JP2007277292A - Thermoplastic resin composition and molded article consisting of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in flowability, and also excellent in mechanical characteristics and impact resistance in its preferable embodiment, and a molded article consisting of the same. <P>SOLUTION: This thermoplastic resin composition contains (b) 0.01 pt.wt. to 20 pts.wt. liquid crystalline resin satisfying formula (1): (melting point)-(liquid crystal onset temperature)≥55°C, based on 100 pts.wt. (a) thermoplastic resin. Further, it is preferable that the melting point of (b) the liquid crystalline resin is at or higher than that of (a) the thermoplastic resin, and the liquid crystal onset temperature of (b) the liquid crystalline resin is at or lower than the melting point of (a) the thermoplastic resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a molded article comprising the same, and more particularly to a thermoplastic resin composition having excellent fluidity and, in a preferred embodiment, excellent mechanical properties and impact resistance, and a molded article comprising the same. Is.

  Thermoplastic resins, especially engineering plastics having excellent mechanical properties and thermal properties, are used in various applications by taking advantage of their excellent properties. Polyamide resin, which is a kind of engineering plastic, has a good balance between mechanical properties and toughness. Therefore, it is used for various electrical and electronic parts, mechanical parts and automobile parts mainly for injection molding. Polybutylene terephthalate (hereinafter referred to as PBT) Is widely used as a material for industrial molded products such as connectors, relays, switches and the like of automobiles and electrical / electronic devices, taking advantage of moldability, heat resistance, mechanical properties and chemical resistance.

  However, in recent years, improvement in fluidity has been demanded as a material to be used in order to cope with the reduction in thickness of molded products accompanying the modularization and weight reduction of large automobile parts. On the other hand, it is known that the fluidity is improved by mixing a liquid crystalline resin with a thermoplastic resin, and various studies have been made so far. Patent Documents 1 and 2 disclose resin compositions in which a liquid crystalline resin is mixed with polyamide. However, when fluidity is evaluated, the fluidity is improved to some extent, but the effect is not sufficient and further fluidity is obtained. There is a need for improvement. The liquid crystalline resin mixed with the polyamide disclosed in Patent Document 1 has a higher carboxyl end group concentration than usual and a high liquid crystal start temperature due to the interaction of the carboxyl end, so the melting point and the liquid crystal start temperature are close, The improvement of the fluidity of polyamide is not sufficient. Further, Patent Document 2 describes an example in which a liquid crystalline resin having a difference between the melting point and the liquid crystal starting temperature is mixed with polyamide, but the difference is not sufficient, and the fluidity improving effect is not sufficient.

Patent Document 3 discloses a method of blocking the polymer end of the polyamide with an acid anhydride in order to suppress the exchange reaction between the polyamide and the liquid crystalline resin. However, the filler is obtained by blocking the polymer end of the polyamide with an acid anhydride. Since there is a tendency for the interface reinforcement and the reaction with the compatibilizing agent to be hindered, there is a need for a method that does not end-block. Further, the liquid crystalline resin mixed with the polyamide disclosed in Patent Document 3 is a liquid crystalline resin having a difference between the melting point and the liquid crystal starting temperature of 30 to 40 ° C. is not.
JP-A-11-315206 (Claims) JP 2001-131405 A (Claims) JP 2000-34404 A (Claims)

  An object of the present invention is to provide a thermoplastic resin composition excellent in fluidity, and in a preferred embodiment, excellent in mechanical properties and impact resistance, and a molded product comprising the same.

  The present invention employs the following means in order to solve such problems.

That is, the present invention
(1) A thermoplastic resin composition comprising 0.01 to 20 parts by weight of a liquid crystalline resin (b) satisfying the following formula (1) with respect to 100 parts by weight of the thermoplastic resin (a):
(Melting point)-(liquid crystal starting temperature) ≥ 55 ° C (1)
(2) The thermoplastic resin composition according to (1), wherein the liquid crystalline resin (b) has a melting point equal to or higher than the melting point of the thermoplastic resin (a),
(3) The thermoplastic resin composition according to (1) or (2), wherein the liquid crystal starting temperature of the liquid crystalline resin (b) is not higher than the melting point of the thermoplastic resin (a),
(4) The thermoplastic resin composition according to any one of (1) to (3), wherein 0.5 to 300 parts by weight of the filler (c) is blended with 100 parts by weight of the thermoplastic resin (a). object,
(5) The thermoplastic resin composition according to (4), wherein the filler (c) is at least one selected from glass fiber, talc, wollastonite, and layered silicate,
(6) The thermoplastic resin composition according to any one of (1) to (5), wherein the thermoplastic resin (a) is a polyamide resin and / or a non-liquid crystalline polyester resin,
(7) A molded product formed by melt-molding the thermoplastic resin composition according to any one of (1) to (6),
(8) The molded product according to (7), wherein the melt molding is at least one melt molding selected from injection molding, injection compression molding and compression molding, and (9) 100 parts by weight of the thermoplastic resin (a) On the other hand, 0.01-20 parts by weight of the liquid crystalline resin (b) satisfying the following formula (1) is kneaded at a temperature not lower than the liquid crystal starting temperature and not higher than the melting point of the liquid crystalline resin (b). Production method of resin composition,
(Melting point)-(liquid crystal starting temperature) ≥ 55 ° C (1)
It is.

  According to the present invention, it is possible to provide a thermoplastic resin composition which is excellent in fluidity and, in a preferred embodiment, excellent in mechanical properties and impact resistance, and a molded article comprising the same.

  The thermoplastic resin (a) used in the present invention may be any resin that can be melt-molded. For example, polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic olefin resin, acrylonitrile / butanediene / styrene (ABS) ) Resin, acrylonitrile / styrene (AS) resin, cellulose resin such as cellulose acetate, non-liquid crystalline polyester resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin, polysulfone resin, polyphenylene sulfide resin, poly Examples include ether ether ketone resins, polyimide resins, and polyetherimide resins, which may be used alone or in combination of two or more. Of these, polyamide resins, non-liquid crystalline polyester resins, polyacetal resins, and polycarbonate resins are preferable, and polyamide resins are more preferable in terms of heat resistance, moldability, fluidity, and mechanical properties. These may be used alone or in combination of two or more as a polymer alloy.

  The polyamide resin is a polyamide mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, pentamethylenediamine , Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosi Chlohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon derived from these raw materials Homopolymers or copolymers, each alone or in the form of a mixture It can be used.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polypentamethylene adipamide (nylon 56), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon) 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide Copolymer (Nai 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / Polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6) Polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynonamethylene terephthalamide (nylon 9T) and Mixtures of al and the like.

  Among these, preferable polyamide resins include nylon 6, nylon 66, nylon 12, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 12, nylon 6T / 6 copolymer, and the like. The copolymer which has the hexamethyl terephthalamide unit of this can be mentioned, Especially preferably, nylon 66 can be mentioned. Furthermore, it is also practically preferable to use these polyamide resins as a mixture depending on necessary properties such as impact resistance and molding processability.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Particularly preferred is a polyamide resin in the range of 2.0 to 6.0.

  Moreover, a copper compound is preferably used in the polyamide resin of the present invention in order to improve long-term heat resistance. Specific examples of copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid. Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate, cuprous iodide, and the like can be exemplified as particularly suitable copper compounds. The addition amount of the copper compound is usually preferably 0.01 to 2 parts by weight and more preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the polyamide resin. If the amount added is too large, metal copper is liberated during melt molding, and the value of the product is reduced by coloring. In the present invention, an alkali halide can be added in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Sodium chloride is particularly preferred.

  The non-liquid crystalline polyester resin (a) used in the present invention is a polymer having an ester bond in the main chain and not exhibiting melt liquid crystallinity, and (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or The ester-forming derivative, (ro) hydroxycarboxylic acid or ester-forming derivative thereof, and (c) a polymer or copolymer having one or more selected from lactone as a main structural unit.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Group dioxy compounds, namely 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and these And ester forming derivatives thereof.

  Polymers or copolymers containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate. , Polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / Terephthalate, polybutylene isophthalate / terephthalate, poly Tylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfo Isophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, polypropylene Terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol , Polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, poly Fragrances such as butylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate Group polyester resin, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, Polypropylene Sebakei , Polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, aliphatic polyester resins such as polybutylene succinate / adipate and the like.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples of the polymer or copolymer having these as a structural unit include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyyoshide. Aliphatic polyester resins such as herbic acid can be mentioned.

  Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Examples of the polymer or copolymer having these as structural units include polycaprolactone. , Polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Among these, a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol. Alternatively, a polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, and an aliphatic diol selected from terephthalic acid or an ester-forming derivative thereof and ethylene glycol, propylene glycol, or butanediol or an ester-forming property thereof. A polymer or copolymer having a derivative as a main structural unit is more preferable, among which polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate. , Aromatic polyester resins such as polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate Are particularly preferred, and polybutylene terephthalate is most preferred.

  In the present invention, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit is It is preferably 30 mol% or more, and more preferably 40 mol% or more.

  In the present invention, it is preferable to use two or more kinds of polyester resins in terms of fluidity and hydrolysis resistance.

  The amount of the carboxyl end group of the non-liquid crystalline polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or less, and 30 eq / t or less in terms of fluidity, hydrolysis resistance and heat resistance. More preferably, it is more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. The lower limit is 0 eq / t. In the present invention, the amount of carboxyl end groups of the non-liquid crystalline polyester resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The vinyl end group amount of the non-liquid crystalline polyester resin used in the present invention is not particularly limited, but is preferably 15 eq / t or less, more preferably 10 eq / t or less, in terms of color tone and fluidity. More preferably, it is 5 eq / t or less. The lower limit is 0 eq / t. In the present invention, the vinyl end group amount of the non-liquid crystalline polyester resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The amount of hydroxyl terminal groups of the non-liquid crystalline polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or more, more preferably 80 eq / t or more in terms of moldability and fluidity. 100 eq / t or more is more preferable, and 120 eq / t or more is particularly preferable. The upper limit is not particularly limited, but is 180 eq / t. In the present invention, the non-liquid crystalline polyester resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The viscosity of the non-liquid crystalline polyester resin used in the present invention is not particularly limited as long as it can be melt kneaded. However, in terms of moldability, the intrinsic viscosity when the o-chlorophenol solution is measured at 25 ° C. is 0.36. It is preferably in the range of ˜1.60 dl / g, more preferably in the range of 0.50 to 1.25 dl / g.

  The molecular weight of the non-liquid crystalline polyester resin used in the present invention is preferably in the range of 50,000 to 500,000, more preferably in the range of 100,000 to 300,000 in terms of heat resistance. The range of 150,000 to 250,000 is more preferable.

  The production method of the non-liquid crystalline polyester resin used in the present invention is not particularly limited and can be produced by a known polycondensation method or ring-opening polymerization method, and may be either batch polymerization or continuous polymerization. In addition, any of transesterification and direct polymerization reactions can be applied, but the amount of carboxyl end groups can be reduced, and the effect of improving fluidity and hydrolysis resistance is increased. Continuous polymerization is preferred, and direct polymerization is preferred in terms of cost.

  When the non-liquid crystalline polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof The dicarboxylic acid or its ester-forming derivative and the diol or its ester-forming derivative can be produced by an esterification reaction or a transesterification reaction and then a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Riphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannon Examples include tin compounds such as alkylstannic acids such as acids, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, and among these, organic titanium compounds and tin compounds include Further, titanic acid tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester are preferred. Properly, tetra -n- butyl ester of titanic acid is especially preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the non-liquid crystalline polyester resin in terms of mechanical properties, moldability and color tone, and 0.01 to 0 The range of 2 parts by weight is more preferred.

  The thermoplastic resin (a) used in the present invention is not particularly limited, but is preferably 120 ° C. or higher, more preferably 180 ° C. or higher, and 200 ° C. or higher in terms of heat resistance. It is preferably 220 ° C. or higher. Although an upper limit is not specifically limited, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less. In the present invention, the melting point of the thermoplastic resin (a) is determined by observing the endothermic peak temperature (Tm1) observed when the thermoplastic resin is measured under a temperature rising condition from room temperature to 20 ° C./min in differential calorimetry. Then, after holding at a temperature of Tm1 + 20 ° C. for 5 minutes, the sample is once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then an endothermic peak temperature (Tm2 ).

  The liquid crystalline resin (b) of the present invention is a polymer that can form anisotropy when melted, and examples thereof include liquid crystalline polyesters, liquid crystalline polyester amides, liquid crystalline polycarbonates, and liquid crystalline polyester elastomers. Those having an ester bond are preferred, and liquid crystalline polyesters, liquid crystalline polyester amides and the like are particularly preferably used.

  Examples of the structural unit of component (b) include aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, and aromatic iminooxy units.

  Specific examples of the aromatic oxycarbonyl unit include, for example, structural units generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and specific examples of the aromatic dioxy unit include, for example, 4,4 ′. -Dihydroxybiphenyl, hydroquinone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, Specific examples of structural units, aromatic and / or aliphatic dicarbonyl units formed from 1,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-di Phenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′diphenyl ether dicarboxylic acid Specific examples of structural units produced from adipic acid, sebacic acid, etc., and alkylenedioxy units include structural units produced from ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, etc. (especially from ethylene glycol) The structural unit produced | generated is preferable.) As a specific example of an aromatic iminooxy unit, the structural unit produced | generated from 4-aminophenol etc. is mentioned, for example.

  Specific examples of the liquid crystalline polyester include a liquid crystalline polyester composed of a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, and 6-hydroxy-2. A structural unit generated from naphthoic acid, a liquid crystalline polyester composed of a structural unit generated from an aromatic dihydroxy compound and / or an aliphatic dicarboxylic acid, a structural unit generated from p-hydroxybenzoic acid, from 4,4′-dihydroxybiphenyl From generated structural units, liquid crystalline polyesters composed of structural units generated from terephthalic acid and / or isophthalic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from terephthalic acid Liquid crystalline polyester , Structural units formed from p-hydroxybenzoic acid, structural units formed from hydroquinone and other aromatic dihydroxy compounds, liquid crystalline polyesters composed of structural units formed from terephthalic acid, p-hydroxybenzoic acid and 6-hydroxy-2- Structural unit produced from naphthoic acid, structural unit produced from 4,4′-dihydroxybiphenyl, liquid crystalline polyester comprising structural unit produced from terephthalic acid, structural unit produced from p-hydroxybenzoic acid, produced from ethylene glycol A structural unit, a liquid crystalline polyester comprising a structural unit produced from terephthalic acid and isophthalic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, and a structure produced from 4,4′-dihydroxybiphenyl Units, liquid crystalline polyesters composed of structural units generated from terephthalic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, terephthalic acid, isophthalic acid, Examples thereof include liquid crystalline polyesters composed of structural units formed from aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid.

  Among them, the component (b) that can be preferably used is a liquid crystalline polyester containing a structural unit composed of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and a liquid crystalline polyester containing an ethylenedioxy unit as a structural unit can also be preferably used. . More preferred are polyesters comprising the following structural units (I), (III) and (IV) or polyesters comprising the structural units of (I), (II), (III) and (IV), most preferred are ( It is a polyester composed of structural units of I), (II), (III) and (IV).

(However, R1 in the formula is

One or more groups selected from R2

One or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. )
The total of the structural units (II) and (III) and the structural unit (IV) are preferably substantially equimolar.

The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4. '-Dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'- A structural unit generated from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, a structural unit (IV) is terephthalic acid, isophthalic acid, 4, 4 '-Diphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid One or more structural units produced from the aromatic dicarboxylic acid obtained are shown. Of these, R ₁ is

And R ₂ is

Are particularly preferred.

  The amount of copolymerization of the structural units (I), (II), (III) and (IV) is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

  That is, in the case of a copolymer comprising the structural units (I), (II), (III), and (IV), the sum of the structural units (I) and (II) is the structural units (I), (II ) And (III) is preferably 30 to 95 mol%, more preferably 40 to 93 mol%. Moreover, 70-5 mol% is preferable with respect to the sum total of structural unit (I), (II), and (III), and, as for structural unit (III), 60-7 mol% is more preferable. The molar ratio [(I) / (II)] of the structural units (I) and (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7. The structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).

  Here, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar.

  On the other hand, when the structural unit (II) is not included, the structural unit (I) is preferably 40 to 90 mol% based on the total of the structural units (I) and (III) from the viewpoint of fluidity. It is particularly preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

  The liquid crystalline polyesteramide is preferably a polyesteramide that forms an anisotropic molten phase containing a p-iminophenoxy unit generated from p-aminophenol in addition to the structural units (I) to (IV).

  The liquid crystalline polyesters and liquid crystalline polyester amides that can be preferably used include 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid in addition to the components constituting the structural units (I) to (IV). Aromatic dicarboxylic acids such as acids, aromatic tricarboxylic acids such as trimesic acid and trimellitic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, aliphatic tricarboxylic acids such as tricarballylic acid, Alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 3 , 4'-Dihydroxybiphenyl Aromatic diols, aromatic triols such as phloroglucinol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc. Aliphatic, cycloaliphatic diols and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, aromatic dihydroxycarboxylic acids such as α-resorcinic acid, β-resorcinic acid and γ-resorcinic acid An acid, p-aminobenzoic acid, and the like can be further copolymerized as long as liquid crystallinity is not impaired. Two or more kinds of liquid crystalline resins may be used in combination.

  The method for producing the component (b) used in the present invention is not particularly limited, and can be produced according to a known polyester polycondensation method.

  For example, in the production of the liquid crystalline polyester, the following production method is preferred.

  (1) Polyester obtained only from components excluding p-hydroxybenzoic acid and p-acetoxybenzoic acid are heated and melted under a dry nitrogen stream to form a copolyester fragment by an acidolysis reaction, and then decompressed to increase the viscosity. To produce liquid crystalline polyester.

  (2) Diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing liquid crystalline polyester by deacetic acid condensation polymerization reaction.

  (3) Acetic anhydride is reacted with aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid. Then, after acylating a phenolic hydroxyl group, a method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction.

  (4) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid Of producing liquid crystalline polyester by dephenol polycondensation reaction.

  (5) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, and isophthalic acid to form diphenyl esters, respectively. A method for producing a liquid crystalline polyester by dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone.

  (6) Polyester polymer such as polyethylene terephthalate, oligomer or liquid crystal by the method of (2) or (3) in the presence of bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate For producing a conductive polyester.

  The polycondensation reaction of the liquid crystalline polyester proceeds even without a catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The liquid crystalline resin (b) used in the present invention needs to have a difference between the melting point and the liquid crystal starting temperature of 55 ° C. or higher, preferably 70 ° C. or higher, particularly preferably 80 ° C. or higher. When the difference between the melting point of the liquid crystalline resin (b) and the liquid crystal starting temperature is less than 55 ° C., the fluidity that is the object of the present invention cannot be improved. The liquid crystalline resin (b) used in the present invention is preferably melt kneaded and melt processed in a liquid crystal state from the viewpoint of improving fluidity. Since the liquid crystalline resin becomes a liquid crystal state in a temperature range below the melting point and above the liquid crystal starting temperature, it is necessary to increase the difference between the melting point of the liquid crystalline resin (b) and the liquid crystal starting temperature, and usually the thermoplastic resin is melted. In the case of kneading, there is a possibility that the temperature rises by 40 to 50 ° C. locally from the set temperature due to shear heat generation or the like. Therefore, the difference between the melting point of the liquid crystalline resin of the present invention and the liquid crystal starting temperature is 55 ° C. or more. The improvement in fluidity, which is the object of the invention, can be achieved.

  In order to make the difference between the melting point of the liquid crystalline resin (b) of the present invention and the liquid crystal starting temperature 55 ° C. or more, the number average molecular weight is preferably 10,000 or less, more preferably 400 to 9000, and particularly preferably 500 to 6000. A liquid crystalline resin having a number average molecular weight is preferably used because it has a large fluidity improving effect. The method for setting the number average molecular weight to 10,000 or less is not particularly limited. However, the method (1) to (6) can be controlled by the reaction rate during polymerization or the methods (1) to (6) can be used to obtain the target number in advance. Examples include a method of polymerizing a liquid crystalline resin having a molecular weight higher than the average molecular weight, and then adding water and melt pelletizing at a temperature of 180 to 380 ° C. using a kneader, a single screw or a twin screw extruder. The number average molecular weight can be measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the liquid crystalline resin is soluble.

  The melting point of the liquid crystalline resin (b) used in the present invention is preferably higher than the melting point of the thermoplastic resin (a). When the liquid crystalline resin (b) having a melting point higher than the melting point of the thermoplastic resin (a) is used, the exchange at the time of melt-kneading is a factor that decreases the liquid crystallinity of the liquid crystalline resin and causes thickening. The reaction can be suppressed. In particular, the liquid crystalline resin (b) having a melting point higher than the melting point of the thermoplastic resin (a) + 20 ° C. is preferably used because it has a large fluidity improving effect. Further, the liquid crystal starting temperature of the liquid crystalline resin (b) used in the present invention is preferably lower than the melting point of the thermoplastic resin (a), and in particular, the liquid crystal starting temperature lower than the melting point of the thermoplastic resin (a) —10 ° C. The liquid crystalline resin (b) is preferably used because it has a large fluidity improving effect.

  The melting point of the liquid crystalline resin (b) in the present invention is the endothermic peak temperature (Tm1) observed when the liquid crystalline resin is measured at room temperature to 20 ° C./min in differential calorimetry, After holding for 5 minutes at a temperature of Tm1 + 20 ° C., after cooling to room temperature under a temperature drop condition of 20 ° C./min, the endothermic peak temperature (Tm2) observed when measured again under a temperature rise condition of 20 ° C./min Point to. The liquid crystal starting temperature of the liquid crystalline resin is measured with a shear stress heating device (CSS-450) at a shear rate of 1000 (1 / sec), a temperature increase rate of 5 ° C./min, and an objective lens of 60 times. The temperature at which the liquid starts to flow is defined as the liquid crystal start temperature.

  The carboxy terminal group and the hydroxy terminal group of the liquid crystalline resin (b) of the present invention are not particularly limited, but from the viewpoint of polymerizability, liquid crystallinity, and fluidity of the thermoplastic resin composition, the one closer to the molar balance is preferred. preferable. If the molar balance is lost and the concentration of one end group is extremely high, it is difficult to make the difference between the melting point and the liquid crystal starting temperature 55 ° C. or higher, which is not preferable. The measuring method of the carboxy end group and the hydroxy end group is not particularly limited, but pentafluorophenol, pentafluorophenol / chloroform = 35/65 (weight ratio) mixed solvent, tetrachloroethane-d2 / pentafluorophenol = 4 ml / 5 g It can melt | dissolve in a mixed solvent etc. and can measure using 1H-NMR.

  The blending amount of the component (b) with respect to 100 parts by weight of the thermoplastic resin (a) used in the present invention is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight. It is. When the blending amount is 0.1 parts by weight or more, a sufficient fluidity improving effect is obtained, and when it is 20 parts by weight or less, the fluidity and mechanical properties at the time of molding, which are the effects of the present invention, are exhibited simultaneously. This is preferable.

In the present invention, in order to impart mechanical strength and other characteristics of the resin composition, 0.5 to 300 parts by weight of the filler (c) is blended with 100 parts by weight of the thermoplastic resin (a) of the present invention. From the viewpoint of fluidity, the amount of the filler (c) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight. If the blending amount of the filler (c) is less than 0.5 parts by weight, the effect of improving the mechanical strength tends to be insufficient, and if it exceeds 300 parts by weight, the fluidity may be lowered or the weight may be increased. is there.
In the present invention, as the type of filler (c), any filler such as fibrous, plate-like, powdery and granular can be used. As filler, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber , Fibrous fillers such as metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, Hydroxides such as calcium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass flakes, glass powder, carbon black and silica, non-fibrous fillers such as graphite, and montmorillonite, beidellite, nontronite, saponite , Smectite clay minerals such as hectorite and soconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica, Li type Layered silicates typified by swelling mica such as tetrasilicon fluorine mica are used. The layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used. Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium. Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium. Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, trioctylmethylammonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecyl. Examples thereof include alkyltrimethylammonium ions such as ammonium, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium. Besides these, it is derived from aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. And ammonium ions. Among these ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid, and the like are preferable. Layered silicates in which exchangeable cations present between layers are exchanged with organic onium ions can be produced by reacting layered silicates having exchangeable cations between layers and organic onium ions by a known method. it can. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or melted ammonium salt may be used. Among these fillers, preferred are glass fibers, talc, wollastonite, layered silicates such as montmorillonite and synthetic mica, and particularly preferred are glass fibers. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said filler (c) can also be used in combination of 2 or more types. The surface of the filler (c) used in the present invention is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agent. You can also. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin.

  Furthermore, in the present invention, in order to maintain thermal stability, one or more heat-resistant agents selected from phenolic and phosphorus compounds can be contained. The blending amount of the heat-resistant agent is preferably 0.01 parts by weight or more, particularly preferably 0.02 parts by weight or more, with respect to 100 parts by weight of the thermoplastic resin composition of the present invention, from the viewpoint of heat resistance improvement effect. From the viewpoint of the gas component generated sometimes, it is preferably 5 parts by weight or less, particularly 1 part by weight or less. In addition, it is particularly preferable to use a phenolic compound and a phosphorus compound in combination because of their large heat resistance, heat stability, and fluidity retention effect.

  As the phenolic compound, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N ′. Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane , Pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl-4- Hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4-hydro) Loxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-). Hydroxyphenyl) propionate] methane and the like are preferably used.

  Next, as phosphorus compounds, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, bis (2,4-di-t-butylphenyl) penta Erythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2 , 4-Di-t-butylphenyl) -4,4′-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate Examples include diethyl ester. Among them, those having a high melting point are preferably used in order to reduce volatilization and decomposition of the heat-resistant material in the thermoplastic resin compound.

  Furthermore, the following compounds can be added to the thermoplastic resin composition of the present invention as long as the effects of the present invention are not impaired. Coupling agents such as organic titanate compounds and organic borane compounds, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds and organic phosphorus compounds, talc, kaolin, organophosphorus compounds, polyether ethers Crystal nucleating agents such as ketones, montanic acid waxes, metal soaps such as lithium stearate and aluminum stearate, release agents such as ethylenediamine, stearic acid and sebacic acid heavy compound, silicone compounds, hypophosphites Ordinary additives such as a lubricant, an ultraviolet light inhibitor, a colorant, a flame retardant, and a foaming agent can be blended. Any of the above compounds is not preferred when the amount exceeds 20 parts by weight relative to 100 parts by weight of the entire polyamide resin composition of the present invention, because the original properties of the thermoplastic resin composition of the present invention are impaired. Is preferably added in an amount of 1 part by weight or less.

  The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, the thermoplastic resin (a), the liquid crystalline resin (b), and other additives as necessary are blended in advance. Thereafter, a method of uniformly melting and kneading with a single or twin screw extruder at a processing temperature not lower than the liquid crystal starting temperature and not higher than the melting point of the liquid crystalline resin (b), a method of removing the solvent after mixing in the solution, etc. are used. . The processing temperature here refers to the set temperature of a single-screw or twin-screw extruder. Among these, from the viewpoint of productivity, a method of uniformly melting and kneading with a single screw or twin screw extruder is preferable, and in particular, using a twin screw extruder, uniformly at a temperature not lower than the liquid crystal starting temperature and not higher than the melting point of the liquid crystalline resin (b). The method of melt kneading is preferably used in that a resin composition having excellent fluidity and mechanical properties can be obtained.

  The resin composition of the present invention can be molded by any method such as generally known injection molding, extrusion molding, blow molding, press molding, and spinning, and can be processed and used in various molded products. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc., as films, as various films such as unstretched, uniaxially stretched, biaxially stretched, as fibers, It can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn. In particular, in the present invention, taking advantage of the excellent fluidity, it can be processed into large injection molded products such as automobile parts and injection molded products having a thin portion having a thickness of 0.01 to 1.0 mm.

  In the present invention, the above-mentioned various molded products can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods. Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blades, washer levers, window regulator handles, knobs for window regulator handles, passing light levers, sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, food louvers, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Car exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and internal parts, Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording medium (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts And electrical / electronic parts such as facsimile housings and internal parts, parabolic antennas, and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection Non-woven fabric, seedling pots, vegetation piles, seed string tape, germination sheets, house lining sheets, farmhouse fasteners, slow-release fertilizers, root-proof sheets, garden nets Insect-proof nets, infant tree nets, printed laminates, fertilizer bags, sample bags, sandbags, animal damage prevention nets, incentive strings, windproof nets and other agricultural materials, paper diapers, sanitary products packaging materials, cotton swabs, towels, toilet seat wipes, etc. Medical supplies such as medical supplies, non-woven fabric for medical use (stitching reinforcing material, anti-adhesion film, prosthetic repair material), wound dressing material, wound tape bandage, sticking material base fabric, surgical suture, fracture reinforcing material, medical film, etc. , Calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets, etc., hot-fill containers, microwave ovens Containers for cooking Cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lids Materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural fibers Various clothing such as composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tapes, prints, thermal Film for stencil printing, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, nonwoven fabric, hot melt binder, magnetic material, zinc sulfide, electrode material powder, etc. Binders, optical elements, conductive embossed tape, C tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag, chair, table, Useful as a cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, wire harness connector, SMJ connector, PCB connector, door grommet connector, etc. It is particularly useful as a connector for various automobiles.

  The thermoplastic resin composition of the present invention and a molded product comprising the same can be recycled. For example, a resin composition obtained by pulverizing a resin composition and a molded product comprising the resin composition, preferably powdered, and then adding additives as necessary, is used in the same manner as the resin composition of the present invention. It can also be a molded product.

  EXAMPLES Hereinafter, although an Example demonstrates the structure and effect of this invention further in detail, this invention is not limited to these.

Reference example 1
Polyethylene terephthalate having 74.5 mol% of p-hydroxy, 7 mol% of 4,4′-dihydroxybiphenyl, 7 mol% of terephthal, and an intrinsic viscosity of about 0.6 dl / g in a reaction vessel equipped with a stirring blade and a distillation pipe. -To 18.6 mol% and acetic anhydride (1.1 equivalents of the total phenolic hydroxyl groups) were allowed to react at 145 ° C for 1.5 hours with stirring under a nitrogen gas atmosphere, and then heated to 280 ° C. The deacetic acid polycondensation reaction was performed. The mixture was stirred for 4 hours, and when 93% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water. The number average molecular weight of the obtained liquid crystalline resin (B-1) was 3,500, the melting point was 286 ° C., and the liquid crystal starting temperature was 180 ° C.

Reference example 2
In a reaction vessel equipped with a stirring blade and a distilling tube, 53.8 mol% of p-hydroxybenzoic acid, 16.2 mol% of 4,4′-dihydroxybiphenyl, 6.9 mol% of hydroquinone, 15 mol% of terephthalic acid, isophthalic acid An acid 8.1 mol% and acetic anhydride (1.1 equivalent of the total phenolic hydroxyl groups) were charged, reacted under stirring in a nitrogen gas atmosphere at 145 ° C for 1.5 hours, and then heated to 260 ° C. A deacetic acid polycondensation reaction was performed. The mixture was stirred for 4 hours, and when 91% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water. The number average molecular weight of the obtained liquid crystalline resin (B-2) was 4000, the melting point was 267 ° C., and the liquid crystal starting temperature was 177 ° C.

Reference example 3
In a reaction vessel equipped with a stirring blade and a distilling tube, 67.5 mol% of p-hydroxybenzoic acid, 7 mol% of 4,4′-dihydroxybiphenyl, 7 mol% of terephthalic acid, and an intrinsic viscosity of about 0.6 dl / g 18.5 mol% of polyethylene terephthalate and acetic anhydride (1.1 equivalents of the total phenolic hydroxyl groups) were charged and reacted at 145 ° C. for 1.5 hours with stirring under a nitrogen gas atmosphere. The acetic acid polycondensation reaction was carried out at an elevated temperature. The mixture was stirred for 4 hours, and when 93% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water. The number average molecular weight of the obtained liquid crystalline resin (B-3) was 3000, the melting point was 240 ° C., and the liquid crystal starting temperature was 180 ° C.

Reference example 4
p-hydroxybenzoic acid 74.7 mol%, 4,4'-dihydroxybiphenyl 7 mol%, terephthalic acid 7 mol%, polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g 11.6 mol% and acetic anhydride (phenol 1.1 equivalent of the total number of functional hydroxyl groups) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacetic acid polycondensation was carried out under the following reaction conditions.
After reacting in a nitrogen gas atmosphere at 100 to 250 ° C. for 1.5 hours, reducing the pressure to 0.5 mmHg at 290 ° C. for 2 hours and further reacting for 1.0 hour to complete the polycondensation, it is almost theoretical. An amount of acetic acid was distilled off to obtain a semi-aromatic liquid crystalline resin (B-4). The number average molecular weight of the obtained liquid crystalline resin was 18000, the liquid crystal starting temperature was 290 ° C., and the melting point was 313 ° C.

Reference Example 5
Reaction vessel equipped with 72.8 mol% p-hydroxybenzoic acid, 27.2 mol% 6-hydroxy-2-naphthoic acid and acetic anhydride (1.1 equivalents of the total phenolic hydroxyl groups) and a distillation tube And deacetic acid polycondensation was carried out. The number average molecular weight of the obtained liquid crystalline resin (B-5) was 14000, the liquid crystal starting temperature was 235 ° C., and the melting point was 283 ° C.

Reference Example 6
78.9 mol% of p-hydroxybenzoic acid and 21.1 mol% of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and 2 at 250 to 300 ° C. After the reaction for a period of time, the pressure was reduced to 0.5 mmHg at 280 ° C. for 1.5 hours, and the reaction was further continued for 0.5 hours to perform polycondensation. The obtained liquid crystalline resin (B-6) had a number average molecular weight of 12000, a liquid crystal starting temperature of 255 ° C., and a melting point of 283 ° C.

Reference Example 7
39.5 mol% p-hydroxybenzoic acid, 7 mol% 4,4'-dihydroxybiphenyl, 7 mol% terephthalic acid, 46.5 mol% polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride (phenol 1.1 equivalent of the total number of functional hydroxyl groups) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacetic acid polycondensation was carried out under the following reaction conditions. In addition, 21.1 mol% of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g was charged into a reaction vessel equipped with a stirring blade and a distilling tube, and reacted at 250 to 300 ° C. for 2 hours. The pressure was reduced to 0.5 mmHg in 5 hours, and polycondensation was performed by reacting for another 0.5 hours. The number average molecular weight of the obtained liquid crystalline resin (B-7) was 15000, the liquid crystal starting temperature was 184 ° C., and the melting point was 205 ° C.

Reference Example 8
100 g of Na-type montmorillonite (Kunimine Industries: Kunipia F, cation exchange capacity 120 m equivalent / 100 g) was stirred and dispersed in 10 liters of hot water, and 48 g of trioctylmethylammonium chloride (equivalent to the cation exchange capacity) was dissolved therein. 2 L of warm water was added and stirred for 1 hour. The resulting precipitate was filtered off and washed with warm water. This washing and filtering operation was performed three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a dried organic layered silicate. When the inorganic ash content of this organically modified layered silicate was measured, the inorganic ash content was 67% by weight. The amount of inorganic ash is a value obtained by ashing 0.1 g of layered silicate in an electric furnace at 500 ° C. for 3 hours.

(1) Melting point An endothermic peak temperature (Tm1) observed when a thermoplastic resin or a liquid crystalline resin is measured under a temperature rising condition from room temperature to 20 ° C./min using a differential scanning calorimeter (Seiko RDC220). ), After maintaining at a temperature of Tm1 + 20 ° C. for 5 minutes, once cooling to room temperature under a temperature drop condition of 20 ° C./min, and then measuring the endothermic peak again when measured under a temperature rise condition of 20 ° C./min. The temperature was measured.

(2) Liquid crystal starting temperature Measured with a shear stress heating device (CSS-450) at a shear rate of 1,000 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens 60 times, and the entire field of view starts to flow. The temperature to be used was defined as the liquid crystal starting temperature.

(3) Fluidity The flow length at a channel thickness of 1 mm was measured using a 1 mm thick bar-shaped molded product mold under the conditions of a melting temperature of 250 ° C. and an injection pressure of 2.0 MPa · G. The longer the flow length, the better the fluidity.

(4) Melt viscosity Measured with a capillograph (manufactured by Toyo Seiki). The measurement conditions are a temperature of 250 ° C., a shear rate of 100 / s, and an orifice diameter of 1 mm.

(5) Tensile strength A tensile test was performed by a test machine Tensilon UTA2.5T (manufactured by Baldwin) at a crosshead speed of 10 mm / min according to ASTM D-638.

(6) Impact resistance According to ASTM D-256, the Izod impact strength of a molded product with a 3 mm thick notch was measured.

(Examples 1-12, Comparative Examples 1-9)
Each component shown below was dry blended in the proportions shown in Tables 1 and 2, and then supplied from an extruder main feeder, and glass fibers were supplied from a side feeder provided downstream of the extruder. Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works, the temperature is set to 250 ° C. and the screw rotation speed is set to 200 rpm, melt kneading is performed. The gut discharged from the die is immediately cooled in a water bath, Pelletized. The pellets obtained were dried at 80 ° C. under reduced pressure for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 250 ° C., mold temperature 80 ° C.). The results of evaluating the fluidity and mechanical properties of each sample are as shown in Tables 1 and 2. Comparative examples 1 and 2 are nylon 6 resin simple substance, but compared with it, Examples 1-8 do not show the fall of a big mechanical physical property, but fluidity | liquidity is improving significantly. In addition, as shown in Examples 9 to 12, it is understood that the fluidity is greatly improved while having excellent mechanical properties even when a filler is added. Although the comparative example 4 is a case where the liquid crystalline resin exceeding the range of description of this invention is added, although the improvement of fluidity | liquidity is seen, the fall is seen in the mechanical characteristic. About Comparative Examples 5-7, although it is a case where the liquid crystalline resin which does not satisfy the requirements of this invention is used, the improvement effect of fluidity | liquidity was a low thing. In Comparative Example 8, the flowability was improved by adding succinic anhydride and endcapping the polyamide, but the mechanical properties tended to decrease. As described above, in this example, compared with the comparative example, the fluidity and mechanical properties were balanced and excellent.

(Examples 13-17, Comparative Examples 10-11)
Each component shown below was dry blended at each ratio shown in Table 3, and then supplied from an extruder main feeder, and glass fibers were supplied from a side feeder provided downstream of the extruder. Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works, the temperature is set to 250 ° C. and the screw rotation speed is set to 200 rpm, melt kneading is performed. The gut discharged from the die is immediately cooled in a water bath, Pelletized. The pellets obtained were dried at 110 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 250 ° C., mold temperature 80 ° C.). The results of evaluating the fluidity and mechanical properties of each sample are shown in Table 3. Compared with Comparative Examples 10 and 11 that are PBT resin alone, Examples 13 to 17 have excellent mechanical properties and fluidity in a well-balanced manner.

(Examples 18 to 20, Comparative Example 12)
Each component shown below was dry-blended in the proportions shown in Table 4 and then supplied from an extruder main feeder. Using a TEX30 twin screw extruder manufactured by Nippon Steel Works, the cylinder set temperature was 250 ° C. and the screw rotation speed was 200 rpm. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The pellets obtained were dried at 110 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 250 ° C., mold temperature 80 ° C.). The results of evaluating the fluidity and mechanical properties of each sample are shown in Table 4. Compared with Comparative Example 12, Examples 18 to 20 have excellent mechanical properties and fluidity in a balanced manner.

The thermoplastic resin (a) used for the present Example and the comparative example is as follows.
A-1: Nylon 6 resin having a melting point of 225 ° C. and 98% sulfuric acid 1 g / dl and a relative viscosity of 2.80 (CM1010 manufactured by Toray Industries, Inc.)
A-2: Nylon 6 resin with a melting point of 225 ° C. and 98% sulfuric acid 1 g / dl and a relative viscosity of 3.40 (CM1021 manufactured by Toray)
A-3: Polybutylene terephthalate resin having a melting point of 225 ° C. and an intrinsic viscosity of 0.85 (1100S manufactured by Toray Industries, Inc.)
A-4: Aromatic polycarbonate “Iupilon” S2000 (manufactured by Mitsubishi Engineering Plastics)

Similarly, the liquid crystalline resin (b) is as follows.
B-1: Reference Example 1
B-2: Reference example 2
B-3: Reference Example 3
B-4: Reference example 4
B-5: Reference Example 5
B-6: Reference Example 6
B-7: Reference Example 7

Similarly, the filler (c) is as follows.
C-1: Glass fiber having a fiber diameter of 13 μm (T-249 manufactured by Nippon Electric Glass)
C-2: Glass fiber having a fiber diameter of 10 μm (CS3J948 manufactured by Nittobo)
C-3: Talc (Nihon Talc SG-200)
C-4: Organized layered silicate prepared according to Reference Example 8 C-5: Wollastonite (NYAD325 manufactured by NYCO)

Claims (9)

A thermoplastic resin composition comprising 0.01 to 20 parts by weight of the liquid crystalline resin (b) satisfying the following formula (1) with respect to 100 parts by weight of the thermoplastic resin (a).
(Melting point)-(liquid crystal starting temperature) ≥ 55 ° C (1) The thermoplastic resin composition according to claim 1, wherein the melting point of the liquid crystalline resin (b) is equal to or higher than the melting point of the thermoplastic resin (a). The thermoplastic resin composition according to claim 1 or 2, wherein a liquid crystal starting temperature of the liquid crystalline resin (b) is not higher than a melting point of the thermoplastic resin (a). The thermoplastic resin composition according to any one of claims 1 to 3, wherein 0.5 to 300 parts by weight of the filler (c) is blended with 100 parts by weight of the thermoplastic resin (a). The thermoplastic resin composition according to claim 4, wherein the filler (c) is at least one selected from glass fiber, talc, wollastonite and layered silicate. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin (a) is a polyamide resin and / or a non-liquid crystalline polyester resin. A molded article formed by melt-molding the thermoplastic resin composition according to claim 1. The molded article according to claim 7, wherein the melt molding is at least one melt molding selected from injection molding, injection compression molding and compression molding. 0.01 to 20 parts by weight of the liquid crystalline resin (b) satisfying the following formula (1) with respect to 100 parts by weight of the thermoplastic resin (a) is brought to a temperature not lower than the liquid crystal start temperature of the liquid crystalline resin (b) and not higher than the melting point Kneading and kneading. A method for producing a thermoplastic resin composition.
(Melting point)-(liquid crystal starting temperature) ≥ 55 ° C (1)