LIQUID CRYSTAL COPOLYESTERS HAVING A BLOCKED TERMINAL OF ITS MOLECULAR CHAIN

Abstract: A liquid crystal copolyester having at its terminal a blocked molecular chain. The liquid crystal copolyester comprising a copolyester which exhibits anisotropy in a molten state and which has a functional group located at the terminal of its molecular chain and which is blocked with a low-molecular compound which includes at least one aromatic ring and which has a molecular weight of 350 or less.

Description: The present invention relates to copolyesters having high flowability, improved moisture resistance and improved hydrolysis resistance which comprise copolyesters exhibiting anisotropy in a molten state the copolyester having a functional group located at the terminal of its molecular chain which is blocked with a low-molecular compound which includes at least one aromatic ring. In recent years, a liquid crystal polymer which exhibits anisotropy in a molten state has attracted attention as a resin having high strength, high heat resistance, and excellent chemical resistance as well as excellent mouldability and processability. Various proposals have been made on the liquid crystal polymer. With respect to representative examples of such proposals, reference may be made to Japanese Patent Laid-Open Nos. 72393/1974, 43223/1975 and 50594/1979. In all of these liquid crystal polymers, a rigid monomer is incorporated in the skeleton thereof to develop liquid crystal properties, which realizes a resin having a high strength and easy processability. As is well known, a resin which exhibits anisotropy in a molten state has an extremely low viscosity because the melt viscosity depends on shear, so that the resin can be utilized per se as thin film parts and fine parts or in the form of a composite material containing a filler and a reinforcing material incorporated therein for various heat-resistant parts and precision parts. In particular, the low viscosity of the polymer per se enables the incorporation of a filler and a reinforcing material in high proportions which directs attention to the use of the resin for applications where an extremely high dimensional stability is required or in the field of magnetic materials in which the performance is proportional to the content of the filler. In the above-mentioned resin, the molecular weight must usually be reduced when a lower viscosity in a molten state is desired. Such an expedient somewhat spoils the mechanical strength, heat resistance, and chemical resistance. Since the bond units of the molecular chain comprise ester bonds, the resistance to hydrolysis greatly depends upon the molecular weight and a reduction in molecular weight for the purpose of further reducing the viscosity of the polymer which exhibits anisotropy in a molten state substantially covers the hydrolysis resistance and thus leads to the lowering in mechanical strength. Although it is self-evident that the terminal of the molecular chain must be blocked in order to improve the hydrolysis resistance of a polyester, it is not easy to block the terminal while neither spoiling the liquid crystal properties nor lowering the heat resistance. This is because not only the development of the liquid crystal properties itself depends on a delicate balance among various molecular skeletons but also the influence of the terminal blocking agent is liable to be more markedly exhibited than in the case of other polymers due to the lowering in the molecular weight. European Patent Specification 0 161 413 discloses completely aromatic polyesters in which at least one end of the molecular chain is composed of the radicals in which Z denotes an aromatic ring system. European Patent No. 0 165 399 discloses thermotropic fully-aromatic polyesters which contain radicals of 3,4'- and/or 4,4'-dihydroxybenzophenone in addition to radicals of p-hydroxybenzoic acid, iso-and optionally terephthalic acid, hydroquinone and/or 4,4'-dihydroxydiphenyl, which may contain as terminal groups -COOH, -H, -OH, -OC₆H₅, acyloxy or radicals deriving from chain terminators. Monofunctional aromatic hydroxyl compounds, such as 4-hydroxy-diphenyl, p-nonylphenol, 4-(1,1,3,3-tetramethylbutyl)-phenol, β-naphthol, and aromatic monocarboxylic acids, such as diphenylcarboxylic acids and naphthalene carboxylic acids are preferred chain terminators. U.S Patent No. 4 473 681 discloses polyester ureas which commonly exhibit -O-CO-CH₃ or -CO-OH and groups which may optionally be capped, e.g. acidic end groups may be capped with a variety of alcohols and hydroxyl end groups may be capped with a variety of organic acids. Thus phenylester -CO-O-Ph and methylester -CO-O-CH₃ end capping units may optionally be included at the end of the polymer chains. Following extensive and intensive studies with a view to realizing a resin having a combination of low viscosity with excellent hydrolysis resistance, it has now been found that the above-mentioned two properties which are contradictory to each other can be simultaneously realized by blocking the molecular chain terminal with a specific compound. Accordingly the present invention provides a liquid crystal copolyester which comprises a copolyester exhibiting anisotropy in a molten state and which has a functional group located at the terminal of its molecular chain said terminal being blocked with a low-molecular compound which includes at least one aromatic ring characterized in that said low-molecular compound used for blocking said terminal is at least one member selected from among the compounds represented by the following formulae (A) to (F): wherein R₁ and R₂ are each a substituent selected from among alkyl having 1 to 10 carbon atoms, -Cl, -Br, -OCH₃, -CN, -NO₂, -NH₂, vinyl, ethynyl, acrylate, phenyl, benzyl, alkylurea, alkyl ester, and maleimino; Y is a group selected from among alkylene having 1 to 4 carbon atoms, alkylidene, -O-, -S-, -SO-, SO₂, and -CO-; n is an integer of 0 to 2; and x is a functional group selected from among aldehyde, hydroxyl, carboxyl, amino, imino, glycidyl ether, glycidyl ester, methyl, isocyanato, acetoxy, carboxyalkyl ester (wherein the alkyl has 1 to 4 carbon atoms), and carboxy-phenyl ester; in that the molecular weight of said low molecular weight compound is 350 or less and in that at least 25% of said terminals are blocked with said low molecular weight compounds. In the present invention, the low-molecular compound used for blocking the molecular chain terminal is a compound having a molecular weight of 350 or less and which includes at least one aromatic ring. A molecular weight exceeding 350 unfavourably leads to an increase in viscosity. This has an adverse effect on the liquid crystal properties. Reduction in viscosity when the skeleton is other than an aromatic ring greatly inhibits the terminal blocking reaction with respect to the main chain polymer. Further, it is required that the low-molecular compound has at least one reactive group capable of reacting with a functional group at the terminal of the polymer, i.e., a hydroxyl group, a carboxyl group and/or an amino group. Examples of the reactive group include aldehyde, hydroxyl, carboxyl, amino, imino, glycidyl ether, glycidyl ester, allylsubstitued methyl, isocyanato, and acetoxy groups. Preferable reactive groups are hydroxyl, carboxyl, amino and their esters, and glycidyl groups. Preferably the compounds represented by the formula (A) include hydroxypyridine, 2-methyl-2-hydroxypyridine, and compounds obtained by acetoxylating them, nicotinic acid, 2-methylnicotinic acid and their methyl esters. Preferably, the compounds represented by the formula (B) include 2-phenyl-2'-p-hydroxy-phenylpropane, 2-phenyl-2'-p-acetoxyphenylpropane, p-isocyanylphenyl, p-phenylurenylphenylmethane, and bis-4,4'-diisocyanylphenylmethane. Preferably, the compounds represented by the formula (C) 1 ○ include 8-hydroxyquinoline, 2-hydroxyquinoline, 8-acetoxyquinoline, 2-acetoxy-quinoline, 2-carboxyquinoline, and its methyl ester, phenyl ester, etc. Preferably, the compounds represented by the formula (C) 2 ○ include 3-carboxyisoquinoline, 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid, and their methyl ester, phenyl ester, etc. Preferably, the compounds represented by the formula (D) include 4-hydroxyindole, 5-hydroxy-indole, 5-hydroxyindoline, 4-acetoxyindole, 5-acetoxy-indole, 5-hydroxyindole. Preferably, the compounds represented by the formula (E) include 7-hydroxyindene, 5-hydroxy-indene, 1-indanol, 5-indanol, 7-acetoxyindanol, 5-acetoxyindene, 1-aminoindane, and 2-aminoindane. Preferably, the compounds represented by the formula (F) include anthranol, anthracene-9-carboxylic acid, and 9-acetoxyanthracene. The resin, having a molecular chain terminal to be blocked, according to the present invention is a thermoplastic, melt-processable polymer composition which is optically anisotropic in a molten state and generally belongs to a thermotropic liquid crystal polymer. The polymer which forms such an anisotropic melt phase has properties such that the molecular chains are regularly arranged parallel to each other in a molten state. The state, in which molecules are arranged in this way, is often called a liquid crystal state or a nematic phase of a liquid crystal material. Such polymer molecules are generally comprised of polymers which are slender and flat and have considerably high rigidity along the major axis of the molecules and a plurality of chain-extending bonds which are usually in either a coaxial relationship or a parallel relationship with each other. The properties of the anisotropic melt phase may be examined by a customary polarimetric method using crossed polarizers. More particularly, the anisotropic melt phase can be examined by observing a molten sample placed on a Leitz hot stage in a nitrogen atmosphere at a magnification of 40 under a Leitz polarization microscope. The above-mentioned polymer is optically anisotropic. Namely, when it is placed between crossed polarizers, it permits transmission of a light beam. If the sample is optically anisotropic, the polarized light will be transmitted, even when it is in a static state. It is preferred that the liquid crystal copolyester which exhibits anisotropy in a molten state and has a terminal to be blocked be comprised mainly of an aromatic polyester or an aromatic polyester-amide. Further, the liquid crystal copolyester may contain a polyester or a polyester-amide having other skeletons which do not exhibit anisotropy in a molten state and are part of the same molecular chain and in such an amount as will not spoil the anisotropy in a molten state. The polyester having other skeletons which do not exhibit anisotropy in themselves and are contained in part of the same molecular chain is preferably a polyalkylene terephthalate in which the alkylene has 4 or less carbon atoms. Polyethylene terephthalate and polybutylene terephthalate are also suitable. The copolyester which exhibits anisotropy in a molten state may be comprised of various compounds. However, it is preferred that the copolyester be comprised of an essential component which is at least one compound selected from among 1 ○ naphthalene compounds, 2 ○ phenyl compounds, 3 ○ 4,4'-biphenyl compounds, and 4 ○ compounds represented by the following general formula: wherein Z is alkylene (c₁ ∿ c₄), alkylidene (C₁ ∿ C₄), -O-, -S-, -SO-, SO₂-' and -CO-, and R and R' are each a reactive group such as hydroxyl or carboxyl, or their ester. Preferably the compounds constituting the copolyester include naphthalene compounds such as 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 6-hydroxy-2naphthoic acid, and their ester derivatives; para-substituted benzene compounds such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol, p-phenylenediamine, and their ester derivatives; metasubstituted benzene compounds such as isophthalic acid and resorcinol; biphenyl compounds such as 4,4'-dihydroxybiphenyl, 4,4'-dicarboxybiphenyl; and compounds represented by the above general formula wherein Z is propane, methane, sulfite, or the like. Among the copolyester comprised of the above-mentioned components, a copolyester containing at least one member selected from among naphthalene compounds, biphenyl compounds, and para-substituted benzene compounds as essential component are more preferable. Particularly preferable para-substituted benzene compounds include p-hydroxybenzoic acid, methylhydroquinone, and 1-phenylethylhydroquinone. Examples of a specific combination of components include: In the above formulae, P is a substituent selected from among -Cℓ, -Br, and -CH₃, Q is a substituent selected from among alkylene (C₁ ∿ C₄), alkylidene, -O-, -SO-, SO₂, -S-, and -CO-. It is preferred that the molecular weight of the copolyester which exhibits anisotropy in a molten state be 30,000. A molecular weight exceeding 30,000 necessarily causes an increase in viscosity when molten, which inhibits the realization of high flowability. The flowability is increased with lowering in molecular weight. However, the molecular weight is preferably 1,000 or more from the standpoint of shape retention. Although it is most preferred that the functional groups located at both of the molecular chain terminals be blocked, the blocking of only one molecular chain terminal is also acceptable. It is preferred that at least 45 percent of the terminal groups are blocked with the low molecular weight compounds. The reaction for blocking the terminal is conducted in a solution, a suspending medium, a molten state, or the like, which is usually employed in the polymerization reaction of polymers. However, a rigid polymer which exhibits anisotropy in a molten state as will be mentioned later is generally insoluble in an organic solvent. Therefore, it is preferred that the reaction be conducted in such a state that the resulting polymer is in a molten state. Further, in the reaction, a blocking agent compound may be added at any time of the initiation of the polymerization, during the polymerization and/or after the polymerization. In the reaction, it is also effective to use a usually employed ester forming catalyst which will be mentioned later. The polyester and/or polyester-amide which exhibit anisotropy in a molten state and is useful for the present invention can be produced various ester forming processes. The monomer compounds can be reacted by a melt acidolysis method in the absence of any heat exchange fluid. According to this method, the monomers are first heated together to form a melt of reactants. As the reaction proceeds, solid polymer particles are suspended in the melt. Vacuum may be applied in order to facilitate the removal of volatile matter (e.g., acetic acid or water) which is produced as a by-product in the final stage of the condensation. Further, a slurry condensation method may also be adopted in forming a wholly aromatic polyester suitable for use in the present invention. In this method, the solid product is obtained in such a state that it is suspended in a heat exchange medium. In both the above-mentioned melt acidolysis process and slurry polymerization process, the organic monomer reactants from which the wholly aromatic polyester is derived may be used in the reaction in a modified form in which the hydroxyl groups of such monomers have been esterified at room temperature (i.e., in the form of a lower acyl ester). The lower acyl group preferably has 2 to 4 carbon atoms. It is preferred that acetates of the organic monomer reactants be used in the reaction. Further, the organic monomer reactants may also be used in a modified form in which the carboxylic acid group has been esterified (i.e., in the form of a phenol ester). Representative examples of the catalyst which can be used at will in both the melt acidolysis and slurry processes include dialkyltin oxides (e.g., dibutyltin oxide), diaryltin oxides, titanium dioxide, antimony trioxide, alkoxytitanium silicate, titanium alkoxide, alkali and alkaline earth metal salts of carboxylic acids (e.g., zinc acetate), Lewis acids (e.g., BF₃) and gaseous catalysts such as hydrogen halides (e.g., HCℓ). The amount of the catalyst is generally about 0.001 to 1% by weight, preferably about 0.01 to 0.2% by weight, based on the total weight of the monomers. The aromatic polymers produced in the present invention tend to be substantially insoluble in usual solvents, which renders them unsuitable for use in solution processing. However, these polymers may be readily processed by ordinary melt processing. The aromatic polymers produced in the present invention are somewhat soluble in pentafluorophenol. The polymers produced in the present invention generally exhibit an inherent viscosity (I.V.) of at least about 0.3 dℓ/g, e.g., about 0.3 to 10.0 dℓ/g, as determined at 60°C in the form of a solution prepared by dissolving the polymer in pentafluorophenol to have a polymer concentration of 0.1% by weight. In order to improve various mechanical characteristics, the resin composition of the present invention may be blended with various additives and/or fillers by the methods known to those skilled in the art. Examples of these additives include materials which are added to general thermoplastic resins and thermosetting resins, i.e., plasticizers, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, coloring materials such as dyes and pigments, foaming agents, crosslinking agents such as divinyl compounds, peroxides and vulcanizing agents, and lubricants for improving the flowability and releasability. Examples of the fillers include general inorganic fibers such as glass fiber, carbon fiber, metallic fiber, ceramic fiber, boron fiber, and asbestos; and powdery or sheet inorganic fillers such as calcium carbonate, highly dispersible silicic acid, alumina, aluminum hydroxide, talc powder, mica, glass flake, glass beads, quartz sand, silica sand, various powdery metals, carbon black, barium sulfate, plaster of Paris, silicon carbide, alumina, boron nitrite, and silicon nitride; and whisker and metallic whisker. The polymers produced in the present invention have excellent flowability in a molten state and resistance to hydrolysis. They can therefore be usefully employed in various applications in the fields of electric and electronic components. The polymers are particularly suitable for use in packaging agents of electronic components and printed circuit boards in which high flowability and moisture resistance are required. Further, when the use is intended in such an application as sealing agents of integrated circuit parts which require remarkably excellent dimensional stability, moisture resistance, and high flowability, the best suited material can be provided by forming a composite material in combination with a suitable filler such as molten silica. The present invention will now be described in more detail with reference to the following examples. The conversions showing pressure in kg/m² have been calculated on the assumption that mmHg measurements were carried out at 0°C. Resins A to C used in the following examples were previously prepared by polymerization as follows. <resin A> A reactor equipped with a stirrer, a nitrogen inlet tube, and a discharge tube was charged with 68 parts by weight of isophthalic acid, 3944 parts by weight of terephthalic acid, 720 parts by weight of p-acetoxybenzoic acid, 216 parts by weight of 4,4′-diacetoxybiphenyl, and 439.2 parts by weight of 2,6-diacetoxynaphthalene. The mixture was heated at 260°C under a stream of nitrogen. The heated mixture was vigorously stirred at 260°C for 3 hr and then at 280°C for 3 hr while formed acetic acid was distilled off from the reactor. The temperature was further raised to 300°C, and the feed of nitrogen was stopped. Then, the inside of the reactor was gradually evacuated so that the pressure was reduced to 0.1 mmHg (1.359kg/m²) 15 min after the initiation of evacuation. The contents of the reactor were stirred at this temperature and pressure for 1 hr. The resulting polymer had an inherent viscosity of 0.82 as determined at 60°C in the form of a pentafluorophenol solution containing 0.1% by weight of the polymer. In the observation under a polarization microscope, the polymer exhibited a pattern of a nematic liquid crystal in a molten state on a hot stage. <resin B> A reactor equipped with a stirrer, a nitrogen inlet tube, and a discharge tube was charged with 768 parts by weight of polyethylene terephthalate having an inherent viscosity of 0.62 and 1080 parts by weight of p-acetoxybenzoic acid. The mixture was heated at 250°C under a stream of nitrogen. The mixture was further heated so that the temperature reached 275°C after 1 hr, and then vigorously stirred for 2 hr. The feed of nitrogen was stopped. Then, the inside of the reactor was gradually evacuated so that the pressure was reduced to 0.2 mmHg (2.718 kg/m²) 30 min after the initiation of evacuation, and the contents of the reactor were further stirred for 6 hr. The resulting polymer exhibited anisotropy in a molten state on a hot stage in the observation under a polarization microscope and had an inherent viscosity of 0.74 as determined in pentafluorophenol. <resin C> A reactor equipped with a stirrer, a nitrogen inlet tube, and a discharge tube was charged with 1188 parts by weight of p-acetoxybenzoic acid, 690 parts by weight of 2-acetoxy-6-naphthoic acid, and 54.4 parts by weight of terephthalic acid. The mixture was heated at 260°C under a stream of nitrogen. The heated mixture was vigorously stirred at 260°C for 3 hr and then at 280°C for 3 hr while formed acetic acid was distilled off from the reactor. The temperature was further raised to 320°C, and the feed of nitrogen was stopped. Then, the inside of the reactor was gradualy evacuated so that the pressure was reduced to 0.1 mmHg (1.359 kg/m²) 15 min after the initiation of evacuation. The contents of the reactor were stirred at this temperature and pressure for 1 hr. The resulting polymer exhibited anisotropy in a molten state on a hot stage in the observation under a polarization microscope and had an inherent viscosity of 0.82 as determined in pentafluorophenol. The easiness of hydrolysis was evaluated based on the data on the lowering in inherent viscosity accompanying the hydrolysis reaction and increase in electrical conductivity of an aqueous solution of the resulting hydrolysis product. Example 1 A reactor equipped with a stirrer, a nitrogen inlet tube, and a discharge tube was charged with 500 parts by weight of the above-mentioned resin B and 104 parts by weight of a monofunctional isocyanate compound obtained by reacting 250 parts by weight of methylenediphenylene diisocyanate with 99 parts by weight of cyclohexanol, and 500 parts by weight of the resin B were placed in a reactor. The mixture was heated at 265°C under a nitrogen stream and was vigorously stirred for 6 hrs. while stirring with the reactor hermetically sealed, thereby causing a reaction. The resulting polymer was pulverized while cooling with liquid nitrogen to obtain powder. The powder was washed with a hot mixed solvent comprised of toluene and acetone. The powder was dried by removing the solvent and then applied to the following tests. The percentage blocking of the terminal of the resulting polymer was 75% as determined from the amount of the recovered excessive terminal blocking agent, had an inherent viscosity of 0.78 and exhibited anisotropy in a molten state in the observation under a polarization microscope. Further, the melting point of the polymer was determined with a DSC, and the polymer exhibited a melting point Tm of 305°C during elevation of temperature. 10 g of the polymer powder as prepared above and 100 mℓ of purified water were placed in a clean Soxhlet extractor and refluxed therein. 300 hr after the initiation of the reflux, the inherent viscosity of the sample was determined and found to be 0.72. The refluxed, extracted water was cooled to room temperature respectively 72 hr and 300 hr after the initiation of the reflux and applied to the determination of electrical conductivity with a conductivity meter manufactured by Toa Denpa. As a result, it was found that the electrical conductivity was 69 µS/cm and 167 µs/cm. Examples 2 to 7 Various terminal blocking agents were used, and the resulting polymers were applied to the same test. The results are shown in Table 1. Comparative Examples 1 to 4 The same test as in Example 1 was conducted without using any terminal blocking agent according to the formulations as shown in Table 1. The results are shown in Table 1. Comparative Example 5 An attempt to block the terminal of the resin A was made using a compound represented by the following formula: wherein n is 4.1. However, the percentage blocking of the terminal was as low as 3% or less. The observation of the resulting blocked polymer under a polarization microscope afforded a dark field in a molten state, and the polymer exhibited no liquid crystal properties.

Claims: A liquid crystal copolyester, which comprises a copolyester exhibiting anisotropy in a molten state and which has a functional group located at the terminal of its molecular chain said terminal being blocked with a low-molecular compound which includes at least one aromatic ring characterized in that said low-molecular compound used for blocking said terminal is at least one member selected from among the compounds represented by the following formulae (A) to (F): wherein R₁ and R₂ are each a substituent selected from among alkyl having 1 to 10 carbon atoms, -Cl, -Br, -OCH₃, -CN, -NO₂, -NH₂, vinyl, ethynyl, acrylate, phenyl, benzyl, alkylurea, alkyl ester, and maleimino; Y is a group selected from among alkylene having 1 to 4 carbon atoms, alkylidene, -O-, -S- -SO-, SO₂-, and -CO-; n is an integer of 0 to 2; and x is a functional group selected from among aldehyde, hydroxyl, carboxyl, amino, imino, glycidyl ether, glycidyl ester, methyl, isocyanato, acetoxy, carboxyalkyl ester (wherein the alkyl has 1 to 4 carbon atoms), and carboxy-phenyl ester; in that the molecular weight of said low molecular weight compound is 350 or less and in that at least 25% of said terminals are blocked with said low molecular weight compounds. A liquid crystal copolyester according to claim 1, characterized in that the functional group X of said low-molecular compound used for blocking said terminal is a reactive group selected from among hydroxyl, carboxyl, amino and their esters, and glycidyl. A liquid crystal copolyester according to claim 1 or 2, characterized in that said copolyester which exhibits anisotropy in a molten state contains in part an aromatic polyester or (and) an aromatic polyesteramide which does not exhibit anisotropy in itself in the same molecular chain. A liquid crystal copolyester according to claim 3, characterized in that said aromatic polyester which does not exhibit anisotropy in itself is polyalkylene terephthalate. A liquid crystal copolyester according to claim 4, characterized in that the alkylene of said polyalkylene terephthalate has 4 or less carbon atoms. A liquid crystal copolyester according to any of claims 1 to 5, characterized in that said copolyester which exhibits anisotropy in a molten state is comprised of at least one component selected from among 1 ○ naphthalene compounds, 2 ○ phenyl compounds, 3 ○ 4,4'-biphenyl compounds, and 4 ○ compounds represented by the following general formula: wherein Z is alkylene (C₁ ∿ C₄), alkylidene (C₁ ∿ C₄), -O-, -S-, -SO-, -SO₂-, and -CO-, and R and R' are each a reactive group such as hydroxyl or carboxyl, or esters thereof. A liquid crystal copolyester according to claim 6, characterized in that said naphthalene compound is at least one compound selected from; 2,6-dicarboxynaphthalene, 2,6-dihydroxynaphthalene, 2-hydroxy-6-naphthoic acid and esters thereof. A liquid crystal copolyester according to claim 6, characterized in that said phenyl compound is at least one compound selected from among p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol, and their substituted derivatives and ester compounds thereof. A liquid crystal copolyester according to claim 7, characterized in that said biphenyl compound is at least one compound selected from among 4,4'-dihydroxybiphenyl, 4,4'-dicarboxybiphenyl, 4-hydroxy-4'-carboxybiphenyl, and esters thereof. A liquid crystal copolyester according to any of the preceding claims, characterized in that said copolyester has a molecular weight of 30,000 or less. A liquid crystal polyester according to any of the preceding claims characterised in that at least 45% of said terminals are blocked with said low molecular weight compound.

Inventors: HIJIKATA, KENJI, SHIKAE, TOSHIO
Applicants: POLYPLASTICS CO. LTD.
Application year: 1987
Main classification: C08G63
IPC codes: C09K19, C08G63