TW201012845A - Liquid crystal polymer and method for producing the same - Google Patents

Abstract

The present invention provides a novel liquid crystal polymer characterized in that an aromatic polyester is obtained by reacting (a) aromatic dicarboxylic acid and aromatic dihydroxyl compound, (b) aromatic dicarboxylic acid, aromatic dihydroxyl compound and aromatic hydroxyl carboxylic acid, or (c) aromatic hydroxyl carboxylic acid. The aromatic dicarboxylic acid, aromatic dihydroxyl compound and aromatic hydroxyl carboxylic acid comprise liquid crystal polymer with structure represented by following formula (1) of the ratio is 0.05 to 48 mole%. The liquid crystal polymer is a novel liquid crystal polymer which does not reduce the flowing property of liquid crystal resin composition and is capable of increasing the welding strength of articles. (in the formula, X1 and X2 are respectively represented oxygen atom or C=O, X3 is an alkylene group having 1 to 8 carbon atoms, a dihydroxyl compound residue having 1 to 8 carbon atoms, oxygen atom, sulfur atom, nitrogen atom, or a linking groupbonding hetero-atom with carbon atom or single bond. R1, R2, R3 and R4 representing hydrogen atom or an alkyl group having 1 to 8 carbon atoms are the same or different, wherein at least one of them is an alkyl group having 1 to 8 carbon atoms).

Description

[Technical Field] The present invention relates to a novel liquid crystal polymer and a method for producing the same, a liquid crystal resin composition using the liquid crystal polymer, and a molded article using the liquid crystal resin composition. [Prior Art] The liquid crystal resin composition is important for its related electrical and electronic parts in recent years due to its excellent fluidity, heat resistance, rigidity, and dimensional stability. However, the fusion strength of the molded article of the liquid crystal resin composition is low. In order to improve the fusion strength of the molded article, a method of blending an inorganic filler with a liquid crystal resin composition has been proposed (for example, Patent Documents 1 and 2), or other resins. A method of melt blending (for example, Patent Documents 3 and 4). However, the liquid crystal resin composition of any of the methods is insufficient in fluidity, heat resistance, formability, mechanical strength, and the like, and the weld strength is also poor. Therefore, there is a need for a material which maintains the above physical properties of the liquid crystal resin composition and has sufficient weld strength. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention provides a novel liquid crystal polymer which can improve the weld strength of a molded article of 201012845 without lowering the fluidity of the liquid crystal resin composition. Means for Solving the Problems The inventors of the present invention have made efforts to solve the above problems and have completed the present invention. That is, the present invention provides a (a) aromatic dicarboxylic acid and an aromatic dihydroxy compound, (b) an aromatic dicarboxylic acid, an aromatic dihydroxy compound, an aromatic hydroxycarboxylic acid, or (C) aromatic An aromatic polyester obtained by reacting a hydroxycarboxylic acid, and the proportion of the structure represented by the following formula (丨) in the aromatic dicarboxylic acid, the aromatic dihydroxy compound, and the aromatic hydroxycarboxylic acid It is a liquid crystal polymer of 0.05 to 48 mol% and a method for producing the same.

(wherein X1 and X2 are each independently an oxygen atom or C=0, an X3 alkylene group having 1 to 8 carbon atoms, a dihydroxy compound having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom or a linking group or a single bond in which a hetero atom is bonded to a carbon atom. R1, R2, R3 and R4 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which are the same or different from each other, at least One of the alkyl groups having 1 to 8 carbon atoms.) According to the liquid crystal polymer of the present invention, a molded article having a thin-walled portion can be formed because of sufficient fluidity, and the obtained molded article has high weld strength. . Therefore, it is helpful for the use of the 201012845 domain for a wide range of electronic components and various parts for automotive applications. It is especially useful for connector parts where thin-walled parts and welded parts occur frequently. [Embodiment] Implementation of the type of invention ❹

The liquid crystal polymer of the present invention is a liquid crystal polymer which forms an anisotropic molten phase, and (a) an aromatic dicarboxylic acid and an aromatic dihydroxy compound, (b) an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and An aromatic polyester obtained by reacting an aromatic hydroxycarboxylic acid or (c) an aromatic hydroxycarboxylic acid, wherein the aromatic dicarboxylic acid, the aromatic dihydroxy compound, and the aromatic hydroxycarboxylic acid have the following The ratio of the structure represented by the formula (1) is 液晶.〇5 to 4 8 mol% of the liquid crystal polymer

(1) A dialkyl group having 1 to 8 subunits, a dihydroxy compound having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a linking group or a single bond in which a hetero atom is bonded to a carbon atom. R1, R2, R3 and R4 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which are the same or different from each other, and at least one of them is an alkyl group having 1 to 8 carbon atoms. When X3 in the above formula (1) is a nitrogen atom, in addition to the NH bond, an azo bond (N = N) is also included. The linking group in which a hetero atom and a carbon atom are bonded is, for example, a ketone bond (C = 0) in which a carbon atom is bonded to an oxygen atom, an ethylene glycol residue (〇CH2CH20), or the like. Further, X3 is a single bond system, and X3 is not ‘201012845 is separated from other atoms, and two benzene rings are directly bonded biphenyl. In the liquid crystal polymer of the present invention, the ratio of the structure represented by the following formula (1) in the aromatic dicarboxylic acid, the aromatic dihydroxy compound, and the aromatic hydroxycarboxylic acid of the raw material of the liquid crystal polymer is 0.0 5-48 mol % ' Especially suitable 3 ~ 4 5 mol%. In the aromatic dicarboxylic acid, the aromatic dihydroxy compound, and the aromatic hydroxycarboxylic acid which are the raw materials of the liquid crystal polymer, the ratio of the structure represented by the above formula (1) is less than 〇.〇5 mol%. However, the strength of the welded portion cannot be sufficiently increased. If it exceeds 48 mol%, the liquid crystal property of the polymer is lowered and the fluidity is poor. The structure of the liquid crystal polymer of the present invention other than the above formula (1), for example, the structure derived from an aromatic dicarboxylic acid described below, the structure derived from an aromatic dihydroxy compound, and the structure derived from an aromatic hydroxycarboxylic acid In such a structure, it is preferable to have a structure represented by the following general formula (2-1) to (2-3). In the following general formulae (2 - 1) to (2 - 3), the formula (2-1) is preferably a structure in which the X4 and X5 groups are bonded to the 1-position and the 3-position or the 1-position and the 4-position of the benzene ring. The formula (2-2) is preferably a structure in which the X4 and X5 groups are bonded to the 1-position and the 5-position or the 2-position and the 6-position of the naphthalene ring, and the general formula (2-3) is preferably bonded to the X4 and X5 systems respectively. The structure of the 4 and 4' positions of the two benzene rings. The polymer chain of the liquid crystal polymer is particularly suitable for forming a linear structure. 201012845 —X4

(2-1)

(2-2) (2-3) (wherein X4 and X5 are independent oxygen atoms or c=0; X4 and χ5 may also be bonded to the same benzene ring; X6 is a carbon number of 1 to 8 An alkyl group, a residue of a dihydroxy compound having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a linking group of a hetero atom bonded to a carbon atom, or a single bond; R1, R2, R3 and R4 a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which are the same or different from each other, at least one of which is an alkyl group having 1 to 8 carbon atoms)

When X6 in the above formula (2-3) is a nitrogen atom, an azo bond (Ν = Ν) is included in addition to the ruthenium bond. The linking group in which a hetero atom and a carbon atom are bonded means, for example, a ketone bond (C = 〇) in which a carbon atom is bonded to an oxygen atom, an ethylene glycol residue (〇CH2CH20), or the like. Further, X6 is a single bond system, and X6 is not separated from other atoms, and two benzene rings are directly bonded biphenyl. Examples of the structure derived from an aromatic carboxylic acid are as follows. 201012845

General och2ch2o Pu ο S'

-C ο Further, examples of the structure derived from the aromatic dihydroxy compound are as follows. ❿ 201012845

〇^^^~CH2CH2^〇 Further, an example of a structure derived from an aromatic hydroxycarboxylic acid is as follows: ο- ΙΙ 〇 . Will c- II 〇 OOl. ο

II ο ·〇

IT ο -10-201012845 Further, the liquid crystal polymer of the present invention is preferably a structure having the following formula (3).

In the formula (3), Ar is an aromatic ring or a heterocyclic ring. Specifically, such Ar is, for example, a benzene ring, a naphthalene ring, a 9-ketopoxime ring, an anthracene ring, an anthracene ring, a heterocyclic ring, a bicyclic ring, a p-tetraphenyl ring, an azobenzene ring, a furan ring, a thiophene ring. Ring, tetrahydropyran ring, 4-keto-tetrahydropyran ring, dibenzofuran ring, dibenzothiophene ring, xanthene ring, dibenzodihydroxysinane ring, phenoxazine ring, thiophene An aromatic ring or a heterocyclic ring structure such as an anthracene ring, a pyrrole ring, an anthracene ring, a carbazole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a quinoline ring, a dipyridine ring or a pyrimidine ring.

Ri'R^R3 and R4 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which are the same or different from each other, and at least one of them is an alkyl group having 1 to 8 carbon atoms. Among them, from the viewpoint of improving mechanical properties and heat resistance, it is preferred that all of R1, R2, R3 and R4 are alkyl groups having 1 to 8 carbon atoms, and most preferably all are methyl groups. X7 is a substituent group of 1 to 8 carbon atoms, a residue of a dihydroxy compound having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a linking group of a hetero atom bonded to a carbon atom, or a single Bonding. Among them, from the viewpoint of improving the mechanical strength of the molded article, etc., it is preferable to use a single bond. In the method for producing a liquid crystal polymer of the present invention, for example, an aromatic dihydroxy compound having a structure of the above formula (1) or an aromatic hydroxycarboxylic acid is an essential component of the formula -11-201012845, and the above formula (2-1) is contained. A method in which an aromatic dihydroxy compound, an aromatic hydroxycarboxylic acid, or an aromatic dicarboxylic acid having a structure of ~(2-3) is directly reacted (hereinafter referred to as "direct method"). The above-mentioned direct method can be carried out by a known manufacturing method, for example, Japanese Patent Publication No. Sho 47-47870, Japanese Patent Publication No. Sho 63-3888, Japanese Patent Publication No. Sho 63-3891, Japanese Patent Publication No. Sho 56-18016, and No. 2-5523 Bulletin, Special Fair 7-47 62 5 Bulletin. Further, the liquid crystal polymer of the present invention may be a liquid crystal polymer having a structure containing the above formula (2-1) to (2-3) in addition to the above direct method (hereinafter referred to as "liquid crystal polymerization". (A)") and an aromatic polyester (hereinafter referred to as "aromatic polyester (B-1)") having a structure containing the above formula (1), and transesterification in the presence of an inorganic carbonate (hereinafter, It is called "transesterification method" and is manufactured. An aromatic polyester (hereinafter referred to as "aromatic polyester (B-2)") having a structure containing the above formula (3) may be used instead of the aromatic polyester having the structure of the above formula (i) ( B-1). The aromatic polyesters (B-1) and (B-2) (hereinafter referred to as "aromatic polyester (B)") are obtained by reacting an aromatic dicarboxylic acid and an aromatic dihydroxy compound. . The aromatic polyester may have the structure of the above formula (1) or (3), and may have other structures in the range which does not impair the effects of the present invention. For glass transfer temperature of 200 °C or more, especially suitable for 230-300 eC. Such an aromatic polyester is preferably one having a weight average molecular weight of from 1 to 1,000,000, particularly preferably from 1 to 300,000. -12- 201012845 Aromatic dicarboxylic acid of a raw material of the above aromatic polyester (B), such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 9-keto fluorene dicarboxylic acid, Terpene dicarboxylic acid, stilbene dicarboxylic acid, heteropoly dicarboxylic acid, terephthalic acid, bis-tetraphenyl dicarboxylic acid, azobenzene dicarboxylic acid, furan dicarboxylic acid, thiophene dicarboxylic acid, tetrahydropyridyl Halodicarboxylic acid, 4-keto-tetrahydropyrandicarboxylic acid, dibenzofuran dicarboxylic acid, dibenzothiophene dicarboxylic acid, xanthene dicarboxylic acid, dibenzodihydroxyquinoline dicarboxylic acid , phenoxazine dicarboxylic acid, thiazide dicarboxylic acid, pyrrole dicarboxylic acid, stilbene dicarboxylic acid, misazodicarboxylic acid, pyrazole dicarboxylic acid, imidazole dicarboxylic acid, dipicolinic acid, quinoline II A carboxylic acid, a dipyridine dicarboxylic acid, a pyrimidine dicarboxylic acid, or the like. In addition to such an aromatic dicarboxylic acid, various aromatic dicarboxylic acid ester derivatives, acid anhydrides, acid halides and the like can be used as a raw material. Among such aromatic dicarboxylic acids, terephthalic acid, isophthalic acid and derivatives thereof are preferred, and they may be used singly or in combination. The proportion of the mixture is expressed in terms of molar ratio, which is preferably terephthalic acid component/isophthalic acid component = 5~1 00/95~0 mol%, especially 60~1〇〇/40~0 mol %. An aromatic dicarboxylic acid used for introducing the structure represented by the above formula (丨) into the above aromatic polyester (B), for example, 3,3,5,5,4-tetraalkyl-(1,1) , a biphenyl)-4,4'-dicarboxylic acid (alkyl group has 1-8), 3,3' one or two bases (1, 丨, a biphenyl)_4,4, a A dicarboxylic acid (having an alkyl group having 1 to 8 carbon atoms) or the like. In addition to such an aromatic dicarboxylic acid, various aromatic diacyl ester derivatives, acid anhydrides, acid halides and the like can be used as a raw material. An aromatic dihydroxy compound used for introducing the above-mentioned general formula (the structure shown) into the above aromatic polyester (B), for example, 3,3,5,5,4-tetraalkyl--13-201012845 (1, 1, 4-biphenyl)-4,4,-diol (the number of carbon atoms in the hospital base is H 3,3'-dialkyl-(1,1,-biphenyl)-4,4'-diol ( The number of the bases is 1~8), 2,2,-bis(4-hydroxy-3-methylphenyl)propane 2,2'-bis(4-hydroxy-3-ethylphenyl)propane, α,α'-bis(trans-based 3,5-dimethylphenyl)-1,4-diisopropylbenzene, bis(4-yl-3-methylphenyl)methane, bis(4-hydroxyl) _3,5-Dimethyldecanoic acid, bis(4-hydroxy-3,5-dimethylphenyl) sulfide, bis(4__3,5-dimethylphenyl)sulfonate, 4,4'- Dihydroxy-3,3'-dimethyl-3-phenyl, 4,4'-dihydroxy-3,3',5,5'-tetramethylbenzophenone has more than 2 aromatic rings and is aromatic There are more than one hospital in the ring. 'It should be 3, 3', 5, 5', 4 yards, _ (1,1'-biphenyl) mono-diol (the number of carbon atoms in the yard is 1~) 8), especially suitable 3,3,5,5-based —(1,1,-biphenyl)-4,4′-diol. In addition to the above aromatic dihydroxy compound, hydroquinone dihydroxybenzene, 1,5-dihydroxynaphthalene, 2,6_ can also be used. Dihydroxynaphthalene, 2,5-diphenyl, 4,4'-diphenol, 4,4'-iso-propyl bisphenol, 4,4'-based benzophenone, 1,2-bis ( 4-hydroxyphenyl)ethane or the like is used as a raw material of the above-mentioned aromatic polyester (Β). Among them, it is preferably a raw material of hydroquinone or 4,4'-diphenyl aromatic polyester (Β), in addition to the above-mentioned aromatic In addition to the group 2 and the aromatic dihydroxy compound, a carboxyl group and a hydroxyaromatic hydroxycarboxylic acid may be used. The aromatic hydroxycarboxylic acid, for example, 3-hydroxy acid, 4-hydroxybenzoic acid, 5-hydroxy-1-naphthalene Acid, 6-hydroxy-2 acid, etc. Among them, 4-hydroxybenzoic acid and 6-hydroxy-2-naphthalene are used. The aromatic hydroxycarboxylic acid is used, and the carbon atom of the above formula (1) is used. Institute, : 4-hydroxyl group) Hydroxy group, etc. 4,4, tetramethyl, m-hydroxydihydroxy phenol, carboxylic acid-based benzo-naphthoquinone. STRUCTURE-14- 201012845 When the above aromatic polyester (B) is ' For example, 3,3',5,5'-tetraalkyl-(1,1'-biphenyl)-tetrahydroxy- 4'-carboxylic acid (the alkyl group has 1 to 8 carbon atoms), 3, 3'-dialkyl-biphenyl)-4-hydroxy- 4'-monocarboxylic acid (the number of carbon atoms of the alkyl group is equal to. The above aromatic polyester (B) can also be produced by a known polymerization method. For example, (1) an aromatic dicarboxylic acid dihalide and an aromatic dihydroxy compound are dissolved in two mutually incompatible solvents, and then mixed in the presence of a base and a catalyst amount of a fourth-order salt or the like. An interfacial polymerization method in which two liquids are stirred and subjected to a polycondensation reaction, and (2) an aromatic dicarboxylic acid dihalide and an aromatic dihydroxy compound are allowed to be present in an organic solvent in the presence of a basic compound such as a third-order amine or the like which receives an acid. a solution polymerization method in which a reaction is carried out, and (3) a melt polymerization method in which a transesterification reaction is carried out in a molten state using an aromatic dicarboxylic acid, an aromatic diester or an aromatic dicarboxylic acid diester and an aromatic diol as a raw material. . The method of the transesterification reaction of the present invention can be carried out by using a known melt-kneading apparatus. For example, a general melt-kneading device such as a 1-axis or 2-axis extruder, a Banbury mixer, a kneading mixer, and a kneader. In the present invention, a one- or two-axis extruder having good productivity is preferably used. For example, the liquid crystal polymer of the present invention can be obtained by melt-kneading at 300 to 370 ° C in a 2-axis extruder having a diameter of 35 mm. The inorganic carbonate used in the present invention, for example, alkali metal carbonate such as lithium carbonate, potassium carbonate or sodium carbonate, alkaline earth metal carbonate such as magnesium carbonate, calcium carbonate or barium carbonate, alkali transition such as iron carbonate, zinc carbonate or silver carbonate A metal carbonate, a hydrogencarbonate such as sodium hydrogencarbonate or calcium hydrogencarbonate. Among them, an alkali metal carbonate or a hydrogencarbonate which is excellent in transesterification reactivity is preferable, and specifically, -15 to 201012845 is preferably lithium carbonate, sodium carbonate or sodium hydrogencarbonate. In the presence of the above inorganic carbonate, the transesterification reaction is efficiently and rapidly carried out between the liquid crystal polymer (A) and the aromatic polyester (B). It is preferable to use a liquid crystal resin composition of the liquid crystal polymer of the present invention in combination with a reinforcing material or a cerium filling material. The reinforcing member or the enamel filler is blended in a range of generally 0 to 400 parts by weight based on 100 parts by weight of the liquid crystal polymer, whereby strength, rigidity, heat resistance and dimensional stability can be further improved. The above-mentioned reinforcing material or enamel filler material such as glass fiber, carbon fiber, glass soft fiber, boron fiber, potassium titanate, zinc oxide or the like, single crystal short fiber, alumina fiber, asbestos, tantalum carbide, aromatic polyamide fiber, ceramic Fiber, metal fiber, gypsum fiber, mica, talc, ash stone, sericite, kaolin, clay, bentonite, asbestos, alumina silicate, zeolite, pyrophyllite, etc., calcium carbonate, magnesium carbonate, Sulphate such as dolomite, calcium sulfate, barium sulfate, etc., aluminum oxide, magnesium oxide, cerium oxide, zirconium oxide, titanium oxide, iron oxide or the like, glass beads, ceramic beads, boron nitride, carbonization矽, calcium phosphate, etc. Reinforcing materials or enamel filling materials can be used alone or in more than 2 types. Further, the reinforcing material or the enamel filler may be treated by a coupling agent such as a decane-based or titanium-based compound. The reinforcing material or the cerium material is kneaded at the stage of producing the liquid crystal resin composition of the present invention, and may be kneaded after the liquid crystal resin composition is produced. Usually this mixing is carried out in a 1-axis or 2-axis extruder having a plurality of feed ports. Thereafter, it is produced by molding into an arbitrary shape by an injection molding machine or the like having an appropriate mold. -16- 201012845 The liquid crystal resin composition of the present invention can be blended with a small amount of a releasing agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a flame retardant, and the like without departing from the object of the present invention. Additives such as flame retardant adjuvants and rust inhibitors. Various ultraviolet absorbers, antioxidants, and antistatic agents may be added to improve weather resistance, oxidative degradation resistance, and antistatic property within a range that does not impair the heat resistance of the liquid crystal polymer of the present invention. The liquid crystal resin composition of the present invention can be prepared by various known methods. The known preparation method is, for example, mixing a raw material in a drum or a mixer in advance, and then feeding it into a 1-axis or 2-axis extruder, a Banbury mixer, a kneading mixer, a kneader, and the like. In the kneading apparatus, the melting temperature of the mixture is about 200 to 500 ° C, and the mixture is melt-kneaded and then granulated. The liquid crystal resin composition of the present invention is formed by a known molding method, whereby the molded article of the present invention can be obtained. Known molding methods such as injection molding, extrusion molding, injection compression molding, compression molding, blow molding, and the like, and injection molding is preferred. The molded article of the present invention is excellent in mechanical strength, heat resistance, electrical properties, solvent resistance, and the like, and is suitable for use in electrical fields, electronic parts, and machine parts. Specifically, for example, connectors, bobbins, various socket sockets, capacitors, variable capacitors, optical pickups, various terminal disks, plugs, magnetic top seats, automotive tubes, intake nozzles, intake manifolds , vaporizer, lamp holder, lamp reflector, lampshade, etc. • 17- 201012845 〆Example (Example 1) In a reaction vessel equipped with a cooler and a mixer, put '121.2g (〇·5 mole) 3,3,5,5,4-tetramethyl-4, 4'-diphenol, 55.1g (0.5 mole) hydrogen awake, 93.1g (0.5 mole) 4,4'-diphenol, 116.3g (0.7 mole) terephthalic acid, 64.9g (0.3m) 2,6-naphthalenedicarboxylic acid, 621_5 g (4.5 mol) of 4-hydroxybenzoic acid and 612.5 g (6 mol) of acetic anhydride were heated under stirring in a nitrogen atmosphere at 170 ° C for 60 minutes. On the other hand, while the acetic acid of the by-product was removed, the reaction vessel was slowly heated to 370 ° C for 4 hours, and then the pressure in the reaction system was reduced to 25 kPa at this temperature. Thereafter, acetic acid of the by-product was removed at this temperature, and the pressure was reduced to about 0.5 to 1 kPa over 2 hours to carry out polymerization. The polymerization was carried out at 370 ° C for 1 hour, and the acetic acid of the by-product was removed, and polymerization was carried out under vigorous stirring. Finally, the reaction system was slowly cooled to 200 ° C, and the resulting resin was taken out of the reaction system to obtain a liquid crystal polymer (LCP - 1 ). (Example 2) 0 In addition to changing the amount of 121.2 g (0.5 mol) of 3,3',5,5,tetramethyl- 4,4'-diphenyl to 484.6 g (2.0 mol), Polymerization was carried out in the same manner as in Example i to obtain a liquid crystal polymer (Lcp-2). (Example 3) In addition to changing the amount of 121.2 g (0.5 mol) of 3,3,5,5,tetramethyl-4,4'-diphenol to 1090.8 g (4.5 m), and examples i was polymerized in the same manner to obtain a liquid crystal polymer (LCP_3). (Synthesis Example 1) -18. 201012845 Polymerization was carried out in the same manner as in Example 1 except that 3,3',5,5'-tetramethyl-4,4,-diphenol was not added to obtain a liquid crystal polymer. (LCP - 4). (Synthesis Example 2) In addition to 55.1 g (0.5 mol) of hydrogen sink, 93. lg (0.5 mol) of 4,4'-diphenol, 116.3 g (0.7 mol) of terephthalic acid, 43.3 g (〇) .2 mol) 2,6-naphthalenedicarboxylic acid, 24.2 g (〇.1 mol) 4,4'-biphenyldicarboxylic acid, 621.5 g (4.5 m) of 4-benzoic acid and 612.5 g (6 mol) other than acetic anhydride' was polymerized in the same manner as in Example 1 to obtain a liquid crystal polymer (LCP-5). (Synthesis Example 3) In addition to 110.1 g (l mole) of hydroquinone, 58.1 g (0.35 mole) of terephthalic acid, 58.1 g (0-35 moles) of isophthalic acid, and 64.9 g (〇_3 mole) A liquid crystal polymer was prepared by the same procedure as in Example 1 except that 2,6-naphthalene diacid, 621.5 g (4.5 mol) of 4-nonylbenzoic acid and 612.5 g (6 mol) of acetic anhydride were used. LCP-6). (Synthesis Example 4) 2.41 g (9.8 mol) of 3,3',5,5'-tetramethyl- 4,4'-diphenol was dissolved in a polymerization apparatus equipped with a stirring blade and a nitrogen introduction port. A solution of 30 kg of dehydrated water of 1.0 kg of sodium hydroxide gives an aqueous solution. In a separate container, 78 g of methyltrioctyl ammonium chloride, 1.58 kg (7.8 mol) of isophthalic acid chloride, and 406 g (2.0 mol) of terephthalic acid chloride were dissolved in 5 liters of deoxygenated Toluene, but an organic solution. While stirring the above aqueous solution under a nitrogen stream, the above-prepared organic solution was slowly added, and stirring was continued at 25 ° C for 30 minutes. Next, remove and remove the aqueous phase by tilting -19-201012845. The organic solution phase containing the product was washed repeatedly with distilled water and then poured into an acetone bath to obtain a precipitate. The precipitate was washed with acetone to make PAR. Thereafter, the mixture was slowly heated from room temperature in a vacuum dryer, and finally vacuum dried at 240 ° C under a reduced pressure of about 400 Pa for 3.5 minutes to obtain 3.5 kg of an aromatic polyester (pAR-1). ). The melting point and load bending temperature of the liquid crystal polymer (LCP -1 to 6) obtained above were measured according to the following method. 〇 (Measurement of melting point) The melting point of each liquid crystal polymer was measured in accordance with JIS K7121 - 1987 using a differential scanning calorimeter ("DSC-7" manufactured by Pajen Emma Japan Co., Ltd.). (Measurement of load bending temperature) The load bending temperature of each liquid crystal polymer is in a coaxial reciprocating screw type injection molding machine, and the cylinder temperature is 3 3 0 to 370 ° C, the mold temperature is 13 (TC, the injection pressure is 80 to 100 MPa, The injection speed was a medium speed forming condition, and a test piece formed to a thickness of 3.1 mm was used, and it was measured according to AS TMD64 8. φ (liquid crystal property evaluation of resin) liquid crystal polymer (LCP_1~6) and aromatic polyester (PAR) —1) The optical anisotropy was evaluated by a polarizing microscope, and the optical anisotropy was evaluated on the basis of the following criteria: 〇: liquid crystallinity, X: no liquid crystallinity, liquid crystal polymer (LCP-1 to 6), and aromatic Polyester (PAR-1), Table 1 shows the amount (mass) of each raw material at the time of synthesis, and the amount of each raw material in the second synthesis (mole) and the synthesis Characteristics of each resin 値 -20- 201012845 [Table 1]

Example 1 Example 2 Example 3 Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Raw material compound functional group LCP-1 LCP-2 LCP-3 LCP4 LCP-5 LCP-6 PAR-1 3, 3', 5, 5' -tetramethyl 4,4,-diphenol OH/OH 121.2 484.6 1090.8 2410.0 Addition of hydroquinone OH/OH 55.1 55.1 55.1 55.1 55.1 110.1 4,4'-diphenyl OH/OH 93.1 93,1 93.1 93.1 93.1 Terephthalic acid COOH/COOH 116.3 116.3 116.3 116.3 116.3 58.1 g isophthalic acid COOH/COOH 58.1 2,6-naphthalenedicarboxylic acid COOH/COOH 64.9 64.9 64.9 64.9 43.3 64.9 4,4'-biphenyldicarboxylic acid COOH /COOH 24.2 4-Amphoteric benzoic acid 0H/C00H 621.5 621.5 621.5 621.5 621.5 621.5 C0C1/C0C1 406.0 C0C1/C0C1 1580Ό

[1 1 2 Table] Put in % Raw material compound functional group LCP-1 LCP-2 LCP-3 LCP-4 LCP-5 LCP-6 PAR-1 3,3',5,5' ·Tetramethyl 4,4 ,-Diphenol OH/OH 0.50 2.00 4.50 9.80 Hydrogen OH/OH 0.50 0.50 0.50 0.50 0.50 1.00 4,4,-Diphenol OH/OH 0.50 0.50 0.50 0.50 0.50 Terephthalic acid COOH/COOH 0.70 0.70 0.70 0.70 0.70 0.35 Isophthalic acid COOH/COOH 0.35 2,6-naphthalenedicarboxylic acid COOH/COOH 0.30 0.30 0.30 0.30 0.20 0.30 4,4'-biphenyldicarboxylic acid COOH/COOH 0.10 4-hydroxybenzoic acid OH/COOH 4.50 4.50 4.50 4.50 4.50 4.50 C0C1/C0C1 2.00 Acacia coccoci 7.80 Moir 5JS 7.00 8.50 11.00 6.50 6.50 6.50 19.60 OH Molar 7.50 10.50 15.50 6.50 6.50 6.50 19.60 COOH Molar 6.50 6.50 6.50 6.50 6.50 6.50 19.60 Containing formula ( 1) Structure of Moer % 7 24 41 0 0 0 50 Characteristics 値 Melting point (°C) 348 346 342 350 365 328 Unmeasured load bending temperature 258 258 255 252 258 270 238 No liquid crystal properties of resin 〇〇〇X -21- 201012845 (production of evaluation test piece) 70 parts by mass of the above-mentioned LCP-1~6 and 30 parts by mass of ΙΟμπι diameter glass fiber surface-treated with amino decane were placed in a 2-axis extruder having a diameter of 35 mm, and melted at 300 to 370 °C. The mixture was kneaded to obtain pellets of a liquid crystal resin composition. Next, the pellet is a coaxial reciprocating screw type injection molding machine, and is formed into a thickness of 3.1 mm at a cylinder temperature of 330-370 ° C, a mold temperature of 130 ° C, an injection pressure of 80 to 100 MPa, and an injection speed of a medium speed. Test piece. ® (Examples 4 to 6 and Comparative Examples 1 to 3) Using the test piece prepared above, the melting point and the load bending temperature were measured in the same manner as above. The weld strength maintenance ratio and fluidity were measured by the following methods using the pellets of the liquid crystal resin composition obtained above. Using LCP1~3, the evaluators were Examples 4 to 6, and LCPs 4 to 6 were used, and the evaluators were Comparative Examples 1 to 3. (Measurement of the welding strength retention rate) The number of switching gate valves is 1 point (non-welding) and 2 points (welding), and the pellets of the liquid crystal resin composition obtained above are injection-molded into a molded article having the shape shown in Fig. 1 (gate valve system) 1) as shown in Figure 1. The molded article of the shape of Fig. 1 is provided with a 50×50×1 mm-thick sheet, and a non-filling portion (2 in Fig. 1) of a plastic plug having a diameter of 10 mm is used, and a thermoplastic resin is further composed. The object is filled in the surroundings to form a shape that is easily welded when formed by a two-point gate valve. Then, the test piece (cut at the broken line 3 in Fig. 1) was cut out at intervals of 1 mm in each molded article, and the welding strength was evaluated by measuring the bending strength. The welding strength maintenance rate was calculated by (bending the bending force of the two-point gate valve -22-201012845/the bending strength x1 〇〇 (%) of the one-point gate valve). When the welding strength maintenance ratio was calculated, the test piece 1 (4 in Fig. 1) and the test piece 2 (5 in Fig. 1) were used. (evaluation of liquidity)

Using the pellet of the liquid crystal resin composition prepared above, a mold having a length of 127 mm, a width of 10 mm, and a thickness of 0.3 mm was passed through a coaxial reciprocating screw type injection molding machine at a cylinder temperature of 3 30 to 370 ° C and a mold temperature of 130 °. C. The injection pressure is 80 to 100 MPa, and the injection speed is a medium-speed molding condition, and the resin flows into the mold in the longitudinal direction to have a flow length (mm), whereby the flow rate is long and the fluidity is evaluated. The compositions and evaluation results of the liquid crystal resin compositions of Examples 4 to 6 and Comparative Examples 1 to 3 are shown in Table 3. In the third table, the "% of the resin having the structure of the general formula (1) in the resin" is an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and an aromatic hydroxycarboxylic acid which are raw materials of the resin, and the following The proportion of the structure of the general formula (1). [Table 3] Example 4 Example 5 Example 6 Ratio_2 Comparative Example 3 Group LCP-1 70 into LCP-2 70 (LCP-3 70 LCP-4 70 LCP-5 70%) LCP-6 70 mam 30 30 30 30 30 30 Resin contains (1) 7 24 41 0 0 0 Evaluation of melting point (. 〇 348 345 343 351 365 330 valence load * 曲 temperature (r) 279 275 270 279 288 258 knot maintenance rate - test piece 1 (%) 70 76 79 41 35 30 Hybrid retention rate - test piece 2 (%) 64 70 74 40 32 29 Fluidity (mm) 46 38 34 48 40 36 -23-

201012845 From the evaluation results of the third table, it is understood that the liquid crystal polymer of the liquid crystal polymer of the present invention having the above-described general structure examples 4 to 6 is composed of a dense liquid crystal resin of a comparative example having no structure of the above formula (1). Comparing the materials, the welding strength is greatly improved, and the melting point, the load bending temperature, and the fluidity are evaluated. It is understood that the structure of the general formula (1) can maintain the liquid crystal polymer almost with the knot I having no formula (1). Characteristics. (Example 7) 60 parts by mass of LCP - 4, 10 obtained in Synthesis Example 1, PAR-1 obtained in Example 4, 1 part by mass of lithium carbonate, and 30 masses of decane were surface-treated with ΙΟμιη diameter glass fibers. The 2-axis extruder is melt-kneaded at 3 00~3 70 °C! a particle of a lipid composition. (Example 8) A pellet of the liquid crystal resin composition was prepared in the same manner as in Example 7 except that LCP-5 obtained in Synthesis Example 2 was used instead of the LCP-4 obtained in Example 1. (Example 9) A particle of a liquid crystal resin composition prepared in the same manner as in Example 7 except that LCP-6 obtained in Synthesis Example 3 was substituted for LCP-4 obtained in Example 1 except Example 1 (Comparative Example 4) The mass fraction was obtained by mass fraction of LCP-4 obtained in Synthesis Example 1, PAR-1 obtained in Example 4, and 30 parts by mass of the composition of the amine decane formula (1). Even if they are the same, the amount of the synthetic component is the same as that of the amine [the 35 mm diameter liquid crystal tree is used, the combined operation is used, and the amount of the synthetic glass surface is at the surface of the composite line - 24 - 201012845. 35 mm of 2 Å 3 00 to 3 70 ° C was melt-kneaded to obtain a liquid crystal resin composition shirt (Comparative Example 5). In addition to the LCP-5 prepared in Synthesis Example 2, the LCP-4 obtained in Comparative Example 1 was replaced. In addition, the granules of the liquid crystal resin composition were prepared and compared. (Comparative Example 6) The particles of the liquid crystal resin composition were prepared except that LCP-6 obtained in Synthesis Example 3 was used in place of LCP-4 obtained in Comparative Example® Synthesis Example 1 (Comparative Example 7). 60 parts by mass of LCP-4, 10 scented polyester obtained in Synthesis Example 1 ("U-100" manufactured by Unichka Co., Ltd.; propyl bisphenol and isophthalic acid and terephthalic acid) Polyester (hereinafter referred to as "PAR-2"), 1 part by mass of 1 part by mass of a 10 μm diameter glass 0 diameter 2 mm 2-axis extruder surface-treated with amino decane, at 300 to 370 t The particles of the liquid crystal resin composition are smoked. (Comparative Example 8) The particles of the liquid crystal resin composition were obtained by substituting LCP-4 obtained in Synthesis Example 2 in place of LCP-4 obtained in Comparative Example 1, except that LCP-4 obtained in Synthesis Example 1 was used. (Comparative Example 9) The particles of the comparative example 丨 extruder, I was replaced by LCP-6 obtained in Synthesis Example 3. 4 used 4 identical 4 used in the same operation 4 of the same mass of the aromatic 4,4' a mixture of aromatic I and 30 mass of glass fiber into the melt mixing, 7 used 7 In the same manner as in Comparative Example 7, except that LCP-4 obtained in Synthesis Example 1 was used, the particles of the liquid crystal resin composition were obtained. (Comparative Example 10) 60 parts by mass of LCP-4 obtained in Synthesis Example 1, 10 parts by mass of calcium thiocyanate whisker, and 30 parts by mass of glass fiber of ι〇μι diameter surface-treated with amino decane were placed. A 2-axis extruder having a diameter of 35 mm was melt-kneaded at 300 to 37 (TC) to obtain pellets of a liquid crystal resin composition. (Comparative Example 1 1) In place of Comparative Example 10, LCP-5 obtained in Synthesis Example 2 was used. In the same manner as in Comparative Example 1 except that LCP-4 obtained in Synthesis Example 1 was used, particles of a liquid crystal resin composition were obtained. (Comparative Example 1 2) LCP-6 obtained by the synthesis example 3 was obtained. The pellets of the liquid crystal resin composition were obtained in the same manner as in Comparative Example 10 except for the LCP-4 obtained in Synthesis Example 1 used in Comparative Example 10. (Measurement and Evaluation of Liquid Crystal Resin Compositions) Example 7~ The melting point, the load bending temperature, the welding strength maintenance ratio, and the fluidity of the liquid crystal resin compositions of Comparative Examples 4 and 12 were evaluated by the above methods. The liquid crystal resin compositions of Examples 7 to 9 and Comparative Examples 4 to 12 were used. The composition and evaluation results are shown in Tables 4 and 5. In addition, in Tables 4 and 5, "Resin" In the total of the aromatic dicarboxylic acid, the aromatic dihydroxy compound, and the aromatic hydroxycarboxylic acid which are the raw materials of the resin, the following formula (1) Ratio of structure. -26- 201012845 [Table 4] Example 7 Example 8 Example 9 Comparative Example 4 Comparative Example 5 Comparative Example 6 Group LCP-4 60 60 into LCP-5 60 60 (LCP-6 60 60 PAR -1 10 10 10 10 10 10 Amount of carbon 1 1 1 %) Glass surface 30 30 30 30 30 30 % of the resin containing the structure of the formula (1) 17 17 17 17 17 17 Ester exchange reaction There are no or no evaluation melting point rc) 348 360 325 347 360 326 Price load 1 «曲 temperature (. 〇 279 286 254 277 285 255 knot dissolution strength maintenance rate - test piece 1 (%) 74 72 68 62 56 51 bet鲢 Maintain rate _ piece 2 (%) 68 66 62 57 52 48 Fluidity (mm) 44 36 31 29 24 21

[Table 5] Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Group LCP-4 60 60 into LCP-5 60 60 (LCP-6 60 60 PAR-2 10 10 10 sulfuric acid Anhydride consumption whiskers 10 10 10 % Carbon 1 1 1 ) Glass 雠 30 30 30 30 30 30 Resin containing the structure of the formula (1) Mox % 0 0 0 0 0 0 Ester exchange reaction Whether or not there is no evaluation point rc) 346 361 327 350 362 327 Price load bending temperature (. 〇 264 276 244 276 285 254 knot welding strength maintenance rate - mode 1 (%) 36 32 28 60 57 50 fruit strength maintenance rate Sheet 2 (%) 34 30 26 53 51 48 Fluidity (mm) 28 22 19 28 22 20 -27- 201012845 In Examples 7 to 9, the liquid crystal polymer (LCP-4-6) was made to contain the above formula (1). The aromatic polyester (PAR-1) of the structure is melt-kneaded in a 2-axis extruder, and the lithium carbonate microcatalyst of inorganic carbonate is obtained by a transesterification reaction to obtain a general formula (1). The liquid crystal polymer of the present invention has a structure. On the other hand, in Comparative Examples 4 to 6, since no carbonic acid clock is used, transesterification does not occur. The reaction was carried out to form a resin mixture of a liquid crystal polymer (LCP-4 to 6) and an aromatic polyester (PAR-1) having a structure of the above formula (1). Comparing the evaluation results, examples 7 to 9 were obtained. The liquid crystal resin composition using the liquid crystal polymer of the present invention has a high weld strength retention ratio, whereas the liquid crystal polymer of Comparative Examples 4 to 6 and the aromatic polyester having the structure of the above formula (1) The resin mixture was lower than the examples 7 to 9 in which the weld strength retention rate was increased, and the fluidity was also lower. Further, in Comparative Examples 7 to 9, the liquid crystal polymer (LCP-4 to 6) was not included. When the aromatic polyester (PAR-2) having the structure of the formula (1) is melt-kneaded in a 2-axis extruder, the lithium carbonate microcatalyst which is an inorganic carbonate is produced by a transesterification reaction. It is a liquid crystal polymer which does not contain the structure of the general formula (1). The liquid crystal resin composition of Comparative Examples 7 to 9 using this liquid crystal polymer has a low weld strength retention rate and low fluidity. In 10~12, the method of generally improving the degree of fusion, that is, adding calcium sulphate The welding strength of the liquid crystal resin composition of Comparative Examples 10 to 12 is improved, and the fluidity is lowered. [Simplified description of the drawing] The first graph is not used for the calculation of the weld strength retention ratio and the cut-out -28 - A picture of the test piece of 201012845. [Description of main component symbols] 1 Gate valve (0.5mmx〇.5mm; angle shape) 2 Use non-filling part of diameter 1 〇mm plastic hole plug 3 Cutting line 4 Test piece 1 5 Test piece 2

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Claims (1)

201012845 VII. Patent application scope: 1. A liquid crystal polymer characterized by (a) an aromatic dicarboxylic acid and an aromatic dihydroxy compound, (b) an aromatic dicarboxylic acid, an aromatic dihydroxy compound and an aromatic An aromatic polyester obtained by reacting a hydroxycarboxylic acid or (c) an aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, an aromatic dihydroxy compound, and an aromatic hydroxycarboxylic acid have the following formula ( 1) The ratio of the structure shown is 〇.〇5~48 mol%. (wherein X1 and X2 are each independently an oxygen atom or c=o, x3 is an alkylene group having 1 to 8 carbon atoms, a dihydroxy compound having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a linking group thereof in which a hetero atom is bonded to a carbon atom, or a single bond; R1, R2, R3 and R4 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which are the same or different from each other, wherein At least one is an alkyl group having 1 to 8 carbon atoms). 2. The liquid crystal polymer of claim 1 which contains any one of the following formulas (2-1) to (2-3), -30-201012845 (2-1) (2- 2) (2-3) (In the formula, 'X4 and X5 are independent oxygen atoms or c=o; x4 and X5 may also be bonded to the same benzene ring; X6 is an alkyl group having 1 to 8 carbon atoms and 1 to 8 carbon atoms. a dihydroxy compound residue, an oxygen atom, a sulfur atom, a nitrogen atom, or a linking group thereof in which a hetero atom is bonded to a carbon atom, or a single bond; R1, R2, R3, and R4 are hydrogen atoms or carbon atoms 1-8 The alkyl groups are the same or different from each other, at least one of which is an alkyl group having 1 to 8 carbon atoms. 3. A method for producing a liquid crystal polymer according to claim 2, characterized in that an aromatic polyester containing any one of the structures (2-1) to (2-3) and containing the same An aromatic polyester having a structure of the formula (1), which is subjected to a transesterification reaction in the presence of an inorganic carbonate. The method for producing a liquid crystal polymer according to claim 3, wherein the inorganic carbonate is at least A group consisting of an alkali metal carbonate, an alumina metal carbonate, and a ruthenium transition metal ruthenium carbonate. A liquid crystal resin composition characterized by containing a liquid crystal polymer as claimed in claim 1 or 2. A molded article characterized by being formed of a liquid crystal resin composition as disclosed in claim 5 of the patent application. -31- 201012845 7. A connector part characterized by being formed of a liquid crystal resin composition as in claim 5 of the patent application. ❿ -32-