a phenylene group.

[0067] The formula 5 may include a repeating unit represented by the following formula 5-1.

[0068] [ka]

[0069] The formula 6 may include a repeating unit represented by the following formula 6-1.

[0070] [ka]

[0071] The liquid crystal polymer for electrical and electronic products may further include one or more repeating units selected from the group consisting of the following Chemical Formula 7, Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, Chemical Formula 11, and Chemical Formula 12. The one or more repeating units selected from the group consisting of Chemical Formula 7, Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, Chemical Formula 11, and Chemical Formula 12 may mean one of each of Chemical Formula 7, Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, Chemical Formula 11, and Chemical Formula 12, or a mixture of two or more of these.

[0072] [ka]

[0073] In the above formula 7, R 34 may be an arylene group having 10 to 20 carbon atoms or a naphthylene group having 10 carbon atoms,

[0074] [ka]

[0075] In the above Chemical Formula 8, R 35 is an arylene group having 10 to 20 carbon atoms or a naphthylene group having 10 carbon atoms, and R 36 is an arylene group having 6 to 9 carbon atoms or a phenylene group having 6 carbon atoms,

[0076] [ka]

[0077] In the above formula 9, R 37 is an arylene group having 10 to 20 carbon atoms or a naphthylene group having 10 carbon atoms, and R 38 is an arylene group having 6 to 9 carbon atoms or a phenylene group having 6 carbon atoms,

[0078] [ka]

[0079] In the above formula 10, R 39 is a cycloalkylene group having 3 to 10 carbon atoms or a cyclohexylene group having 6 carbon atoms, and R 40 is an arylene group having 10 to 20 carbon atoms or a naphthylene group having 10 carbon atoms,

[0080] [ka]

[0081] In the above formula 11, R 41 is a cycloalkylene group having 3 to 10 carbon atoms or a cyclohexylene group having 6 carbon atoms, and R 42 is an arylene group having 6 to 9 carbon atoms or a phenylene group having 6 carbon atoms,

[0082] [ka]

[0083] In the above formula 12, R 43 is an arylene group having 6 to 9 carbon atoms or a phenylene group having 6 carbon atoms, and R 44 is an arylene group having 6 to 9 carbon atoms or a phenylene group having 6 carbon atoms.

[0084] More specifically, the chemical formulas 7, 8, 9, 10, 11, and 12 may contain repeating units represented by chemical formulas 7-1, 8-1, 9-1, 10-1, 11-1, and 12-1, respectively.

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] The content of one or more repeating units selected from the group consisting of Chemical Formula 7, Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, Chemical Formula 11, and Chemical Formula 12 may be 1 mol % to 10 mol %, or 1 mol % to 7 mol %, or 1 mol % to 4 mol %. In other words, by mainly containing the repeating unit represented by Chemical Formula 5 (a repeating unit formed by an esterification reaction between an alicyclic dicarboxylic acid or a derivative thereof and an aromatic diol) and the repeating unit represented by Chemical Formula 6 (a repeating unit formed by an esterification reaction of an aromatic monocarboxylic acid having 7 to 10 carbon atoms and containing a hydroxy group) in the liquid crystal polymer, it is possible to ensure both heat resistance and insulating properties.

[0092] The liquid crystalline polymer for electrical and electronic products can be used as a component for electrical and electronic products, more preferably as a component for high-voltage electrical and electronic products or a component for large-capacity transmission electronic equipment. The liquid crystalline polymer for electrical and electronic products meets the comparative tracking index required for high-voltage component materials while maintaining excellent heat resistance and possessing the outstanding flowability unique to liquid crystalline polymers, making it possible to provide a material that meets all the physical properties required for high-voltage component materials.

[0093] Meanwhile, the method for producing the liquid crystal polymer for electrical and electronic products according to the embodiment is not particularly limited, but may include, for example, reacting a liquid crystal polymer synthesis composition containing an alicyclic dicarboxylic acid or a derivative thereof; an aromatic diol; an aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group; and an aromatic monocarboxylic acid having 11 to 20 carbon atoms and a hydroxyl group at a molar ratio of 0.9 to 1.1 per mole of the aromatic diol, and a total molar content of the alicyclic dicarboxylic acid or a derivative thereof and the aromatic diol of 20 mol% to 80 mol% based on the total composition, at 300°C to 400°C and atmospheric pressure; and then reducing the pressure of the reaction product to 1 torr or less. The liquid crystal polymer according to the other embodiment can be produced by the above-described method. The details regarding the liquid crystal polymer synthesis composition include those described in the above embodiment.

[0094] Specifically, the composition for synthesizing a liquid crystal polymer may have a molar ratio of the alicyclic dicarboxylic acid or its derivative to 1 mole of aromatic diol of 0.9 to 1.1, preferably 1, and the total molar content of the alicyclic dicarboxylic acid or its derivative and the aromatic diol may be 20 mol% to 80 mol%, or 20 mol% to 36 mol%, or 66 mol% to 80 mol% based on the total composition.

[0095] The molar ratio of the alicyclic dicarboxylic acid or its derivative is adjusted to 0.9 to 1.1, preferably 1, and the total molar content of the alicyclic dicarboxylic acid or its derivative and the aromatic diol is adjusted to 20 mol% to 80 mol% based on the total composition. The acetylation reaction of the monomer is completed at an initial reaction temperature of 100°C to 200°C and atmospheric pressure, followed by heating to 300°C to 400°C. After the final heating, the liquid crystal polymer is gradually depressurized from atmospheric pressure to a pressure of less than 1 torr. Since the liquid crystal polymer contains mainly repeating units between the alicyclic dicarboxylic acid or its derivative and the aromatic diol, it can ensure both heat resistance and insulating properties.

[0096] In particular, the composition for synthesizing a liquid crystalline polymer may further contain, in addition to the alicyclic dicarboxylic acid or its derivative and aromatic diol, an aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group and an aromatic monocarboxylic acid having 11 to 20 carbon atoms, in order to adjust the heat resistance of the liquid crystalline polymer to be produced.

[0097] In this case, the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is added so that the total molar content of the alicyclic dicarboxylic acid or its derivative, the aromatic diol, and the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is 90 mol% or more, or 90 mol% to 99 mol%, based on the total composition. In the step of reacting at an initial reaction temperature of 100°C to 200°C and atmospheric pressure, an acetylation reaction of the monomer occurs, and after a final temperature increase to 300°C to 400°C, the pressure is gradually reduced from atmospheric pressure to less than 1 torr, whereby an esterification reaction of the alicyclic dicarboxylic acid or its derivative, the aromatic diol, and the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group occurs, thereby inducing an alicyclic-aromatic mesogen to form the main repeating unit in the final liquid crystal polymer.

[0098] In addition, aromatic monocarboxylic acids having 11 to 20 carbon atoms and containing a hydroxyl group have relatively strong aromatic properties per unit compound, and even a small amount can significantly reduce the insulating properties of the entire polymer. Therefore, by using a content of the aromatic monocarboxylic acid below a certain amount, the insulating properties of the mesogen formed by the alicyclic dicarboxylic acid or its derivative and the aromatic diol can be fully realized.

[0099] More specifically, based on 100 mol% of the entire composition for synthesizing a liquid crystal polymer, the alicyclic dicarboxylic acid or its derivative may be 10 mol% to 40 mol%, the aromatic diol may be 10 mol% to 40 mol%, the molar content of the aromatic monocarboxylic acid having 7 to 10 carbon atoms and containing a hydroxy group may be 15 mol% to 75 mol%, and the molar content of the aromatic monocarboxylic acid having 11 to 20 carbon atoms and containing a hydroxy group may be 1 mol% to 6 mol% based on the entire composition.

[0100] In particular, when the alicyclic dicarboxylic acid or its derivative is added in an amount of 10 mol% to 18 mol%, or 33 mol% to 40 mol%, and the aromatic diol is added in an amount of 10 mol% to 18 mol%, or 33 mol% to 40 mol%, and the total amount of the alicyclic dicarboxylic acid or its derivative and the aromatic diol is added in an amount of 20 mol% to 36 mol%, or 66 mol% to 80 mol%, better heat resistance and insulating properties are ensured. When the amount is outside the above content range, the insulating properties or heat resistance may be reduced, or it may be difficult to fully realize the liquid crystal properties.

[0101] The alicyclic dicarboxylic acid or its derivative is a compound for introducing an alicyclic moiety into the liquid crystal polymer, thereby improving the insulating properties of the liquid crystal polymer. The alicyclic dicarboxylic acid or its derivative may include a cycloalkane dicarboxylic acid having 5 to 20 carbon atoms or an ester compound thereof.

[0102] Specific examples of the cycloalkanedicarboxylic acid having 5 to 20 carbon atoms or its ester compound include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-dimethylcyclohexane dicarboxylate, 1,3-dimethylcyclohexane dicarboxylate, and 1,2-dimethylcyclohexane dicarboxylate, and preferably, 1,4-cyclohexanedicarboxylic acid can be used.

[0103] Meanwhile, the aromatic diol is used as a reactive monomer for esterification with the alicyclic dicarboxylic acid or its derivative, thereby improving the heat resistance and mechanical properties of the liquid crystal polymer. An example of the aromatic diol is a benzenediol having 6 to 10 carbon atoms. If the carbon number of the benzenediol increases to 10 or more, the insulating properties may decrease due to the increase in the aromatic moieties introduced into the liquid crystal polymer.

[0104] Examples of the benzenediol having 6 to 10 carbon atoms include hydroquinone and resorcinol, and preferably, hydroquinone can be used.

[0105] On the other hand, the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group is added to adjust the heat resistance of the liquid crystal polymer to be produced. Specifically, 4-hydroxybenzoic acid can be used as the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group.

[0106] The aromatic monocarboxylic acid having 11 to 20 carbon atoms and containing a hydroxy group is specifically 6-hydroxy-2-naphthalenecarboxylic acid.

[0107] Meanwhile, the composition for synthesizing a liquid crystal polymer may further contain a cycloalkane monocarboxylic acid having 5 to 20 carbon atoms and containing a hydroxy group; a bicycloalkane monocarboxylic acid having 5 to 30 carbon atoms and containing a hydroxy group; or an ester compound thereof.

[0108] A specific example of the cycloalkane monocarboxylic acid containing a hydroxy group and having 5 to 20 carbon atoms is 4-hydroxycyclohexanecarboxylic acid.

[0109] A specific example of the bicycloalkane monocarboxylic acid containing a hydroxy group and having 5 to 30 carbon atoms is decahydro-6-hydroxy-2-naphthalenecarboxylic acid.

[0110] Additionally, the liquid crystal polymer synthesis composition may further contain, if necessary, an alicyclic diol having 5 to 20 carbon atoms, or a derivative compound of an aromatic diol, or an aromatic dicarboxylic acid.

[0111] Examples of the alicyclic diol having 5 to 20 carbon atoms include 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 4,4'-bicyclohexanol, 3,3'-bicyclohexanol, and 2,2'-bicyclohexanol.

[0112] Examples of the aromatic diol derivative compounds include acetaminophen, and examples of the aromatic dicarboxylic acids include terephathalic acid and isophthalic acid.

[0113] The composition for synthesizing the liquid crystal polymer may contain various additives to improve physical properties, etc. The type, method, and timing of addition of the additives are not particularly limited, and various known additives may be used without limitation. Specific examples of the additives include impact modifiers, antioxidants, compatibilizers, hydrolysis stabilizers, UV stabilizers, heat stabilizers, color additives, fixatives, flame retardants, electrically conductive materials for dissipating static electricity, and mixtures of two or more of these.

[0114] By reacting the composition for synthesizing a liquid crystal polymer at 300 to 400° C. and atmospheric pressure, a polymer can be formed by polycondensing an oligomer formed by the reaction between reactive monomers.

[0115] Also, by carrying out the reaction while reducing the pressure of the reaction product to 1 torr or less, a liquid crystal polymer with an excellent comparative tracking index can be produced.

[0116] Before reacting the composition for synthesizing a liquid crystalline polymer at 300°C to 400°C and atmospheric pressure, the method may further include adding an acid anhydride to the composition for synthesizing a liquid crystalline polymer and reacting the mixture at 100°C to 200°C and atmospheric pressure, thereby inducing an acetylation reaction of the functional group of the reactive monomer contained in the composition for synthesizing a liquid crystalline polymer.

[0117] After adding an acid anhydride to the liquid crystal polymer synthesis composition and reacting at 100°C to 200°C and atmospheric pressure, the method may further include increasing the temperature at a rate of 0.5°C / min to 1.5°C / min, thereby forming an oligomer through a reaction between reactive monomers.

[0118] That is, the specific method for producing the liquid crystal polymer includes an acetylation step in which an acid anhydride is added to a composition for synthesizing a liquid crystal polymer and reacted at 100 to 200°C and atmospheric pressure; a step in which the temperature of the contents is increased to 300 to 400°C at a rate of 0.5 to 1.5°C / min to produce an oligomer; and a step in which, after the final temperature increase, the pressure is gradually reduced from atmospheric pressure to a pressure less than 1 torr for 30 minutes to 1 hour to polycondense the polymer.

[0119] Meanwhile, the method for preparing the liquid crystal polymer may further include a step of removing by-products generated after each step, if necessary.

[0120] The liquid crystal polymer for electrical and electronic products was measured by a capillary viscometer at a temperature 20°C higher than the melting point and a shear rate of 1000 s -1 The melt viscosity measured by the method may be 10 poise to 2000 poise, or 15 poise to 1500 poise, or 20 poise to 1000 poise.

[0121] The liquid crystal polymer for electrical and electronic products may have a melting temperature (Tm) measured by differential scanning calorimetry of 275°C to 350°C, or 280°C to 340°C, or 285°C to 330°C, and a heat of fusion of 0.4J / g to 5J / g, or 0.7J / g to 4.0J / g, or 1.0J / g to 3.0J / g. A liquid crystal polymer having such a melting temperature and heat of fusion may have excellent flowability and heat resistance.

[0122] Specifically, the liquid crystal polymer for electrical and electronic products may have a flow temperature (Tf) measured by a flow tester of 250°C to 320°C, or 255°C to 310°C, or 260°C to 300°C, and a crystallization temperature (Tc) measured by differential scanning calorimetry of 265°C to 350°C, or 270°C to 340°C, or 275°C to 330°C.

[0123] In addition, the liquid crystal polymer for electrical and electronic products has a comparative tracking index of 0 to 1 when a test piece of 35mm*35mm*1T is prepared by hot pressing at a temperature 20°C higher than the melting point of the polymer and evaluated under various voltages.

[0124] The comparative tracking index grades of 2 and 3 indicate that tracking due to contaminants occurs at high voltages of 450V or more, resulting in poor insulation properties, while grades 0 and 1 indicate that excellent insulation properties can be exhibited even at high voltages of 450V or more.

[0125] Meanwhile, according to still another embodiment of the present invention, there is provided a polymer resin composition or a molded article thereof containing the liquid crystal polymer for electric and electronic products.

[0126] The liquid crystal polymer for electrical and electronic products includes all of the contents described in the other embodiments.

[0127] The polymer resin composition may consist solely of a liquid crystal polymer for electrical and electronic products, or may further contain other polymers or additives.

[0128] The other polymer may be any of conventionally known thermoplastic resins, thermosetting resins, or their homopolymers, blends, or copolymers, without limitation. Specific examples include one or more resins selected from the group consisting of epoxy resins, phenolic resins, nylon, polyester resins, and polyphenylene sulfide (PPS) resins.

[0129] Examples of the additives include fiber reinforcement, inorganic filler, impact modifier, nucleating agent, antioxidant, lubricant, release agent, color toning agent, compatibilizer, heat stabilizer, UV stabilizer, hydrolysis stabilizer, viscosity enhancer, fluorescent brightener, physical property enhancer, main chain extender, pigment, dye, antistatic agent, or a mixture of two or more thereof. The specific types of the additives are not particularly limited, and various additives widely used in the field of conventional resin compositions can be used without limitation.

[0130] Meanwhile, according to yet another embodiment of the present invention, there is provided a molded article comprising the polymer resin composition of the other embodiment.

[0131] The molded article can be obtained by molding the polymer resin composition using various molding methods, such as injection molding, extrusion molding, extrusion blow molding, injection blow molding, and profile extrusion molding, depending on the application. As described above, the molded article can include electronic products, specifically, components of electrical and electronic products, such as components of electrical and electronic devices or components of electronic devices for large-capacity transmission.

[0132] In particular, a high-speed micro-injection machine can be used to inject components for electrical and electronic devices that require micro-molding. The liquid crystalline polymer produced by the present invention has excellent fluidity, allowing for the production of micro-molded injection products by high-speed injection. In particular, the liquid crystalline polymer produced by the present invention has excellent insulating properties, allowing for the production and application of molded components for electronic devices that require physical properties that can withstand high voltages, such as USB 3.1 connector components for large-capacity data transmission.

[0133] The specific shape and size of the molded product may vary depending on the application, and examples thereof are not particularly limited, but may be, for example, a sheet, a container, or a pellet.

[0134] The content relating to the polymer resin composition includes the content described in relation to the other embodiments. [Effects of the Invention]

[0135] According to the present invention, it is possible to provide a composition for synthesizing a liquid crystal polymer, which can synthesize a liquid crystal polymer having excellent insulating properties, heat resistance and processability, a liquid crystal polymer for electric and electronic products, a polymer resin composition and a molded article. DETAILED DESCRIPTION OF THE INVENTION

[0136] The present invention will be described in more detail in the following examples, but the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

[0137] <Examples 1 to 5> Example 1: Preparation of liquid crystal polymer containing alicyclic mesogens A 500ml glass reactor was charged with 65.42g of 1,4-cyclohexanedicarboxylic acid, 41.80g of hydroquinone, 7.55g of 6-hydroxy-2-naphthalenecarboxylic acid, 27.63g of 4-hydroxybenzoic acid, and 106.11g of acetic anhydride. The mixture was heated to 150°C and reacted for 2 hours. The acetic acid generated as a by-product was refluxed. The temperature was then increased to 350°C at a rate of 1°C / min. The reaction by-product was cooled and collected in a receiver. After reaching 350°C, the pressure was gradually reduced from ambient pressure to below 1 torr for 30 minutes. The reaction was continued for an additional 10 minutes at less than 1 torr to produce the liquid crystalline polymer.

[0138] The liquid crystal polymer prepared in Example 1 has a melting temperature of 329°C measured by a differential scanning calorimeter, a flow temperature of 297°C measured by a flow tester, and a melting point of 37 poise (at a shear rate of 1000 s) measured by a capillary viscometer. -1 ) was confirmed.

[0139] At this time, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid in the liquid crystal polymer prepared in Example 1 was 90 mol% or more.

[0140] Example 2: Preparation of liquid crystal polymer containing alicyclic mesogens The polymerization reaction was carried out under the same conditions as in Example 1, except that the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 56.81 g, the amount of hydroquinone added was changed to 36.30 g, and the amount of 4-hydroxybenzoic acid added was changed to 41.45 g.

[0141] The liquid crystal polymer prepared in Example 2 had a melting temperature of 323°C and a crystallization temperature of 310°C measured by a differential scanning calorimeter, a flow temperature of 287°C measured by a flow tester, and a melting point of 99 poise (at a shear rate of 1000 s) measured by a capillary viscometer. -1 ) was confirmed.

[0142] In this case, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid in the liquid crystal polymer prepared in Example 2 was 90 mol% or more.

[0143] Example 3: Preparation of liquid crystal polymer containing alicyclic mesogens The polymerization reaction was carried out under the same conditions as in Example 1, except that the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 48.21 g, the amount of hydroquinone added was changed to 30.80 g, and the amount of 4-hydroxybenzoic acid added was changed to 55.27 g.

[0144] The liquid crystal polymer prepared in Example 3 had a melting temperature of 295°C and a crystallization temperature of 281°C measured by a differential scanning calorimeter, a flow temperature of 264°C measured by a flow tester, and a melting point of 189 poise (at a shear rate of 1000 s) measured by a capillary viscometer. -1 ) was confirmed.

[0145] At this time, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid in the liquid crystal polymer prepared in Example 3 was 90 mol% or more.

[0146] Example 4: Preparation of liquid crystal polymer containing alicyclic mesogens The polymerization reaction was carried out under the same conditions as in Example 1, except that the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 39.60 g, the amount of hydroquinone added was changed to 25.30 g, and the amount of 4-hydroxybenzoic acid added was changed to 69.09 g.

[0147] The liquid crystal polymer prepared in Example 4 had a melting temperature of 286°C and a crystallization temperature of 277°C measured by a differential scanning calorimeter, a flow temperature of 272°C measured by a flow tester, and a melting point of 993 poise (at a shear rate of 1000 s) measured by a capillary viscometer. -1 ) was confirmed.

[0148] At this time, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid in the liquid crystal polymer prepared in Example 4 was 90 mol% or more.

[0149] Example 5: Preparation of liquid crystal polymer containing alicyclic mesogens The polymerization reaction was carried out under the same conditions as in Example 1, except that the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 30.99 g, the amount of hydroquinone added was changed to 19.8 g, and the amount of 4-hydroxybenzoic acid added was changed to 82.87 g.

[0150] The liquid crystal polymer prepared in Example 5 has a melting temperature of 325°C and a crystallization temperature of 282°C measured by a differential scanning calorimeter, a flow temperature of 300°C measured by a flow tester, and a melting point of 23 poise (at a shear rate of 1000 s) measured by a capillary viscometer. -1 ) was confirmed.

[0151] At this time, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid in the liquid crystal polymer prepared in Example 5 was 90 mol% or more.

[0152] <Comparative Examples 1 to 5> Comparative example 1: Fully aromatic liquid crystal polymer Solvay's SRT-900 resin, which is a commercially available fully aromatic liquid crystal polymer, was used as Comparative Example 1. The liquid crystal polymer of Comparative Example 1 had a melting temperature of 347°C, a crystallization temperature of 301°C, a flow temperature of 319°C, and a melting point of 128 poise (at a shear rate of 1000 s), as measured by a differential scanning calorimeter. -1 ) was confirmed.

[0153] Comparative example 2: Fully aromatic liquid crystal polymer Vectra A950 resin from Celanese, which is a commercially available fully aromatic liquid crystal polymer, was used as Comparative Example 2. The liquid crystal polymer of Comparative Example 2 had a melting temperature of 278°C, a crystallization temperature of 235°C, a flow temperature of 253°C, and a melting point of 525 poise (at a shear rate of 1000 s), as measured by a differential scanning calorimeter. -1 ) was confirmed.

[0154] Comparative Example 3: Preparation of liquid crystal polymer containing alicyclic groups A polymerization reaction was carried out under the same conditions as in Example 1, except that a mixture of 14.39 g of 1,4-cyclohexanedicarboxylic acid, 33.63 g of hydroquinone, 42.00 g of 2,6-naphthalenedicarboxylic acid, 57.55 g of 4-hydroxybenzoic acid, and 111.20 g of acetic anhydride was placed in a 500 ml glass reactor.

[0155] The liquid crystal polymer prepared in Comparative Example 3 had a melting temperature of 251°C, a crystallization temperature of 226°C, and a flow temperature of 205°C, as measured by a differential scanning calorimeter and a flow tester, respectively.

[0156] In this case, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid was less than 90 mol% compared to the liquid crystal polymer prepared in Comparative Example 3.

[0157] Comparative Example 4: Preparation of liquid crystal polymer containing alicyclic groups A polymerization reaction was carried out under the same conditions as in Example 1, except that a mixture of 38.79 g of 1,4-cyclohexanedicarboxylic acid, 54.98 g of hydroquinone, 48.57 g of 2,6-naphthalenedicarboxylic acid, 8.40 g of terephthalic acid, and 108.07 g of acetic anhydride was placed in a 500 ml glass reactor.

[0158] The liquid crystal polymer prepared in Comparative Example 4 had a melting temperature of 322°C, a crystallization temperature of 300°C, and a flow temperature of 293°C, as measured by a differential scanning calorimeter and a flow tester, respectively.

[0159] Comparative Example 5: Preparation of liquid crystal polymer containing alicyclic groups A polymerization reaction was carried out under the same conditions as in Example 1, except that a mixture of 17.90 g of 1,4-cyclohexanedicarboxylic acid, 34.33 g of hydroquinone, 10.70 g of 2,6-naphthalenedicarboxylic acid, 14.80 g of terephthalic acid, 61.54 g of 4-hydroxybenzoic acid, and 115.69 g of acetic anhydride was placed in a 500 ml glass reactor.

[0160] The liquid crystal polymer prepared in Comparative Example 5 was confirmed to have a melting temperature of 351°C as measured by a differential scanning calorimeter and a flow temperature of 260°C as measured by a flow tester.

[0161] In this case, the total molar content of the polymer repeating units of 1,4-cyclohexanedicarboxylic acid-hydroquinone and 4-hydroxybenzoic acid-4-hydroxybenzoic acid in the liquid crystal polymer prepared in Comparative Example 5 was less than 90 mol%.

[0162] <Experimental Example: Measurement of physical properties of liquid crystal polymers obtained in Examples and Comparative Examples> The physical properties of the liquid crystal polymers obtained in the above Examples and Comparative Examples were measured by the following methods. The results are shown in Table 1.

[0163] Experimental Example 1: Comparative Tracking Index (CTI) Measurement Test specimens were prepared using the liquid crystal polymers obtained in the examples and comparative examples, and the comparative tracking index was measured according to the IEC 60112 standard by dropping a standard contaminant onto the test specimen and measuring the maximum voltage at which tracking due to the contaminant did not occur between two electrodes. The results are shown in Table 1 below.

[0164] Experimental Example 2: Measurement of flow temperature, melting temperature, and crystallization temperature The liquid crystal polymers prepared in the examples and comparative examples were heated to a temperature 20°C higher than the melting temperature at a heating rate of 10°C / min using a differential scanning calorimeter (manufacturer: TA instrument, device name: Q-20 model), rapidly cooled, and then scanned again at a heating rate of 10°C / min to measure the melting temperature (Tm) and crystallization temperature (Tc). 2 The temperature at which the polymer showed a viscosity of 48,000 poise was measured with a change in temperature under a load of 100 psi. This temperature was defined as the flow temperature (Tf) at which the polymer showed a change in viscosity with temperature under a constant load. The results are shown in Table 1 below.

[0165] [Table 1]

[0166] As shown in Table 1, the liquid crystal polymers of the examples had excellent insulating properties with a comparative tracking index of 0 or 1, and had excellent flow and heat resistance with a flow temperature (Tf) of 264°C or higher (specifically, 264°C to 300°C) and a melting temperature (Tm) of 286°C or higher (specifically, 286°C to 329°C). Furthermore, the crystallization temperature (Tc) was excellent, being 277°C or higher (specifically, 277°C to 328°C).

[0167] In contrast, in the case of Comparative Examples 1 and 2, which are representative fully aromatic liquid crystal polymers among commercially available liquid crystal polymers, the comparative tracking index was grade 3, which limited the insulating properties making it difficult to apply to high-voltage components.

[0168] Furthermore, unlike Examples 1 to 5, the liquid crystal polymers of Comparative Example 3, which had a different molar ratio of 1,4-cyclohexanedicarboxylic acid (CHDA) and hydroquinone (HQ) and contained an excess of 4 mol% or more of 2,6-naphthalenedicarboxylic acid (NDA) instead of 6-hydroxy-2-naphthalenecarboxylic acid (HNA), and Comparative Example 4, which did not use 4-hydroxybenzoic acid (HBA) and used terephthalic acid (TPA) as part of the dicarboxylic acid, had a comparative tracking index of grade 2, indicating reduced insulating properties. In particular, the liquid crystal polymer of Comparative Example 3 had a flow temperature of 205°C and a melting temperature of 251°C, indicating reduced heat resistance.

[0169] On the other hand, the liquid crystal polymer of Comparative Example 5, which used 5 mol% NDA and part of the CHDA as TPA, had a comparative tracking index of grade 2, which reduced the insulating properties, and the flow temperature was 260°C and the melting temperature was 351°C, confirming that the heat resistance was too high.

Claims

1. Alicyclic dicarboxylic acids or derivatives thereof; Aromatic diols; Aromatic monocarboxylic acids containing 7 to 10 carbon atoms and containing a hydroxy group; and It contains an aromatic monocarboxylic acid having 11 to 20 carbon atoms and containing a hydroxy group, The alicyclic dicarboxylic acid or a derivative thereof includes a cyclohexanedicarboxylic acid having 8 to 20 carbon atoms or an ester compound thereof, The molar content of the aromatic monocarboxylic acid having 11 to 20 carbon atoms and a hydroxy group is 1 mol% to 6 mol% based on the total composition; the molar ratio of the alicyclic dicarboxylic acid or a derivative thereof to 1 mole of the aromatic diol is 0.9 to 1.1; The total molar content of the alicyclic dicarboxylic acid or its derivative and the aromatic diol is 20 mol% to 80 mol% based on the total composition; The molar content of the alicyclic dicarboxylic acid or its derivative is 33 mol% to 40 mol% based on 100 mol% of the total composition for synthesizing a liquid crystal polymer; The liquid crystal polymer for electrical and electronic products, which is a polymerization reaction result of the composition for synthesizing a liquid crystal polymer, has a comparative tracking index grade (measured according to IEC 60112 standard) of grade 0.

2. 2. The composition for synthesizing a liquid crystal polymer according to claim 1, wherein the total molar content of the alicyclic dicarboxylic acid or its derivative, the aromatic diol, and the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxyl group is 90 mol% or more based on the total composition.

3. 2. The composition for synthesizing a liquid crystal polymer according to claim 1, wherein the molar content of the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group is 15 mol % to 75 mol % based on the total composition.

4. 2. The composition for synthesizing a liquid crystal polymer according to claim 1, wherein the aromatic diol comprises a benzenediol having 6 to 10 carbon atoms.

5. The composition for synthesizing a liquid crystal polymer according to claim 1, wherein the aromatic monocarboxylic acid having 7 to 10 carbon atoms and a hydroxy group is represented by the following chemical formula 1: 【Chemistry 1】 In the above formula 1, R １ ~R ５ At least one of the groups is a hydroxy group, and the rest are hydrogen.

6. The composition for synthesizing a liquid crystal polymer according to claim 1, wherein the aromatic monocarboxylic acid having 11 to 20 carbon atoms and a hydroxy group is represented by the following chemical formula 2: 【Chemistry 2】 In the above formula 2, R ６ ~R １２ At least one of the groups is a hydroxy group, and the rest are hydrogen.

7. 2. The composition for synthesizing a liquid crystal polymer according to claim 1, further comprising one or more additives selected from the group consisting of impact modifiers, antioxidants, compatibilizers, hydrolysis stabilizers, ultraviolet light stabilizers, heat stabilizers, color additives, fixatives, flame retardants, and electrically conductive materials for dissipating static electricity.

8. A polymerizable compound obtained by polymerization of the composition for synthesizing a liquid crystal polymer according to claim 1, which comprises a repeating unit represented by the following chemical formula 5: It comprises a repeating unit represented by the following chemical formula 6: A liquid crystal polymer for electrical and electronic products, wherein the sum of the molar content of the repeating unit represented by Chemical Formula 5 and the molar content of the repeating unit represented by Chemical Formula 6 is 90 mol % to 99 mol %: 【Transformation 3】 In the above formula 5, R ３１ is a cycloalkylene group having 3 to 10 carbon atoms, and R ３２ is an arylene group having 6 to 20 carbon atoms, 【Chemistry 4】 In the above formula 6, R ３３ is an arylene group having 6 to 9 carbon atoms.

9. In the above formula 5, R ３１ is a cycloalkylene group having 4 to 8 carbon atoms, and R ３２ The liquid crystal polymer for electrical and electronic products according to claim 8, wherein is an arylene group having 6 to 10 carbon atoms.

10. In the above formula 6, R ３３ The liquid crystal polymer for electrical and electronic products according to claim 8, wherein is a phenylene group.

11. 9. The liquid crystal polymer for electrical and electronic products according to claim 8, further comprising one or more repeating units selected from the group consisting of the following Formulas 7, 8, 9, 10, 11, and 12: 【Transformation 5】 In the above formula 7, R ３４ is an arylene group having 10 to 20 carbon atoms, 【Transformation 6】 In the above formula 8, R ３５ is an arylene group having 10 to 20 carbon atoms, and R ３６ is an arylene group having 6 to 9 carbon atoms, 【Transformation 7】 In the above formula 9, R ３７ is an arylene group having 10 to 20 carbon atoms, and R ３８ is an arylene group having 6 to 9 carbon atoms, 【Transformation 8】 In the above formula 10, R ３９ is a cycloalkylene group having 3 to 10 carbon atoms, and R ４０ is an arylene group having 10 to 20 carbon atoms, 【Chemistry 9】 In the above formula 11, R ４１ is a cycloalkylene group having 3 to 10 carbon atoms, and R ４２ is an arylene group having 6 to 9 carbon atoms, 【Chemistry 10】 In the above formula 12, R ４３ is an arylene group having 6 to 9 carbon atoms, and R ４４ is an arylene group having 6 to 9 carbon atoms.

12. A polymer resin composition comprising the liquid crystal polymer for electrical and electronic products described in claim 8.

13. A molded article comprising the polymeric resin composition of claim 12.

Images