JP5309896B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent mechanical properties, heat resistance and improved flowability and a molded article comprising the same. <P>SOLUTION: The thermoplastic resin composition is obtained by mixing 100 pts.wt. of a resin composition composed of 5-95 wt.% of at least one kind of an amorphous resin (a) and 5-95 wt.% of a thermoplastic resin (b) except an amorphous resin (a) with 0.01-30 pts.wt. of a dendritic polyester resin (c) comprising at least one kind of a structural unit selected from an aromatic oxycarbonyl unit (S), an aromatic and/or aliphatic dioxy unit (T) and an aromatic dicarbonyl unit (U) and a tri- or more functional organic residue (D) in which the content of (D) is 7.5-50 mol% based on the total monomers constituting the dendritic polyester. <P>COPYRIGHT: (C)2009,JPO&amp;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 excellent in mechanical properties and heat resistance and having significantly improved fluidity and a molded article comprising the same. is there.

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 used as a material for industrial molded products such as connectors, relays, switches, etc. of automobiles and electrical / electronic devices, taking advantage of moldability, heat resistance, mechanical properties and chemical resistance. In addition, these engineering plastics are used in a wide variety of applications, so often they cannot exhibit sufficient properties alone, and may be used by being melt mixed with different types of resins in order to improve their insufficient properties. Many (Patent Documents 1 to 3 etc.) However, when different types of resins are kneaded, the mechanical properties are improved and the fluidity is greatly reduced, so that a good product may not be obtained. In recent years, fluidity has been regarded as important as a material to be used in order to cope with the modularization and thinning of molded products accompanying weight reduction of large automobile parts. Patent Documents 4 to 8 disclose resins using hyperbranched polymers. Although the composition is described and has a certain degree of fluidity improvement effect, development of a better fluidization method is required in order to cope with the modularization and thinning of the molded products accompanying the recent reduction in the weight of automobile large parts. It has been.
JP 2007-186704 A (claim) JP 2006-328287 A (Claims) JP 2007-197695 A (Claims) JP 2005-520028 A (claim) International Publication No. 2005/75563 (Claims) International Publication No. 2005/75565 (Claims) International Publication No. 2006/42705 (Claims) European Patent No. 142360 (claim)

  An object of the present invention is to provide a thermoplastic resin composition excellent in mechanical properties and heat resistance, and improved in fluidity, and a molded article comprising the same.

The present invention employs the following means as a result of intensive studies to solve the above problems.
1. At least one amorphous resin selected from polyphenylene ether resin, polycarbonate resin, polyetherimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, amorphous polyamide resin, polyphenylene sulfide sulfone resin ( a) 5 to 95% by weight and at least one thermoplastic resin (b) selected from crystalline polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene sulfide resin, ABS resin The aromatic oxycarbonyl unit (S) represented by the following formula (1), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit with respect to 100 parts by weight of the resin composition Choose from (U) At least one structural unit and a trifunctional or tetrafunctional aromatic organic residue (D), and the total content of S, T, U and D is 7.5%. P / q is 5/95 or more and p / r is 5/95 when the average molar content of the structural units S, T, and U is p, q, and r, respectively. The thermoplastic resin composition obtained by blending 0.01 to 30 parts by weight of the dendritic polyester resin (c) exhibiting molten liquid crystallinity.

(Here, R1, R2 and R3 are each at least one structural unit selected from structural units represented by the following formula.)

(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.)
2. 2. The thermoplastic resin composition as described in 1 above, wherein the dendritic polyester resin (c) contains a basic skeleton represented by the following formula (2).

(Here, D is an organic residue of a trifunctional compound, and DD is bonded directly by an ester bond and / or an amide bond, or bonded via a structural unit selected from S, T and U. Yes.)
3. 2. The thermoplastic resin composition as described in 1 above, wherein the dendritic polyester resin (c) contains a basic skeleton represented by the following formula (3).

(Here, D is an organic residue of a tetrafunctional compound, and DD is bonded directly by an ester bond and / or an amide bond or via a structural unit selected from S, T and U. Yes.)
4). 3. The thermoplastic resin composition as described in 1 or 2 above, wherein the organic residue D of the dendritic polyester resin (c) is an organic residue of a compound represented by the following formula (4).

5. 5. The thermoplastic resin composition as described in any one of 1 to 4 above, wherein the thermoplastic resin (b) is a crystalline polyamide resin.
6 . 6. The thermoplastic resin composition as described in any one of 1 to 5 above, wherein the amorphous resin (a) is a polyphenylene ether resin.
7 . A molded article obtained by melt-molding the thermoplastic resin composition according to any one of 1 to 6 above.
8 . 8. The molded article according to 7 above, wherein the melt molding is any one selected from injection molding, injection compression molding, and compression molding.
9 . The film which consists of a thermoplastic resin composition in any one of said 1-6 .

  According to the present invention, it is possible to provide a thermoplastic resin composition that is excellent in fluidity and highly balanced in mechanical properties and heat resistance. The thermoplastic resin composition of the present invention has good fluidity, and has excellent surface appearance (color tone), mechanical properties by molding methods such as ordinary injection molding, injection compression molding, compression molding, extrusion molding, and press molding. It can be processed into shaped articles, sheets, pipes, films, fibers and the like having properties.

  The thermoplastic resin composition of the present invention includes polycarbonate resin, polyphenylene ether resin, polyetherimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, amorphous polyamide resin, polyphenylene sulfide. It is essential to contain at least one amorphous resin (a) selected from sulfone resins.

  The polycarbonate resin used in the present invention is a resin having a carbonate bond, and examples thereof include a thermoplastic resin obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. A polycarbonate resin having a concentration of 1.0 g / dl in methylene chloride and a logarithmic viscosity measured at 20 ° C. of 0.2 to 3.0 dl / g, particularly 0.3 to 1.5 dl / g is preferably used. . Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl- 1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.

The amount of the end group of the polycarbonate is not particularly defined, but in order to further develop the effect of the present invention, the equivalent ratio (E _P ) / phenolic end group (E _P ) / non-phenolic end group (E _N ) / A polycarbonate resin having (E _N ) of 1/19 or less is preferably used, more preferably 1/40 or less, and even more preferably 1/70 or less.

  The end group of the polycarbonate resin can be measured, for example, by dissolving the polycarbonate resin in acetic acid methylene chloride, adding titanium tetrachloride, and photometrically determining the resulting red complex at 546 nm.

  The polyphenylene ether resin used in the present invention is a thermoplastic resin represented by the following structural unit (9), and a polymer having an intrinsic viscosity of 0.01 to 0.80 dl / g measured at 30 ° C. in chloroform. Preferably used.

(R4 to R7 are groups such as hydrogen, halogen, aliphatic group having 1 to 10 carbon atoms, aromatic group, alicyclic group, sulfonyl group, and nitro group, and these may be the same or different. May be.)

  Specific examples of R4 to R7 include groups such as hydrogen, chlorine, methyl, ethyl, propyl, isopropyl, allyl, butyl, phenyl, benzyl, methylbenzyl, chloromethyl, cyanomethyl, cyanomethoxy, ethoxy, phenoxy, and nitro. These may be the same or different.

  Specifically, poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,4,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3 , 6-triethylphenol copolymer and the like. Further, the polyphenylene ether-based resin may have a graft structure, and can be used even if it is partially modified by adding another third component. Polyphenylene ether resins can be preferably used regardless of the terminal group structure and amount, but for example, polystyrene or cyclic polyolefin resins are added to improve compatibility with them or for other purposes. The modified polyphenylene ether to which a suitable amount of a compound having a reactive group such as maleic anhydride or glycidyl methacrylate is added can be preferably used.

  The polyetherimide resin used in the present invention is not particularly limited as long as it is a polymer having an ether bond and an imide bond in the main chain, but 2,2-bis [4- (2,3-dicarboxyl) is not particularly limited. Phenoxy) phenyl] propane dianhydride and m-phenylenediamine, or p-phenylenediamine, and a polycondensate of a mixture of m-phenylenediamine and p-phenylenediamine are preferred. This polyetherimide is available from GE Plastics under the trade name “Ultem” (registered trademark).

  Examples of the polyamideimide resin used in the present invention include a polymer having a repeating unit represented by the following structural unit (10).

(Wherein R8 represents a divalent aromatic and / or aliphatic group, R9 represents hydrogen, a methyl group or a phenyl group, and Ar represents a trivalent aromatic group containing at least one 6-membered ring.)

  More specifically, the polymer which has a repeating unit represented by following formula (11) and / or (12) with the repeating unit represented by the said Formula (10) can be mentioned.

(In the formula, R8 is the same as above. Ar 'represents a divalent aromatic group or divalent alicyclic group containing one or two or more carbon 6-membered rings.)

(In the formula, R8 is the same as above. Ar ″ represents an aromatic group linked by a tetravalent carbonyl group containing one or two or more carbon 6-membered rings.)

  In the above, a part of the imide bond in the structural units (10) and (12) may have a structure that remains in the state of an amic acid bond as the ring-closing precursor.

  The polyamideimide resin composed of the repeating unit represented by the above formula (10) is produced, for example, by reacting raw material compounds having the following combinations in a polar organic solvent. Examples of the polar organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, cresol and the like.

  As a method for producing a polyamideimide resin, for example, (i) an acid chloride method using an aromatic diamine and trimellitic anhydride monochloride (for example, described in JP-B-42-15637), (ii) derived from an aromatic diamine Isocyanate method in which aromatic diisocyanate and trimellitic anhydride are reacted (for example, described in JP-B No. 44-19274), (iii) Aromatic diamine and trimellitic anhydride are heated to a high temperature in the presence of a dehydration catalyst. And direct polymerization method (for example, described in JP-B-49-4077) and the like, and is not particularly limited, and can be produced by a conventionally known method.

  Although there is no restriction | limiting in particular in the polymerization degree of these polyamide imide resin, 0.2-0.7 dl is obtained as a solution logarithmic viscosity measured at 30 degreeC in the N-methyl-2-pyrrolidone solution of sample concentration 0.25g / 50ml. Those in the range of / g are preferred.

  The polysulfone resin used in the present invention is a polymer having a repeating unit represented by the following formula (13), but may contain a functional group such as an alkyl group, for example. These structural units may be copolymerized to some extent. In that case, 0.1-30 mol% of other structural units copolymerized is preferable.

  The polyethersulfone resin used in the present invention is a resin having a sulfone bond and an ether bond in a repeating skeleton. The following formula (14) can be exemplified as a typical structural unit.

  Generally, it is marketed under the trademarks "Victorel", "Sumika Excel", and "Radel A".

  The polyarylate resin used in the present invention can be exemplified by the structural unit represented by the following formula (15) as a representative example, and is a polymer having the structure described by the formula (15) as a single or a plurality of repeating units. In addition, structural units other than those described in formula (15) may be copolymerized within a range not impairing the effects of the present invention.

  The amorphous polyamide resin used in the present invention is a polyamide resin having no crystallinity. Here, having no crystallinity means that an endothermic peak due to crystal melting occurs when the temperature is measured from a solid state to a molten state at a temperature rising rate of 20 ° C./min in a differential scanning calorimetry under an inert gas atmosphere. In addition, it shows that there is no exothermic peak due to crystallization when cooled from a molten state to a solid state at a rate of temperature decrease of 20 ° C./min. Examples of amorphous polyamide resins include polycondensates of dicarboxylic acids and diamines, specifically, C6-C20 dicarboxylic acids and C6-C18 diamines, C6-C12 cyclic lactams, It is an amorphous polyamide resin obtained by polymerizing an aminocarboxylic acid having 6 to 12 carbon atoms, and is preferably used for two or more kinds of copolymers. Examples of the dicarboxylic acid having 6 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pracillic acid, tetradecanedioic acid, and pentadecanedioic acid. , Aliphatic dicarboxylic acids such as octadecanedioic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid. Acid, sebacic acid, undecadioic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid are preferably used. Moreover, as a C2-C20 diamine component, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylene Aliphatic diamines such as diamine, dodecamethylenediamine, tridecamethylenediamine, hexadecamethylenediamine, octadecamethylenediamine, bis-P-aminocyclohexylmethane, bis-P-aminocyclohexylpropane, 2,2'- or 3 , 3'-dimethylbis-P-aminocyclohexylmethane, alicyclic diamine, xylenediamine, aromatic diamine such as metaphenylenediamine, and the like. Amine, bis -P- aminocyclohexyl methane, bis -P- aminocyclohexyl propane, 2,2'-or 3,3'-dimethyl bis -P- aminocyclohexyl methane is preferably used. It is also possible to use a ring-opening polymer of cyclic lactam or a polycondensate of aminocarboxylic acid as a copolymerization component. Specific examples of the cyclic lactam include ε-caprolactam, ζ-enantolactam, η-capryllactam, and ω-laurolactam. Examples of the aminocarboxylic acid include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-amino. Examples include dodecanoic acid, and ε-caprolactam and 6-aminocaproic acid are particularly preferably used. The glass transition temperature of the amorphous polyamide resin used here is not particularly limited, but is preferably 80 ° C. or higher, particularly 100 ° C. or higher from the viewpoint of heat resistance.

  Further, the degree of polymerization of the amorphous polyamide resin used here is not particularly limited, but the relative viscosity measured at 25% at 98% sulfuric acid is 1% in accordance with JIS K6810, and is 1.5 to 8.0. It is preferably 1.7 or more and 6.0 or less, and more preferably 1.8 or more and 4.0 or less. The method for polymerizing the amorphous polyamide resin used in the present invention is not particularly limited, and melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, increasing the degree of polymerization by an extruder, and a method combining these methods. Can be used. Usually, melt polymerization is preferably used.

  The polyphenylene sulfide sulfone resin used in the present invention can be exemplified by the structural unit represented by the following formula (16) as a representative example, and is a polymer having the structure described in the formula (16) as a single or a plurality of repeating units. In addition, structural units other than those described in formula (16) may be copolymerized as long as the effects of the present invention are not impaired.

  The thermoplastic resin (b) used in the present invention is polycarbonate resin, polyphenylene ether resin, polyetherimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, amorphous polyamide. Any resin other than the amorphous resin (a) selected from the resins may be used as long as it is a melt-moldable resin. For example, crystalline polyamide resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyketone resin , Polyetherketone resin, polyetheretherketone resin, thermoplastic polyurethane resin, high density polyethylene resin, low density polyethylene resin, linear low density polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic olefin resin Resin, poly 1-butene resin, poly 1-pentene resin, polymethyl pentene resin, ethylene / α-olefin copolymer, polyvinyl chloride resin, polystyrene resin, polyacrylate resin, polymethacrylate resin Acrylic resins such as acrylonitrile, acrylonitrile copolymers based on acrylonitrile, acrylonitrile / butanediene / styrene (ABS) resins, acrylonitrile / styrene (AS) resins, cellulose resins such as cellulose acetate, vinyl chloride / ethylene copolymers Vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, saponified ethylene / vinyl acetate copolymer, and the like. Of these, crystalline polyamide resins, polyester resins, polyphenylene sulfide resins, and ABS resins are preferable in terms of heat resistance, moldability, and mechanical properties, and crystalline polyamide resins, polyester resins, and polyphenylene sulfide resins are more preferable. A preferred polyamide resin is preferred.

  In the present invention, the preferred crystalline polyamide resin is a polyamide mainly composed of amino acid, lactam or diamine and dicarboxylic acid, and is a polyamide having crystallinity. Here, the presence or absence of crystallinity was determined by using a differential scanning calorimeter to raise the temperature in an inert gas atmosphere at a rate of temperature increase of 20 ° C./min to a molten state, and then cooled at a rate of temperature decrease of 20 ° C./min. Then, it can be determined by the presence or absence of an endothermic peak due to crystal melting that occurs when the temperature rise is measured again at a temperature rise rate of 20 ° C./min. Representative examples of the main components of the crystalline polyamide resin include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, and lactams such as ε-caprolactam and ω-laurolactam. , Pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methyl Aliphatic and aromatic diamines such as nonamethylenediamine, metaxylylenediamine, paraxylylenediamine, bis (aminopropyl) piperazine, aminoethylpiperazine, and adipic acid, superic acid, azelaic acid, sebacic acid, dodecanedioic acid Terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, etc. In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used singly or in the form of a mixture, respectively.

  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 invention can be mentioned, Especially, nylon 66 can be mentioned from a viewpoint of heat resistance and a mechanical characteristic. 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, it is preferable to add a copper compound to 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, liberation of metallic copper occurs 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.

  Preferred polyester resins in the present invention have an ester bond in the main chain, and (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, or (b) a hydroxycarboxylic acid or an ester-forming derivative thereof. (C) A polymer or copolymer having at least one selected from lactones 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. , Polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polylactic acid, polyglycol Non-liquid crystalline polyester resins such as acids are preferable because they have a large fluidity improving effect by adding the dendritic polyester resin (c), more preferably polyethylene terephthalate, polybutylene terephthalate, and polylactic acid, and particularly preferably polybutylene terephthalate. .

  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 hydrolysis resistance.

  The amount of carboxyl end groups of the polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or less, more preferably 30 eq / t or less in terms of hydrolysis resistance and heat resistance. 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 polyester resin is a value measured by dissolving in an o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The amount of vinyl end groups of the 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, and 5 eq / t or less in terms of color tone. More preferably. The lower limit is 0 eq / t. In the present invention, the amount of vinyl end groups of the polyester resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

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

  The viscosity of the polyester resin used in the present invention is not particularly limited, but the intrinsic viscosity when the o-chlorophenol solution is measured at 25 ° C. is preferably in the range of 0.36 to 1.60 dl / g. A range of 50 to 1.25 dl / g is more preferable.

  The molecular weight of the polyester resin used in the present invention is preferably in the range of 50,000 to 500,000 in weight average molecular weight (Mw), more preferably in the range of 100,000 to 300,000 in terms of heat resistance. More preferably, it is in the range of 10,000 to 250,000.

  The production method of the 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. Either a transesterification reaction or a reaction by direct polymerization can be applied, but continuous polymerization can be performed in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity and hydrolysis resistance is increased. Direct polymerization is preferred from the viewpoint of cost.

  When the 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, a dicarboxylic acid Alternatively, an ester-forming derivative thereof and a diol or an ester-forming derivative thereof can be produced by an esterification reaction or an ester exchange 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, and 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polyester resin in terms of mechanical properties, moldability and color tone. A range of parts is more preferred.

  As the polyphenylene sulfide resin preferably used in the present invention, a polymer having a repeating unit represented by the following structural unit (8) can be used.

  From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the structural formula is preferable. In addition, in the polyphenylene sulfide resin, about less than 30 mol% of the repeating units may be composed of repeating units having any of the following structures. Of these, a p-phenylene sulfide / m-phenylene sulfide copolymer (m-phenylene sulfide unit of 20% or less) can be preferably used because it has both moldability and barrier properties.

  Such a polyphenylene sulfide resin can be produced in high yield by recovering and post-treating a polyphenylene sulfide resin obtained by reacting a polyhalogen aromatic compound and a sulfiding agent in a polar organic solvent. Specifically, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or a relatively molecular weight described in JP-B-52-12240 and JP-A-61-7332 is disclosed. It can also be produced by a method for obtaining a large polymer. Crosslinking / high molecular weight of the polyphenylene sulfide resin obtained as described above by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, etc., acid anhydride It can also be used after various treatments such as activation with functional group-containing compounds such as products, amines, isocyanates, functional group-containing disulfide compounds.

  Specific methods for crosslinking / high molecular weight polyphenylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Thus, a method of heating at a predetermined temperature in a heating container until a desired melt viscosity is obtained can be exemplified. The heat treatment temperature is usually 170 to 280 ° C, preferably 200 to 270 ° C. The heat treatment time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both of these, the target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. It is preferable to use an apparatus.

  As a specific method for heat-treating the polyphenylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200, under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at ˜270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. More preferably, an apparatus is used.

  The polyphenylene sulfide resin used in the present invention is preferably a polyphenylene sulfide resin that has been subjected to a washing treatment. Specific examples of the cleaning treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment. These treatments may be used in combination of two or more methods.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing polyphenylene sulfide resin. Sulfoxides such as sulfoxide and dimethylsulfone, sulfone solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, ether solvents such as dimethyl ether, dipropyl ether and tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, Halogenated solvents such as dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol , Propylene glycol, phenol, cresol, alcohols such as polyethylene glycol, phenolic solvents, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable. These organic solvents are used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing a polyphenylene sulfide resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyphenylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to develop a preferable chemical modification effect of the polyphenylene sulfide resin by hot water washing. The operation of the hot water treatment is usually performed by charging a predetermined amount of polyphenylene sulfide resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyphenylene sulfide resin and water is preferably as much as possible, but usually a bath ratio of 200 g or less of polyphenylene sulfide resin is selected per liter of water.

  Further, when washing with hot water, it is preferable to use an aqueous solution containing a Group II metal element of the periodic table. The aqueous solution containing a Group II metal element of the periodic table is obtained by adding a water-soluble salt containing a Group II metal element of the periodic table to the water. The concentration of the water-soluble salt having a Group II metal element in the periodic table with respect to water is preferably in the range of about 0.001 to 5% by weight.

Examples of preferable metal elements among Group II metal elements of the periodic table used herein include Ca, Mg, Ba and Zn. Other anions include acetate ions, halide ions, hydroxide ions, and the like. Examples include carbonate ions. More specific and preferred compounds include Ca acetate, Mg acetate, Zn acetate, CaCl ₂ , CaBr ₂ , ZnCl ₂ , CaCO ₃ , Ca (OH) ₂ and CaO, and particularly preferably Ca acetate. is there.

  The temperature of the aqueous solution containing a Group II metal element in the periodic table is preferably 130 ° C. or higher, more preferably 150 ° C. or higher. Although there is no restriction | limiting in particular about the upper limit of washing | cleaning temperature, When using a normal autoclave, about 250 degreeC is a limit.

  The bath ratio of the aqueous solution containing the Group II metal element in the periodic table is preferably selected in the range of 2 to 100, more preferably 4 to 50, and 5 to 15 with respect to the dry polymer 1 by weight. More preferably, it is in the range.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with an acid aqueous solution. That is, there is a method of immersing a polyphenylene sulfide resin in an acid or an acid aqueous solution, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing polyphenylene sulfide resin, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted fatty acids such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acid such as aromatic saturated carboxylic acid, acrylic acid, crotonic acid, aromatic carboxylic acid such as benzoic acid, salicylic acid, dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, Examples include inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The polyphenylene sulfide resin that has been subjected to acid treatment is preferably washed several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the polyphenylene sulfide resin by acid treatment is not impaired.

  The amount of ash content of the polyphenylene sulfide resin used in the present invention is preferably a relatively large range of 0.1 to 2% by weight from the viewpoint of imparting characteristics such as fluidity during processing and molding cycle, and is preferably 0.2 to 1% by weight. % Is more preferable, and a range of 0.3 to 0.8% by weight is more preferable.

Here, the amount of ash refers to the amount of inorganic components in the polyphenylene sulfide resin determined by the following method.
(1) Weigh 5-6 g of polyphenylene sulfide resin in a platinum dish fired and cooled at 583 ° C.
(2) A polyphenylene sulfide resin is pre-fired at 450 to 500 ° C. together with a platinum dish.
(3) A polyphenylene sulfide sample pre-fired with a platinum dish is placed in a muffle furnace set at 583 ° C. and fired for about 6 hours until it completely incinerates.
(4) Weigh after cooling in a desiccator.
(5) Calculate the ash content by the formula: ash content (% by weight) = (weight of ash content (g) / sample weight (g)) × 100.

The melt viscosity of the polyphenylene sulfide resin used in the present invention is in the range of ¹ to 2000 Pa · s (300 ° C., shear rate 1000 sec ⁻¹ ) from the viewpoint of imparting characteristics such as improved chemical resistance and fluidity during processing. Is preferably selected, more preferably in the range of 1 to 200 Pa · s, and still more preferably in the range of 1 to 50 Pa · s. Here, the melt viscosity is a value measured by a Koka flow tester using a nozzle having a nozzle diameter of 0.5 mmφ and a nozzle length of 10 mm under the condition of a shear rate of 1000 sec ⁻¹ .

  The melt flow rate (MFR) of the polyphenylene sulfide resin used in the present invention is a value measured at a temperature of 315.5 ° C. and a load of 5 kg according to ASTM D1238. The range is preferably 10,000 g / 10 minutes, more preferably 20 to 5000 g / 10 minutes, and particularly preferably 50 to 3000 g / 10 minutes.

  Chloroform extraction amount (calculated from the residual amount at the time of Soxhlet extraction for 5 hours) as an index of the amount of organic low polymerization component (oligomer) of polyphenylene sulfide resin used in the present invention is chemical resistance. From the point of imparting characteristics such as improvement of the fluidity and fluidity during processing, a relatively large range of 1 to 5% by weight is preferable, a range of 1.5 to 4% by weight is more preferable, and a range of 2 to 4% by weight More preferably it is.

  The ABS resin used in the present invention is composed of a diene rubber, a vinyl cyanide monomer, an aromatic vinyl monomer and another copolymerizable monomer as required, and the total amount of the monomer. Is a resin composition of a graft copolymer obtained by graft copolymerization with a diene rubber and a copolymer obtained by copolymerization of the remaining monomers.

  Examples of the diene rubber used in the present invention include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and polyisoprene rubber. These may be used alone or in combination of two or more. it can. Polybutadiene and / or styrene-butadiene copolymer rubber is preferably used. Examples of the vinyl cyanide include acrylonitrile and methacrylonitrile. Among them, acrylonitrile is preferable. Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, and pt-butylstyrene. Of these, styrene and / or α-methylstyrene is preferably used. Examples of other copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, α, β such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, and cyclohexyl methacrylate. Α, β-unsaturated dicarboxylic anhydrides such as unsaturated carboxylic acid esters, maleic anhydride, itaconic anhydride, α, β such as N-phenylmaleimide, N-methylmaleimide, Nt-butylmaleimide -The imide compound of unsaturated dicarboxylic acid etc. can be mentioned.

  The composition of the ABS resin is not particularly limited, but from the viewpoint of molding processability and impact resistance of the resulting thermoplastic resin composition, the diene rubber is preferably 5 to 85 parts by weight with respect to 100 parts by weight of the ABS resin. More preferably, the amount is 15 to 75 parts by weight. Similarly, the vinyl cyanide is preferably 5 to 50 parts by weight, particularly 7 to 45 parts by weight, and more preferably 8 to 40 parts by weight. The aromatic vinyl is preferably 10 to 90 parts by weight, particularly preferably 13 to 83 parts by weight, and more preferably 17 to 77 parts by weight. There is no restriction | limiting in particular about the manufacturing method of ABS resin, Generally well-known methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. It is also possible to obtain the above composition by blending separately (grafted) copolymerized resins.

  A compatibilizing agent is added to the thermoplastic resin composition of the present invention for the purpose of improving the compatibility between the amorphous resin (a) and the thermoplastic resin (b) other than the amorphous resin (a). Can do. Specific examples of the compatibilizer include organic silane compounds such as alkoxysilanes having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. A functional epoxy compound etc. are mentioned, These can also be used simultaneously 2 or more types. Here, the polyfunctional epoxy compound contains two or more epoxy groups in the molecule, and a liquid or solid one can be used. For example, a copolymer of an α-olefin such as ethylene, propylene, and 1-butene and an α, β-unsaturated glycidyl ester such as glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, having an unsaturated double bond Epoxy group-containing polymer compound obtained by epoxidizing the double bond part of the polymer, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyl Bisphenol-glycidyl ether type epoxy compounds such as dimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, phthalate Glycidyl ester type epoxy compounds such as glycidyl esters, N- glycidyl amine-based epoxy compound glycidyl aniline, novolac type phenolic resin novolak type epoxy resins obtained by reacting epichlorohydrin and the like. Preferably, a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester, an organic silane compound having an epoxy group or an isocyanate group, or a bisphenol-glycidyl ether epoxy compound is used. Among these, the use of an organosilane compound having an isocyanate group is preferable because the mechanical properties are particularly excellent.

  The blending ratio of the compatibilizer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the thermoplastic resin (b) other than the amorphous resin (a) and the amorphous resin (a). Preferably it is 0.1-5 weight part. When the addition amount is 0.01 parts by weight or less, a sufficient compatibility improving effect cannot be obtained, and when it exceeds 10 parts by weight, the melt viscosity of the thermoplastic resin composition is remarkably increased and the fluidity is lowered.

The dendritic polyester resin (c) of the present invention is at least one selected from aromatic oxycarbonyl units (S), aromatic and / or aliphatic dioxy units (T), and aromatic dicarbonyl units (U). Of the structural unit and the trifunctional or tetrafunctional aromatic organic residue (D), and the D content is 7.5 to 50 mol% with respect to the total monomers constituting the dendritic polyester. Dendritic polyester resin in range.

  Here, the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) are structural units represented by the following formula (1), respectively. is there.

  Here, R1 and R3 are each an aromatic residue. R2 is an aromatic residue or an aliphatic residue. R1, R2, and R3 may each include a plurality of structural units.

  Examples of the aromatic residue include a substituted or unsubstituted phenylene group, naphthylene group, and biphenylene group. Examples of the aliphatic residue include ethylene, propylene, and butylene. R1, R2 and R3 are preferably at least one structural unit selected from structural units represented by the following formulas.

  In the formula, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. In the formula, n is an integer of 2 to 8.

In the dendritic polyester of the present invention, the trifunctional or tetrafunctional aromatic organic residue (D) is selected directly from each other by an ester bond and / or an amide bond, or from S, T and U which are branched structure parts. The basic skeleton is a tri- or tetrafunctional branched structure bonded via a structural unit. The branched structure may be formed of a single basic skeleton such as three branches and four branches, or a plurality of basic skeletons such as three branches and four branches may coexist. It is not necessary for all of the polymers to be composed of the basic skeleton, and other structures may be included at the ends, for example, for end-capping. Further, when D is a trifunctional aromatic organic residue, the dendritic polyester has a structure in which all three functional groups of D are reacted, a structure in which only two are reacted, And a structure in which only one is reacted may be mixed. Preferably, the structure in which all three functional groups of D are reacted is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more with respect to the entire D. When D is a tetrafunctional aromatic organic residue, the dendritic polyester has a structure in which all four functional groups of D are reacted, a structure in which only three are reacted, A structure in which only two react and a structure in which only one reacts may be mixed. Preferably, the structure in which all four functional groups of D have reacted is preferably 10 mol% or more and the structure in which three functional groups have reacted with respect to the entire D is preferably 20 mol% or more, more preferably four functional groups. The structure in which is reacted is 20 mol% or more with respect to the entire D and the structure in which three functional groups are reacted is 30 mol% or more with respect to the entire D, and more preferably the structure in which four functional groups are reacted is the entire D The structure in which three functional groups have reacted with each other at 25 mol% or more is 35 mol% or more with respect to the entire D.

D is 3 the aromatic organic residue der functional compound and / or tetrafunctional compound is, and most preferably an aromatic organic residue trifunctional compound.

  The above three-branch basic skeleton is schematically represented by the formula (2). Further, the above four-branch basic skeleton is schematically represented by the formula (3).

Dendritic polyesters of the present invention, shows the liquid crystalline. The term “showing molten liquid crystallinity” means that the liquid crystal state is exhibited in a certain temperature range when the temperature is raised from room temperature. The liquid crystal state is a state showing optical anisotropy under shear.

  In order to exhibit molten liquid crystallinity, the basic skeleton in the case of three branches is composed of a structural unit in which the organic residue (D) is selected from S, T and U as shown in the following formula (5) It is preferable that they are bonded via the branch structure portion R.

  Similarly, the basic skeleton in the case of four branches is preferably a structure represented by the following formula (6).

Although it does not specifically limit about the trifunctional organic residue represented by D, It is preferable that it is an organic residue of the compound containing the functional group chosen from a carboxyl group, a hydroxyl group, and an amino group. For example, preparative Rimeshin acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, alpha-resorcylic acid, beta-resorcylic acid, .gamma. resorcinol acid, tricarboxyethylene naphthalene, dihydroxy-naphthoic acid, aminophthalic Examples include acids derived from aromatic compounds such as 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid, melamine, and cyanuric acid . It is good preferable are those represented by the following formula (4). Specifically, those derived from trimesic acid and α-resorcylic acid are preferred, and those derived from trimesic acid are particularly preferred.

Further, the tetrafunctional or higher functional organic residue D is preferably an organic residue of a compound containing a functional group selected from a carboxyl group, a hydroxyl group and an amino group. For example , 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5-benzenetetraol, 1,2,3, 4,5-benzenepentaneol, 1,2,3,4,5,6-benzenehexaneol, 2,2 ′, 3,3′-tetrahydroxybiphenyl, 2,2 ′, 4,4 '-Tetrahydroxybiphenyl, 3,3', 4,4'-tetrahydroxybiphenyl, 3,3 ', 5,5'-tetrahydroxybiphenyl, 2,3,6,7-naphthalenetetraol, 1,4 5,8-naphthalenetetraol, pyromellitic acid, merophanic acid, planitic acid, meritic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,2 ′, 4,4′-biphenyltetracarboxylic acid 3,3 ′, 4,4′-biphenyltetracarboxylic acid 3,3 ′, 5,5′-biphenyltetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalene Tetraol, 1,4,5,8-naphthalenetetraol, 1,2,4,5,6,8-naphthalenehexaol, 1,2,4,5,6,8-naphthalenehexacarboxylic acid, gallic acid A residue of an aromatic compound such as The residue represented by the following formula (7) is more preferable.

  Specific examples of the tetrafunctional organic residue of the above formula include 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5. Residues such as benzenetetraol, pyromellitic acid, merophanic acid, planitic acid, gallic acid and the like are preferred, and the residue of gallic acid is particularly preferred.

  Further, the aromatic hydroxycarbonyl unit (S), aromatic and / or aliphatic dioxy unit (T), and aromatic dicarbonyl unit (U) of the dendritic polyester resin represent the branch structure portion between the branches of the dendritic polyester. It is a unit that composes. p, q, and r are the average contents (molar ratio) of the structural units S, T, and U, respectively, and it is preferable that p + q + r = 1 to 10 when the content d of D is 1 mol. More preferably, p + q + r is in the range of 2-6. If the branch length is too long, it is not preferable because effects such as shear responsiveness based on a rigid and detailed dendritic structure are reduced. The values of p, q, and r are obtained, for example, by dissolving dendritic polyester resin in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of chloroform and performing nuclear magnetic resonance spectrum analysis of proton nuclei at 40 ° C. It can obtain | require from the peak intensity ratio derived from each structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off. From the area intensity ratio with the peak corresponding to the content d of the branched structure D, the average chain length of the branch portion R is calculated and set as the value of p + q + r. In this case, the three decimal places are rounded off.

The ratio of p and q and the ratio of p and r (p / q, p / r) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, more preferably 20 / 80-80 / 20. If it is this range, liquid crystallinity is easy to express and it is preferable. By setting the ratio of p / q and p / r to 95/5 or less, the melting point of the dendritic polyester resin can be within an appropriate range, and p / q and p / r should be 5/95 or more. in Ru can express liquid crystalline dendritic polyester resin.

  q and r are preferably substantially equimolar, but either component can be added in excess to control the end groups. The ratio of q / r is preferably in the range of 0.7 to 1.5, more preferably 0.9 to 1.1. Equimolar here means that the molar amount in the repeating unit is equal and does not include the terminal structure. Here, the term “end structure” means the end of the branch structure portion, and when the end is blocked, it means the end of the branch structure portion closest to the end.

  Furthermore, R1, R2, and R3 are the structural units.

  R1 is a structure derived from an aromatic oxycarbonyl unit, and examples thereof include structural units generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and are preferably structural units derived from p-hydroxybenzoic acid. It is also possible to use a part of those derived from 6-hydroxy-2-naphthoic acid. Further, structural units derived from aliphatic hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, and hydroxycaproic acid may be contained within a range not impairing the effects of the present invention.

  R2 is a structure derived from aromatic and / or aliphatic dioxy units, such as 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1 , 3-propylene glycol, structural units generated from 1,4-butanediol, and the like. Preferred are structural units generated from 4,4′-dihydroxybiphenyl, hydroquinone, ethylene glycol, and 4,4 ′. -Dihydroxy biphe May include the Le hydroquinone or 4,4'-dihydroxybiphenyl and a structural unit derived from ethylene glycol is preferable from the viewpoint of the control of the liquid crystal.

  R3 is a structural unit generated from an aromatic dicarbonyl unit. For example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane Examples include structural units formed from -4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and the like. It is a structural unit formed from terephthalic acid and isophthalic acid, and particularly when both are used in combination, the melting point can be easily adjusted. Moreover, a part of structural unit produced | generated from aliphatic dicarboxylic acids, such as sebacic acid and adipic acid, may be included in the range which does not impair the effect of this invention.

  The branch structure portion of the dendritic polyester resin of the present invention is preferably mainly composed of a polyester skeleton, but it is also possible to introduce a carbonate structure, an amide structure, a urethane structure, etc. to such an extent that the characteristics are not greatly affected. Among them, it is preferable to introduce an amide structure. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted, which is preferable. As a method for introducing an amide bond, p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, m-phenylenediamine, tetramethylenediamine pentamethylenediamine, hexamethylene Diamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xyl Range amine, p-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-Aminocyclohexyl Aliphatic, alicyclic or aromatic such as methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine It is preferable to copolymerize such an amine compound, and among them, copolymerization of p-aminophenol and p-aminobenzoic acid is preferable.

  Specific examples of the structure of R include a structural unit formed from p-hydroxybenzoic acid and a structural unit generated from 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, 6- A structural unit produced from hydroxy-2-naphthoic acid, a structural unit produced from 4,4′-dihydroxybiphenyl, a structure comprising a structural unit produced from terephthalic acid, a structural unit produced from p-hydroxybenzoic acid, 4,4 Structural units generated from '-dihydroxybiphenyl, structural units generated from terephthalic acid, structures composed of structural units generated from isophthalic acid, structural units generated from p-hydroxybenzoic acid, generated from 4,4'-dihydroxybiphenyl Structural unit, structural unit generated from hydroquinone, generated from terephthalic acid Structural units, structural units formed from isophthalic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from terephthalic acid, p-hydroxybenzoic acid Structural unit generated from ethylene, structural unit generated from ethylene glycol, structural unit generated from 4,4′-dihydroxybiphenyl, structure composed of structural unit generated from terephthalic acid, structural unit generated from p-hydroxybenzoic acid, hydroquinone A structural unit generated from 4,4′-dihydroxybiphenyl, a structural unit generated from terephthalic acid, a structure consisting of a structural unit generated from 2,6-naphthalenedicarboxylic acid, generated from p-hydroxybenzoic acid Structural unit, 6-hydroxy- - structural unit derived from naphthoic acid, a structural unit derived from hydroquinone, etc. structure comprising a structural unit derived from terephthalic acid.

  Particularly preferred is R composed of the following structural units (I), (II), (III), (IV) and (V) or the following structural units (I), (II), (VI) and (IV) R).

  In the case of R composed of the structural units (I), (II), (III), (IV) and (V), the content p of the structural unit (I) is based on the total p + q + r of the structural units. It is 30 to 70%, more preferably 45 to 60%.

  Further, the content q (II) of the structural unit (II) is 60 to 75%, more preferably 65 to 73% with respect to the total q of the structural units (II) and (III). The content r (IV) of the structural unit (IV) is 60 to 92%, preferably 60 to 70%, more preferably 62 with respect to the total r of the structural units (IV) and (V). ~ 68%.

  In such a case, the shear response and the addition effect to the thermoplastic resin which are the characteristics of the present invention are remarkably exhibited, which is preferable.

  Preferably, the sum q of structural units (II) and (III) and the sum r of (IV) and (V) are substantially equimolar, but the carboxylic acid component or hydroxyl to adjust the end groups of the polymer Ingredients may be added in excess. That is, “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. Here, when the terminal is a derivative or blocked, it means the terminal of the skeleton R.

  In the case of R composed of the structural units (I), (II), (VI) and (IV), the content p of the structural unit (I) is the structural units (I), (II) and ( It is preferably 30 to 90 mol%, more preferably 40 to 80 mol%, based on the total of VI). Moreover, 70-5 mol% is preferable with respect to the sum q of (II) and (VI), and, as for content q (VI) of structural unit (VI), 60-8 mol% is more preferable. Further, the structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (VI), but either component may be added in excess.

  The terminal of the dendritic polyester of the present invention is preferably a carboxyl group, a hydroxyl group, an amino group, or a derivative thereof. Examples of the hydroxyl derivative or carboxylic acid derivative include alkyl esters such as methyl ester and aromatic esters such as phenyl ester and benzyl ester. It is also possible to end-block using a monofunctional epoxy compound, an oxazoline compound, an ortho ester, an acid anhydride compound, or the like. The end-capping method includes adding a monofunctional organic compound in advance when synthesizing the dendritic polyester, or adding a monofunctional organic compound when the dendritic polyster skeleton is formed to some extent. The method etc. are mentioned.

  Specifically, when blocking the hydroxyl terminal or acetoxy terminal, benzoic acid, 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4- It is possible by adding methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid, and the like.

  Moreover, the carboxyl group terminal blockade can be performed by reacting a carboxylic acid-reactive monofunctional compound. Here, the carboxylic acid-reactive monofunctional compound refers to a compound having one functional group in the molecule that can react with carboxylic acid at room temperature or when heated to form an ester, amide, urethane, or urea bond. The carboxylic acid-reactive monofunctional compound reacts with the carboxylic acid group present at the molecular end of the dendritic polyester, and the monofunctional compound is introduced at the molecular end, thereby improving the residence stability and hydrolysis resistance of the dendritic polyester. When it is improved and further kneaded with other thermoplastic resins and fillers, it can suppress the decomposition of thermoplastic resins and fillers, and improve the dispersibility of dendritic polyester, thereby improving fluidity and physical properties. Can be expected.

  The carboxylic acid-reactive monofunctional compound that can be used in the dendritic polyester of the present invention is at least one compound selected from oxazoline, epoxide, orthoester, isocyanate, carbodiimide, and diazo compound. From the viewpoint of reactivity with carboxylic acid and handling properties, oxazoline, epoxide, orthoester, and isocyanate can be preferably used. The carboxylic acid-reactive monofunctional compound may be used alone or in combination of two or more carboxylic acid-reactive monofunctional compounds.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the oxazoline compound include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, and 2-butoxy. 2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2 -Cyclopentyloxy-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline, 2-p-phenylphenoxy- -Oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2 -Sec-butyl-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline , 2-crotyl-2-oxazoline, 2-phenyl-2- Kisazorin, 2-biphenyl-2-oxazoline. Of these, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2 from the viewpoints of reactivity and affinity with dendritic polyester and heat resistance -Oxazoline, 2-isopropyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2-sec-butyl-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-biphenyl 2-Oxazoline is preferable, and 2-phenyl-2-oxazoline is particularly preferable.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the epoxy compound include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N- Glycidyl-3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N- Glycidylsuccinimide, N-glycidylhexahydrophthalimide, N-glycidylmaleimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, o-phenylphenyl Sidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 3- (2-xenyloxy) -1,2-epoxypropane, allyl glycidyl ether, butyl glycidyl ether, lauryl glycidyl ether, benzyl glycidyl ether, cyclohexyl glycidyl ether, α -Cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate ether, ethylene oxide, propylene oxide, styrene oxide, octane oxide, glycidyl acetate, glycidyl propionate, glycidyl butanoate, pentanoic acid Glycidyl ester, hexanoic acid glycidyl ester, octanoic acid glycidyl ester, decanoic acid glycidyl And glycidyl ester of neodecanoic acid and glycidyl benzoate. Of these, ethylene oxide, propylene oxide, butyl glycidyl ether, phenyl glycidyl ether, and benzoic acid glycidyl ester are preferred, and benzoic acid glycidyl ester is particularly preferred from the viewpoints of reactivity and affinity with the dendritic polyester.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, ortho ester compounds include, for example, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, ortho Triethyl formate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tribenzyl orthopropionate, trimethyl orthobenzoate, trimethyl orthobenzoate Triethyl, tripropyl orthobenzoate, tributyl orthobenzoate, tribenzyl orthobenzoate and the like can be mentioned. Of these, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate are preferred, and trimethyl orthoacetate or triethyl orthoacetate is particularly preferred from the viewpoints of reactivity and affinity with dendritic polyester and handling properties. .

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the isocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, Examples include decyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, benzyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, stearoyl isocyanate, and p-toluosulfonyl isocyanate. Of these, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, and phenyl isocyanate are preferable from the viewpoint of reactivity and affinity with the dendritic polyester, and phenyl isocyanate is particularly preferable.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the diazo compound include diazomethane, diazoethane, diazopropane, diazobutane, and trimethylsilyldiazomethane. Of these, diazomethane and trimethylsilyldiazomethane are preferably used from the viewpoint of reactivity and affinity with the dendritic polyester.

  Theoretically, it is possible to block the end by adding the organic compound used for blocking the end in an amount corresponding to the end group to be blocked. It is preferable to use 1.005 times equivalent or more, more preferably 1.008 times equivalent or more of the organic compound used for terminal blocking with respect to the equivalent amount of the terminal group to be blocked. Moreover, it is preferable that the addition amount of the organic compound used for terminal blockage is 2.5 times equivalent or less. If the amount of the compound used for terminal blocking is too small, the terminal blocking is not sufficient. On the other hand, if the addition amount is too large, an excessively added compound remains in the system and generates gas, which is not preferable.

  Further, the content of the organic residue D is 7.5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol%, based on the content of all monomers constituting the dendritic polyester. That's it. In such a case, the chain length of the branch structure portion is preferable because the dendritic polyester is suitable for taking a dendritic form. The upper limit of the content of the organic residue D is 50 mol% or less, preferably 45 mol% or less, and more preferably 40 mol% or less. In addition, the dendritic polyester resin of the present invention may have a partially crosslinked structure as long as the properties are not affected.

  There is no restriction | limiting in particular in the manufacturing method of the said dendritic polyester resin used in this invention, It can manufacture according to the well-known polyester polycondensation method. After acylating the raw material monotonic pair constituting the structural units represented by R1, R2, and R3, when the trifunctional monomer is reacted, the addition amount (mol) of the trifunctional monomer is all charged. A method of producing such that it is 7.5 mol% or more with respect to the monomer (mol) is preferable. The addition amount of the polyfunctional monomer is more preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more. Moreover, as an upper limit of addition amount, 50 mol% or less is preferable, More preferably, it is 33 mol% or less.

  For example, in the production of a dendritic polyester resin composed of R and trimesic acid composed of the structural units (I), (II), (III), (IV) and (V), the following production method is preferred. Can be mentioned.

  (1) A liquid crystalline polyester oligomer is synthesized from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, and isophthalic acid by a deacetic acid condensation polymerization reaction, and trimesic acid is added to remove acetic acid polymerization. A method of producing by reacting.

  (2) A process for producing by a deacetic acid condensation polymerization reaction from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, isophthalic acid and trimesic acid.

  (3) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then liquid crystalline polyester by deacetic acid polycondensation reaction. A method of producing an oligomer by synthesizing it and adding trimesic acid to cause a deacetic acid polymerization reaction.

  (4) Acetic anhydride is reacted with p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid and trimesic acid to acylate the phenolic hydroxyl group, and then by deacetic acid polycondensation reaction. How to manufacture.

  (5) A liquid crystalline polyester oligomer is synthesized from a phenyl ester of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and diphenyl ester of isophthalic acid by a dephenol polycondensation reaction, and trimesic acid is added. A method of producing by dephenol polycondensation reaction.

  (6) A method of producing by dephenol polycondensation reaction from phenyl ester of p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl, hydroquinone and terephthalic acid, diphenyl ester of isophthalic acid and phenyl ester of trimesic acid.

  (7) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and trimesic acid to form phenyl esters, respectively, and then 4,4′-dihydroxybiphenyl and hydroquinone. A method in which an aromatic dihydroxy compound such as is added and produced by a dephenol polycondensation reaction.

  Especially, the manufacturing method of (1)-(4) is preferable, More preferably, the manufacturing method of (3) or (4) is preferable from the point of chain length control and a stereoregulation.

  The amount of acetic anhydride used is preferably 0.95 equivalents or more and 1.10 equivalents or less, more preferably 1.00 equivalents or more and 1.05 equivalents or less of the total of phenolic hydroxyl groups from the viewpoint of chain length control. preferable.

  The dendritic polyester resin of the present invention is characterized in that it has a reactive carboxylic acid or hydroxyl group and its derivative group at the terminal, and controls the amount of acetic anhydride and dihydroxy or dicarboxylic acid depending on the type of thermoplastic resin to be blended. It is possible to control the end groups by excessive addition of acid monomers. In order to increase the molecular weight, it is preferable to add an excess of dihydroxy monomer equivalent to the excess amount of carboxylic acid in trimesic acid or 4,4'-dihydroxybiphenyl to match the carboxylic acid with the hydroxyl equivalent, while preferentially using carboxylic acid It is preferable not to add an excessive amount of dihydroxy monomer to the terminal group, and to preferentially leave a hydroxyl group at the terminal, the dihydroxy monomer is added in excess of the carboxylic acid equivalent of trimesic acid and anhydrous. The acetic acid molar ratio is preferably less than 1.00.

  By these methods, the dendritic polyester resin of the present invention can be selectively provided with a terminal group structure rich in reactivity with various thermoplastic resins. However, depending on the thermoplastic resin, in order to suppress the reactivity, it is easier to control the dispersion state by selectively generating the end and then blocking the end with a monofunctional epoxy compound, monofunctional carboxylic acid or the like. In some cases.

  When the dendritic polyester resin of the present invention is produced by a deacetic acid polycondensation reaction, the dendritic polyester resin is reacted at a temperature at which the dendritic polyester resin melts, in some cases under reduced pressure, to distill a predetermined amount of acetic acid, and polycondensation reaction A melt polymerization method that completes is preferable.

  For example, in a reaction vessel equipped with a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. After charging and heating with stirring in a nitrogen gas atmosphere to acetylate the hydroxyl group, the temperature was raised to 200 to 350 ° C. to distill acetic acid, and at the stage of distilling to 50% of the theoretical distillate, trimesic acid A predetermined amount is added, and acetic acid is distilled to 91% of the theoretical distillation amount to complete the reaction.

  The conditions for the acetylation are usually 130 to 170 ° C., preferably 135 to 155 ° C., usually 0.5 to 6 hours, preferably 135 to 145 ° C. for 1 to 2 hours.

  The temperature for polycondensation is the melting temperature of the dendritic polyester resin, for example, in the range of 200 to 350 ° C., preferably the melting point of the dendritic polyester resin + 10 ° C. or higher, specifically 240 to 280 ° C. preferable. When polycondensation is performed, there is no problem even under atmospheric pressure nitrogen, but it is preferable to reduce the pressure because the reaction proceeds faster and the residual acetic acid in the system decreases. The degree of vacuum is usually 0.1 mmHg (13.3 Pa) to 200 mmHg (26600 Pa), preferably 10 mmHg (1330 Pa) to 100 mmHg (13300 Pa). In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

The obtained dendritic polyester resin is pressurized at about 0.01 to 1.0 kg / cm ² (0.001 to 0.1 MPa) in the reaction vessel at a temperature at which it melts, and is provided at the lower portion of the reaction vessel. It can be discharged in the form of a strand from the discharged outlet. A mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets. The discharged dendritic polyester resin is cooled by passing through air or water, and then cut or pulverized as necessary. The obtained pellets or granular or powdery dendritic polyester resin can further remove water, acetic acid, etc. by heat drying or vacuum drying, if necessary, to finely adjust the polymerization degree and further increase the polymerization degree. Therefore, it is possible to carry out solid phase polymerization. For example, under a nitrogen stream or under reduced pressure, the dendritic polyester resin is heated for 1 to 50 hours in the range of melting point −5 ° C. to melting point −50 ° C. (for example, 200 to 300 ° C.), and polycondensed to a desired degree of polymerization. And a method for completing the reaction.

  The polycondensation reaction of the dendritic polyester resin proceeds even without 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 dendritic polyester resin of the present invention preferably has a number average molecular weight of 1,000 to 40,000, more preferably 1,000 to 20,000. In particular, dendritic polyester resins having a number average molecular weight in the range of 10,000 to 20,000 have a high molecular weight, so that they are excellent in handling properties and heat resistance, and have a specific fluidity improving effect when melt-kneaded into a thermoplastic resin. It is preferably used because it is good.

  The number average molecular weight is a value measured as an absolute molecular weight by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the dendritic polyester resin is soluble.

  The melt viscosity of the dendritic polyester resin in the present invention is preferably 0.01 to 30 Pa · s, more preferably 0.5 to 20 Pa · s, and particularly preferably 1 to 10 Pa · s.

  In addition, this melt viscosity is a value measured by a Koka flow tester under the condition of the liquid crystal starting temperature of the dendritic polyester resin + 10 ° C. and the shear rate of 100 / s.

  The dendritic polyester resin of the present invention thus obtained has a melt liquid crystallinity, a high shear response, and a high elastic modulus and a high gas barrier by orientation. Can be used.

  The addition amount of the dendritic polyester resin (c) in the thermoplastic resin composition of the present invention is 100 parts by weight in total of the amorphous resin (a) and the thermoplastic resin (b) other than the amorphous resin (a). And 0.01 to 30 parts by weight. Preferably it is 0.1-20 weight part, Most preferably, it is 0.5-10 weight part. When the addition amount is in the above range, the effect of the present invention is remarkably obtained, which is preferable.

  In the thermoplastic resin composition of the present invention, a filler can be further blended in order to impart mechanical strength and other characteristics. Although a filler is not specifically limited, Any fillers, such as fibrous form, plate shape, powder form, and a granular form, can be used. Fillers include 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. Examples of the primary ammonium ion 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. Moreover, said filler can also be used in combination of 2 or more types. The surface of the filler used in the present invention can be used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. . The type of glass fiber used in the present invention 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 or a short fiber type chopped strand, a milled fiber, or the like. Further, weakly alkaline glass fibers are excellent in terms of mechanical strength and can be preferably used. The glass fiber is preferably treated with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and an epoxy-based resin is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable. The blending amount of the filler is usually 5 to 400 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  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.

  The thermoplastic resin composition of the present invention further includes an ultraviolet absorber (for example, resorcinol, salicylate), a coloring preventing agent such as phosphite and hypophosphite, a lubricant and a release agent (stearic acid, montanic acid and Its metal salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc., colorants including dyes and pigments, carbon black, crystal nucleating agents, plasticizers, flame retardants (bromine based) Normal additives such as flame retardants, phosphorus flame retardants, red phosphorus, silicone flame retardants), flame retardant aids, and antistatic agents, and polymers other than thermoplastic resins are blended to achieve predetermined characteristics. Further, it can be given.

  The method for producing the thermoplastic resin composition of the present invention is preferably by melt kneading, and a known method can be used for melt kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single screw or a twin screw extruder, etc., it can be melt kneaded at a temperature higher than the melting temperature of the thermoplastic resin to obtain a resin composition. Among these, a twin screw extruder is preferable. As a kneading method, 1) a method of kneading a thermoplastic resin, an impact resistance improving material, and a dendritic polyester resin all together, 2) first, a thermoplastic resin and an impact resistance improving material are melt-kneaded to obtain a resin composition, 3. Method of melt-kneading resin composition and dendritic polyester resin, 3) First, melt and knead thermoplastic resin and dendritic polyester resin to obtain a resin composition, and then melt-knead the resin composition and impact resistance improving material. Method 4) Create a resin composition (master pellet) containing dendritic polyester at a high concentration in a thermoplastic resin, and then add the resin composition, thermoplastic resin, and impact resistance improver so as to obtain a specified concentration. Method of melt kneading (master pellet method) 5) First, thermoplastic resin and impact modifier are introduced from the supply port upstream of the extruder, melt kneaded, and then dendritic polyester resin is introduced from the supply port downstream of the extruder Melting and kneading method, 6) First, a thermoplastic resin and dendritic polyester resin are introduced from the supply port upstream of the extruder and melt-kneaded, and then an impact resistance improving material is introduced from the supply port downstream of the extruder and melt-kneaded. Any kneading method may be used.

  The resin composition of the present invention can be molded by any known method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc., and processed into various molded products for use. can do. 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 blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, 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, cable ties, clips, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, prevention Bird sheet, Non-woven fabric for vegetation protection, Pot for seedling, Vegetation pile, Seed string tape, Germination sheet, House lining sheet, Agricultural fastener, Slow-release fertilizer, Agricultural materials such as root sheets, garden nets, insect nets, infant tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage nets, inducement strings, windproof nets, paper diapers, sanitary wrapping materials, cotton swabs, towels , Hygiene items such as toilet seat wipes, medical non-woven fabric (stitching reinforcement, anti-adhesion membrane, prosthetic repair material), wound dressing, wound tape bandage, sticker base fabric, surgical suture, fracture reinforcement, medical Medical supplies such as film, calendar, stationery, clothing, food packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, Containers such as shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, wrapping films for electrical and electronic parts, etc. Packaging, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, Print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode Powder binders for materials, optical elements, Electric embossed tape, IC 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 Useful as chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc., automotive interior parts, automotive exterior parts It is particularly useful as a connector for 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.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

Reference example 1
In a reaction vessel equipped with a stirring blade and a distillation tube, p-hydroxybenzoic acid 870 g (6.300 mol), 4,4′-dihydroxybiphenyl 327 g (1.890 mol), hydroquinone 89 g (0.810 mol), terephthalate 292 g (1.755 mol) of acid, 157 g (0.945 mol) of isophthalic acid and 1367 g of acetic anhydride (1.03 equivalent of total phenolic hydroxyl groups) were charged and reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere. Then, the temperature was raised to 320 ° C. over 4 hours. Thereafter, the polymerization temperature was maintained at 320 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued for 90 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter. The liquid crystal starting temperature was 295 ° C., and a liquid crystalline polyester (B-5) having a number average molecular weight of 12,000 was obtained.

Reference example 2
Dissolve 11.00 kg of 4,4′-diaminodiphenyl ether (DDE) and 2.54 kg of metaphenylenediamine (MPDA) in 65 liters of N, N-dimethylacetamide (DMAC) and cool in an ice bath. Trimellitic acid monochloride (TMAC) 15.10 kg was added at such a rate that the internal temperature did not exceed 30 ° C. After all TMAC was added, 1.443 kg of trimellitic anhydride (TMA) was added, and the mixture was stirred and held at 30 ° C. for 2 hours. The polymer solution which became viscous was put into 100 liters of water stretched on a cutter mixer, and the polymer was precipitated in a slurry state by stirring at high speed. The resulting slurry was dehydrated with a centrifuge. The dehydrated cake was washed with 200 liters of 80 ° C. water and again dehydrated with a centrifuge. The obtained cake was dried using a hot air drier at 220 ° C./5 hours to obtain a powdery polymer (A-4) having a solution viscosity of 0.5 dl / g.

Reference example 3
Sodium sulfide / 9-hydrate 240.2 g (1.00 mol), sodium hydroxide 0.15 g, and N-methylpyrrolidone 500 g, 4,4′-dichlorodiphenylsulfone 287.2 g (1.00 mol) in an autoclave, 5.4 g (0.05 mol) of 1,4-benzoquinone was charged, the temperature was raised to 200 ° C., and the temperature was further maintained for 1 hour. Immediately after completion of the reaction, the mixture was cooled to room temperature. A 100 mesh sieve was used to separate the polymer from the reaction mixture. The polymer was washed several times with dilute hydrochloric acid, and further washed twice with hot water at 160 ° C. to obtain 238.4 g of polymer (A-9). A-9 was 0.69 dl / g when the viscosity of 1.0% in N-methylpyrrolidone was measured at 30 ° C. with an Ubbelohde viscometer.

Reference example 4
In a reaction vessel equipped with a stirring blade and a distillation tube, 48.0 g (0.35 mol) of p-hydroxybenzoic acid, 30.9 g (0.17 mol) of 4,4′-dihydroxybiphenyl, 5.41 g of terephthalic acid ( 0.033 mol), 10.4 g (0.054 mol) of PET having an intrinsic viscosity of about 0.6 dl / g, 42.0 g (0.20 mol) of trimesic acid, and 76.3 g of acetic anhydride (total of phenolic hydroxyl groups) 1.1 equivalents), and the mixture was reacted at 145 ° C. for 1.5 hours with stirring in a nitrogen gas atmosphere, and then heated to 280 ° C. to carry out a deacetic acid polycondensation reaction. The mixture was stirred for 4 hours, and when about 76% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-1).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-1) was found to have an R portion structure having a p-oxybenzoate unit content p of 2.0, 4,4′-dioxybiphenyl units and ethylene oxide. The unit content q was 0.5, the terephthalate unit content r was 0.5, p + q + r = 3, and the branching point content was 25 mol%. The terminal structure had a carboxylic acid / acetyl group ratio of 75:25.

  The obtained dendritic polyester resin had a melting point Tm of 180 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2100.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after once cooling to room temperature under a temperature drop condition of 20 ° C./min, the endothermic peak temperature (Tm) observed when measured again under a temperature rise condition of 20 ° C./min was used.

  The liquid crystal starting temperature is measured with a shear stress heating device (CSS-450) at a shear rate of 100 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens of 60 times. It was measured.

  The molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method using pentafluorophenol, which is a solvent in which the dendritic polyester resin is soluble, and the number average molecular weight was determined.

Reference Example 5
In a reaction vessel equipped with a stirring blade and a distillation tube, 48.0 g (0.35 mol) of p-hydroxybenzoic acid, 30.9 g (0.17 mol) of 4,4′-dihydroxybiphenyl, 5.41 g of terephthalic acid ( 0.033 mol), 10.4 g (0.054 mol) of PET having an intrinsic viscosity of about 0.6 dl / g, 42.0 g (0.20 mol) of trimesic acid, and 76.3 g of acetic anhydride (total of phenolic hydroxyl groups) 1.1 equivalents), and the mixture was reacted at 145 ° C. for 1.5 hours with stirring in a nitrogen gas atmosphere, and then heated to 250 ° C. to conduct a deacetic acid condensation reaction. After the reactor internal temperature reached 250 ° C., 14.7 g (0.12 mol) of benzoic acid was added and the temperature was raised to 280 ° C. When 100% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-2).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-2) was found to have an R-part structure having a p-oxybenzoate unit content p of 2.0, 4,4′-dioxybiphenyl units and ethylene oxide. The unit content q was 0.5, the terephthalate unit content r was 0.5, p + q + r = 3, and the branching point content was 25 mol%. The terminal structures were carboxylic acid and benzoic acid ester.

  The obtained dendritic polyester resin had a melting point Tm of 182 ° C., a liquid crystal starting temperature of 163 ° C., and a number average molecular weight of 2500.

Reference Example 6
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and 7. 48 g (0.045 mol), 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 62.48 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) The mixture was stirred and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Then, 31.52 g (0.15 mol) of trimesic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of the amount was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-3).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-3) was found to have an R-part structure having a p-oxybenzoate unit content p of 2.66, 4,4′-dioxybiphenyl units and ethylene oxide. The unit content q was 0.66, the terephthalate unit content r was 0.66, p + q + r = 4, and the branching point content was 20 mol%. The terminal structure was an acetyl group.

  In addition, about the branch state, since the information obtained from a nuclear magnetic resonance spectrum analysis is an average value, the decimal degree was rounded off and the branching degree was calculated as an integer. The degree of branching represents how many of the three functional groups are reacted at the branch point D. The nuclear magnetic resonance spectrum was measured at 40 ° C. with a 50% pentafluorophenol: 50% chloroform mixed solvent in the proton nucleus, and the peaks of 7.44 ppm and 8.16 ppm derived from p-oxybenzoate units, 4,4′-di- Detection of 7.04 ppm, 7.70 ppm peak derived from oxybiphenyl unit, 8.31 ppm peak derived from terephthalate unit, 4.75 ppm peak derived from ethylene oxide unit, 9.25 ppm peak derived from structural unit derived from trimesic acid From the peak intensity ratio, the content p, q, r and branch point content of each structural unit were calculated.

  The obtained dendritic polyester resin had a melting point Tm of 185 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2300.

Reference Example 7
In a 500 mL reaction vessel equipped with a stirring blade and a distillation pipe, 58.01 g (0.42 mol) of p-hydroxybenzoic acid, 23.46 g (0.126 mol) of 4,4′-dihydroxybiphenyl, 5.95 g of hydroquinone. (0.054 mol), 19.44 g (0.117 mol) of terephthalic acid, isophthalic acid (0.063 mol) and 79.63 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) were charged in a nitrogen gas atmosphere. The mixture was reacted at 145 ° C. for 2 hours with stirring, and then added with 31.52 g (0.15 mol) of trimesic acid, heated to 260 ° C., stirred for 3 hours, and 91% of the theoretical distillation amount of acetic acid. When distilling, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-4).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-4) has a structure in which the R portion has a p-oxybenzoate unit content p of 2.14, 4,4′-dioxybiphenyl units and di-esters. The oxybenzene unit content q was 0.92, the terephthalate unit and isophthalate unit content r was 0.92, p + q + r = 4, and the branching point content was 20 mol%. The terminal structure excluding the terminal functional group of trimesic acid had a ratio of carboxylic acid to acetyl group of 75:25.

  The obtained dendritic polyester resin had a melting point Tm of 186 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2,100.

Reference Example 8
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 60.50 g (0.44 mol) of p-hydroxybenzoic acid, 30.49 g (0.162 mol) of 6-hydroxy-2-naphthoic acid, 4,4 After charging 18.62 g (0.10 mol) of '-dihydroxybiphenyl and 61.25 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups), the mixture was reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere. Then, 31.52 g (0.176 mol) of trimesic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of the theoretical distillation amount of acetic acid was distilled, the heating and stirring were stopped, and the contents Was discharged into cold water to obtain a dendritic polyester resin (C-5).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-5) has a structure in which the R portion has a p-oxybenzoate unit and 6-oxy-2-naphthoate unit content p of 3.42, 4, The content q of 4′-dioxybiphenyl units was 0.58, p + q + r = 4, and the branching point content was 20 mol%. The terminal structure excluding the functional group of trimesic acid had a ratio of carboxylic acid to hydroxyl group of 75:25.

  The obtained dendritic polyester resin had a melting point Tm of 168 ° C., a liquid crystal starting temperature of 145 ° C., and a number average molecular weight of 2,100.

Reference Example 9
In a 500 mL reaction vessel equipped with a stirring blade and a distillation pipe, 58.01 g (0.42 mol) of p-hydroxybenzoic acid, 23.46 g (0.126 mol) of 4,4′-dihydroxybiphenyl, 5.95 g of hydroquinone. (0.054 mol), 19.44 g (0.117 mol) of terephthalic acid, isophthalic acid (0.063 mol) and 79.63 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) were charged in a nitrogen gas atmosphere. The mixture was reacted at 145 ° C. for 2 hours with stirring, and then added with 15.13 g (0.072 mol) of trimesic acid, heated to 260 ° C., stirred for 3 hours, and 91% of the theoretical distillation amount of acetic acid. When distilling, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-6).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-6) was found to have a structure with an R portion having a p-oxybenzoate unit content p of 4.84, 4,4′-dioxybiphenyl units and di-esters. The oxybenzene unit content q was 2.09, the terephthalate unit and isophthalate unit content r was 2.09, p + q + r = 9, and the branching point content was 10 mol%. The terminal structure excluding the functional group of trimesic acid had a ratio of carboxylic acid to acetyl group of 75:25.

  The obtained dendritic polyester resin had a melting point Tm of 208 ° C., a liquid crystal starting temperature of 189 ° C., and a number average molecular weight of 4500.

Reference Example 10
In a 500 mL reaction vessel equipped with a stirring blade and a distillation pipe, 58.01 g (0.42 mol) of p-hydroxybenzoic acid, 23.46 g (0.126 mol) of 4,4′-dihydroxybiphenyl, 5.95 g of hydroquinone. (0.054 mol), 19.44 g (0.117 mol) of terephthalic acid, isophthalic acid (0.063 mol) and 79.63 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) were charged in a nitrogen gas atmosphere. The mixture was reacted at 145 ° C. for 2 hours with stirring, and then 23.12 g (0.15 mol) of α-resorcillic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-7).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-7) was found to have an R portion structure having a p-oxybenzoate unit content p of 2.14, 4,4′-dioxybiphenyl units and ethylene oxide. The unit content q was 0.92, the terephthalate unit content r was 0.92, p + q + r = 4, and the branching point content was 20 mol%. The terminal structure had a ratio of carboxylic acid to acetyl group of 42:58.

  The obtained dendritic polyester resin had a melting point Tm of 176 ° C., a liquid crystal starting temperature of 152 ° C., and a number average molecular weight of 2,000.

Reference Example 11
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.30 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and terephthalic acid 7. 48 g (0.045 mol), 14.40 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 42.72 g (0.28 mol) of α-resorcillic acid, and acetic anhydride 78 .26 g (1.08 equivalent of the total of phenolic hydroxyl groups) was charged and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Thereafter, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled out, 25.6 g of benzoic acid (0.21 mol; 1.000 times the theoretical acetoxy terminal). ) Was added and acetic acid was distilled off to 100%. Then, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (C-8).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (C-8) was found to have an R-part structure having a p-oxybenzoate unit content p of 1.32, a 4,4′-dioxybiphenyl unit and an ethylene oxide. The unit content q was 0.33, the terephthalate unit content r was 0.33, p + q + r = 2, and the branching point content was 30 mol%. The terminal structure had a ratio of carboxylic acid to acetyl group of 50:50.

  The obtained dendritic polyester resin had a melting point Tm of 182 ° C., a liquid crystal starting temperature of 152 ° C., and a number average molecular weight of 3,500.

Reference Example 12
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and 7. 48 g (0.045 mol), 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 62.48 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) The mixture was charged and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere, then heated to 260 ° C. and stirred for 3 hours. When 91% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were performed. The operation was stopped, and the contents were discharged into cold water to obtain a linear liquid crystal resin (E-1).

  The melting point of this liquid crystal resin (E-1) was 264 ° C., the liquid crystal starting temperature was 232 ° C., and the number average molecular weight was 2200.

Reference Example 13
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and 7. 48 g (0.045 mol), 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 62.48 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) The mixture was stirred and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Then, 6.62 g (0.032 mol) of trimesic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of the amount was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (E-2).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (E-2) was found to have an R-part structure of p-oxybenzoate unit content p of 10.22, 4,4′-dioxybiphenyl unit and ethylene oxide. The unit content q was 4.41, the terephthalate unit content r was 4.41, p + q + r = 19, and the branching point content was 5 mol%.

  The obtained polyester had a melting point Tm of 232 ° C., a liquid crystal starting temperature of 215 ° C., and a number average molecular weight of 2200.

Reference Example 14
The reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then 5 parts of trimethylolpropane, 50 parts of 2,2′-bis (hydroxymethyl) heptanoic acid, 7 parts of stearic acid, and 0.2 of p-toluenesulfonic acid The mixture was reacted for 2 hours while stirring at 140 ° C. under a nitrogen stream, and further reacted at 140 ° C. and 67 Pa for 1 hour to obtain a dendritic resin (E-3). As a result of analyzing E-3, it was number average molecular weight 1900.

Reference Example 15
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 51.93 g (0.38 mol) of p-hydroxybenzoic acid, 19.1 g (0.10 mol) of 4,4′-dihydroxybiphenyl, and terephthalic acid 5. 86 g (0.035 mol), 21.2 g (0.10 mol) trimesic acid, 5.55 g (0.045 mol) benzoic acid, 11.3 g polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g (0.059 mol) and 65.3 g of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were charged and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. After heating up to 290 ° C over 3 hours, the polymerization temperature was reduced to 1.0 mmHg (133 Pa) in 30 minutes while maintaining the polymerization temperature at 290 ° C, and the polymerization reaction was stopped when the stirring torque reached 2.5 kg · cm. The contents were discharged into the water. The obtained dendritic polyester resin (C-9) was heated and dried at 110 ° C. for 4 hours, pulverized using a blender, and washed with ethanol and deionized water. Then, it vacuum-dried at 110 degreeC for 16 hours using the vacuum heat dryer, and obtained powdery dendritic polyester was used for various measurements.

  As a result of conducting a nuclear magnetic resonance spectrum analysis about the obtained dendritic polyester resin (C-9), trimesic acid content was 14 mol%.

  For the nuclear magnetic resonance spectrum, the sample was dissolved in a mixed solvent of 50% pentafluorophenol: 50% deuterated chloroform, and nuclear magnetic resonance spectrum analysis of proton nuclei was performed at 40 ° C. 7.44 ppm and 8.16 ppm peaks derived from p-oxybenzoate units, 7.04 ppm, 7.70 ppm peaks derived from 4,4′-dioxybiphenyl units, 8.31 ppm peaks derived from terephthalate units, ethylene oxide units A peak at 4.75 ppm derived from 9.25 ppm derived from trimesic acid was detected. The trimesic acid content was calculated from the area intensity ratio of each peak, and the numbers after the decimal point were rounded off.

  The obtained dendritic polyester resin had a melting point of 235 ° C., a liquid crystal starting temperature of 191 ° C. and a number average molecular weight of 12,500. Using a Koka flow tester, the melt viscosity measured at a temperature of 260 ° C. and a shear rate of 100 / s was 18 Pa · s.

Reference Example 16
The monomer weight used in the reaction was 50.4 g (0.37 mol) of p-hydroxybenzoic acid, 12.4 g (0.067 mol) of 4,4′-dihydroxybiphenyl, 25 of 2-hydroxy-6-naphthoic acid. .4 g (0.14 mol), trimesic acid 21.0 g (0.10 mol), benzoic acid 5.50 g (0.045 mol) and acetic anhydride 71.1 g (1.10 equivalents of total phenolic hydroxyl groups) A dendritic polyester resin (C-10) was obtained in the same manner as in Reference Example 15 except that.

  The obtained dendritic polyester resin (C-10) had a trimesic acid content of 14 mol%, a melting point of 225 ° C, a liquid crystal starting temperature of 186 ° C, and a number average molecular weight of 11,900. Using a Koka flow tester, the melt viscosity measured at a temperature of 260 ° C. and a shear rate of 100 / s was 14 Pa · s.

(1) Fluidity Using SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., set the cylinder temperature and mold temperature shown in the table, set the injection pressure to 30 MPa, 200 mm length x 10 mm width x 1 mm thickness rod flow test Using a piece, the rod flow length at a holding pressure of 0 was measured. The larger the flow length, the better the fluidity.

(2) Melt viscosity This is a shear rate of 100 / s measured using a capillary with a capillary length (L) of 10 mm × capillary diameter (D) of 1 mm at a measurement temperature shown in the table by a capillograph (manufactured by Toyo Seiki). .

(3) Tensile Strength, Tensile Elongation According to ASTM D638, a tensile test was performed on an ASTM No. 1 dumbbell test piece at a crosshead speed of 10 mm / min using a tester Tensilon UTA2.5T (manufactured by Baldwin).

(4) Impact resistance According to ASTM D256, the Izod impact strength of a molded product with a 3 mm thick notch at 23 ° C. was measured.

(5) Heat resistance Using a bending test piece (1/4 inch thick), a deflection temperature under load (1.82 MPa) was measured according to ASTM method D648.

(Examples 1-15, Comparative Examples 1-11)
Each component shown below was dry blended in the proportions shown in Tables 1 and 2 and then supplied from an extruder main feeder. Using a TEX30 type twin screw extruder manufactured by Nippon Steel Co., Ltd., at the cylinder set temperature shown in the table Then, melt kneading was performed at a screw rotation speed of 200 rpm, and the gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and the test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at the cylinder temperature and mold temperature shown in the table. The results of evaluating the fluidity, mechanical properties, and heat resistance of each sample are as shown in Tables 1 and 2. In Comparative Examples 1 to 6, as compared with Comparative Example 7 in which the amorphous resin (a) is not added, the heat resistance is improved, but the fluidity is greatly reduced. Comparative Example 8 is a linear liquid crystal resin, and Comparative Example 9 is a case where a dendritic polyester resin that does not satisfy the requirements of the present invention is used, but the effect of improving fluidity was not observed. Comparative Examples 10 and 11 were cases where a dendritic resin having a structure different from that of the present invention was blended. However, although there was an effect of improving fluidity, a decrease in physical properties was observed. In contrast, this example has a good balance of mechanical properties, heat resistance and fluidity.

(Examples 16-18 , 20-29 , Reference Example 1, Comparative Examples 12-22 )
Each component shown below was dry blended in the proportions shown in Tables 3 and 4 and then supplied from an extruder main feeder. The TEX30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. Melting and kneading were performed at a screw rotation speed of 200 rpm, and the gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. Among the obtained pellets, Examples 16 to 20, 20 to 24, Reference Example 1 and Comparative Examples 12 to 17 were hot-air dried at 110 ° C. for 12 hours, and Examples 25 to 28 and Comparative Examples 18 to 21 were 80. After drying under reduced pressure at 12 ° C. for 12 hours, a test piece was prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at the cylinder temperature and mold temperature shown in the table. The results of evaluating the fluidity, mechanical properties, and heat resistance of each sample are as shown in Tables 3 and 4. As compared with Comparative Examples 11 to 21 in which the dendritic polyester resin (c) is not added, it is clear that this example is excellent in balance of mechanical properties, heat resistance and fluidity.

(Examples 30 to 33)
After dry blending each component shown below at each ratio shown in Table 5, it is supplied from an extruder main feeder, and is a TEX30 type twin screw extruder manufactured by Nippon Steel, Ltd. Melt kneading was performed at 200 rpm, and the gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. Among the obtained pellets, Examples 30 to 31 were dried under reduced pressure at 80 ° C. for 12 hours, then Examples 32 to 36 and Comparative Examples 18 to 21 were hot air dried at 110 ° C. for 12 hours, and then shown in the table. Test pieces were prepared by injection molding (SG75H-MIV, manufactured by Sumitomo Heavy Industries) with the cylinder temperature and mold temperature set. The results of evaluating the fluidity, mechanical properties, and heat resistance of each sample are as shown in Table 5. As compared with the comparative example in which the dendritic polyester resin (c) is not added, it is clear that this example has excellent fluidity specifically.

The amorphous resin (a) used in this example and the comparative example is as follows.
A-1: Poly (2,6-dimethyl-1,4-phenylene) ether resin having a glass transition temperature of 220 ° C. and an intrinsic viscosity of 0.50 dL / g (30 ° C. in chloroform) and 1 part by weight of maleic anhydride And a radical generator (perhexine 25B: manufactured by NOF Corporation) by dry blending, and melt-kneading at a cylinder temperature of 320 ° C.
A-2: Polycarbonate resin having a glass transition temperature of 145 ° C. and a total light transmittance of 89% (“Taflon” A1900 manufactured by Idemitsu Kosan Co., Ltd.)
A-3: Polyetherimide resin having a glass transition temperature of 214 ° C. (“Ultem” 1010 manufactured by GE Plastics)
A-4: Polyamideimide resin obtained in Reference Example 2.
A-5: Polysulfone resin having a glass transition temperature of 185 ° C. (“Udel” P1700 manufactured by Solvay Advanced Polymers)
A-6: Polyethersulfone resin having a glass transition temperature of 220 ° C. (“Radel A” A300 manufactured by Solvay Advanced Polymers)
A-7: Polyarylate resin having a glass transition temperature of 195 ° C. (“U polymer” U-100 manufactured by Unitika)
A-8: Amorphous polyamide resin having a glass transition temperature of 160 ° C. (“Grillamide” TR55 manufactured by MMS)
A-9: Polyphenylene sulfide sulfone resin obtained in Reference Example 3.
Similarly, the thermoplastic resin (b) is as follows.
B-1: Nylon 66 resin having a melting point of 265 ° C. and 98% sulfuric acid of 1 g / dl and a relative viscosity of 2.95 (“Amilan” CM3001N manufactured by Toray)
B-2: Nylon 6 resin (melting point 225 ° C., 98% sulfuric acid 1 g / dl, relative viscosity 2.80 (“Amilan” CM1010 manufactured by Toray)
B-3: Polybutylene terephthalate resin having a melting point of 225 ° C. and an intrinsic viscosity of 0.85 dl / g (“Toraycon” 1100S manufactured by Toray)
B-4: Poly L lactic acid resin having a melting point of 170 ° C., a weight average molecular weight (in terms of PMMA) of 160,000, and a D-form content of 1.2%.
B-5: Liquid crystal polyester resin obtained in Reference Example 1.
B-6: PPS resin having a melting point of 280 ° C. and MFR = 200 g / 10 minutes (315.5 ° C., 5 kg load) (“Torelina” M2588 manufactured by Toray)
B-7: ABS resin measured according to ISO 1133 = 18 g / 10 min (220 ° C., 10 kg load) (“Toyolac” ABS900-352 manufactured by Toray)
B-8: Polyethylene terephthalate resin having a melting point of 260 ° C., an intrinsic viscosity of 1.27, and a carboxyl end group amount of 14 eq / t.

Similarly, the fluidity improver (c) is as follows.
C-1: Reference Example 4
C-2: Reference example 5
C-3: Reference Example 6
C-4: Reference example 7
C-5: Reference Example 8
C-6: Reference Example 9
C-7: Reference Example 10
C-8: Reference Example 11
C-9: Reference Example 15
C-10: Reference Example 16.

Similarly, the following was added and used.
D-1: Reference example 12
D-2: Reference example 13
D-3: Reference example 14
D-4: Hyperbranched polymer with molecular weight of 3500 manufactured by Perstorp (“BOLTORN” H30 manufactured by Perstorp)
Similarly, the following were used as impact resistance improvers.
E-1: Styrene-ethylene / butylene-styrene copolymer (“Clayton” G1651 manufactured by Kraton Polymer Japan)
Similarly, the following was used as a compatibilizing agent.
F-1: 3-isocyanatopropyltriethoxysilane (Shin-Etsu Silicone KBE-9007)
F-2: Glycidyl ester type epoxy resin ("Epicoat" 191P manufactured by Japan Epoxy Resin)

Claims (9)

At least one amorphous resin selected from polyphenylene ether resin, polycarbonate resin, polyetherimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, amorphous polyamide resin, polyphenylene sulfide sulfone resin ( a) 5 to 95% by weight and at least one thermoplastic resin (b) selected from crystalline polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene sulfide resin, ABS resin The aromatic oxycarbonyl unit (S) represented by the following formula (1), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit with respect to 100 parts by weight of the resin composition Choose from (U) At least one structural unit and a trifunctional or tetrafunctional aromatic organic residue (D), and the total content of S, T, U and D is 7.5%. P / q is 5/95 or more and p / r is 5/95 when the average molar content of the structural units S, T, and U is p, q, and r, respectively. The thermoplastic resin composition obtained by blending 0.01 to 30 parts by weight of the dendritic polyester resin (c) exhibiting molten liquid crystallinity.

(Here, R1, R2 and R3 are each at least one structural unit selected from structural units represented by the following formula.)

(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.) The thermoplastic resin composition according to claim 1, wherein the dendritic polyester resin (c) contains a basic skeleton represented by the following formula (2).

(Here, D is an organic residue of a trifunctional compound, and DD is bonded directly by an ester bond and / or an amide bond, or bonded via a structural unit selected from S, T and U. Yes.) The thermoplastic resin composition according to claim 1, wherein the dendritic polyester resin (c) contains a basic skeleton represented by the following formula (3).

(Here, D is an organic residue of a tetrafunctional compound, and DD is bonded directly by an ester bond and / or an amide bond or via a structural unit selected from S, T and U. Yes.) The thermoplastic resin composition according to claim 1 or 2, wherein the organic residue D of the dendritic polyester resin (c) is an organic residue of a compound represented by the following formula (4).

The thermoplastic resin composition according to any one of claims 1 to 4 , wherein the thermoplastic resin (b) is a crystalline polyamide resin. The amorphous resin (a) is a thermoplastic resin composition according to any one of claims 1-5, characterized in that the polyphenylene ether resin. The molded article formed by melt-molding the thermoplastic resin composition of any one of Claims 1-6 . The molded article according to claim 7 , wherein the melt molding is any one selected from injection molding, injection compression molding, and compression molding. The film which consists of a thermoplastic resin composition in any one of Claims 1-6 .