JP2008031439A - Thermoplastic resin composition, manufacturing method of the same and molded article consisting of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in fluidity and mechanical characteristics, its manufacturing method and a molded article consisting of it. <P>SOLUTION: The thermoplastic resin composition is obtained by blending 0.1-4 parts by weight of a compound (B) having three or more functional groups in 100 parts by weight of a thermoplastic resin (A). It is preferable that the compound (B) having the three or more functional groups contains one or more alkylene oxide units, and it is more preferable that the thermoplastic resin (A) is one or more selected from among polyester resins, polycarbonate resins and polyamide resins. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in fluidity and mechanical properties useful as electrical / electronic equipment parts, automobile parts, machine parts and the like, and in a preferred embodiment, it is excellent in hydrolysis resistance and toughness, thermoplastic resin and three or more specific ones. The present invention relates to a thermoplastic resin composition comprising a compound having a functional group, a method for producing the same, and a molded product comprising the same.

  Polyester resins, polyamide resins, and polycarbonate resins, which are thermoplastic resins, have excellent mechanical properties, heat resistance, moldability, and recyclability, and thus are widely used in various containers, films, electrical / electronic parts, and the like. Among them, polybutylene terephthalate, polypropylene terephthalate, and polyethylene terephthalate, which are one type of polyester resin, have a higher reinforcing effect with inorganic fillers and excellent chemical resistance. It is widely used as a material for industrial moldings.

  However, in recent years, there has been an increasing demand for miniaturization and weight reduction of industrial molded products. In particular, polybutylene terephthalate for use in automobiles and electrical / electronic equipment can meet these requirements without deteriorating mechanical properties. It is desired to improve the fluidity at the time of melting.

  Patent Document 1 describes a polyester resin having a polyvalent carboxylic acid or a polyhydric alcohol having a valence of 3 or more and a melt tension of 0.8 to 5.0 g. There was a problem that the fluidity was lowered.

Patent Document 2 describes a fluidity improving method in which a combination of a specific thermoplastic resin and a compound having a specific at least three functional groups is melt-mixed, but the fluidity improving effect is insufficient. In addition, the mechanical properties tended to decrease.
JP 2001-200038 A (Claims) JP-A-7-304970 (Claims)

  The present invention is a thermoplastic resin composition comprising a thermoplastic resin and a compound having three or more specific functional groups, which are excellent in fluidity and mechanical properties, and in a preferred embodiment, excellent in hydrolysis resistance and toughness. It is an object to provide a product, a method for producing the product, and a molded product comprising the product.

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

That is, the present invention
(1) (A) A thermoplastic resin composition obtained by blending 0.1 to 4 parts by weight of a compound having three or more functional groups with respect to 100 parts by weight of a thermoplastic resin,
(2) (B) The compound having three or more functional groups is a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having the functional groups is represented by the formula (1). The thermoplastic resin composition according to (1), which is a compound having a structure

(3) The thermoplastic resin composition according to (1), wherein the compound (B) having three or more functional groups contains one or more alkylene oxide units,
(4) The thermoplastic resin according to any one of (1) to (3), wherein the thermoplastic resin composition (A) is at least one selected from a polyester resin, a polycarbonate resin, and a polyamide resin. Resin composition,
(5) The functional group of the compound having three or more functional groups (B) is at least one group selected from a hydroxyl group, a carboxylic acid group, an amino group, a glycidyl group, and an isocyanate group. (1) to the thermoplastic resin composition according to any one of (4),
(6) The thermoplastic resin composition according to any one of (1) to (5), further comprising (C) a terminal blocking agent having less than three functional groups.
(7) The thermoplastic resin composition according to any one of (1) to (6), wherein at least one of the thermoplastic resins (A) is a polyester, and (D) a transesterification catalyst is further blended.
(8) At least one of the above-mentioned (A) thermoplastic resins is a polyester, and (E) a polyester having a weight average molecular weight of 100 to 8000 is further blended. Thermoplastic resin composition,
(9) The thermoplastic resin composition according to any one of (1) to (8), further comprising (F) an inorganic filler.
(10) The thermoplastic resin composition according to any one of (1) to (9), further comprising (G) an impact resistance improver,
(11) When producing the thermoplastic resin composition according to any one of (1) to (10), assuming that the screw length of the twin screw extruder is L and the screw diameter is D, L / D> 30 A method for producing a thermoplastic resin composition that is melt-kneaded using a twin-screw extruder of
(12) A molded article obtained by molding the thermoplastic resin composition according to any one of (1) to (10) is provided.

  According to the present invention, a thermoplastic resin composition comprising a thermoplastic resin and a compound having three or more functional groups, which are excellent in fluidity and mechanical properties, and in a preferred embodiment, excellent in hydrolysis resistance and toughness. Product, a method for producing the product, and a molded product comprising the product.

  The thermoplastic resin (A) used in the present invention may be any resin that can be melt-molded. For example, polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic olefin resin, acrylonitrile / butanediene / styrene (ABS) Resin, acrylonitrile / styrene (AS) resin, cellulose resin such as cellulose acetate, polyester resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyether ether ketone resin , Polyimide resins and polyetherimide resins, and the like may be used alone or in combination of two or more. Among them, polyester resin, polyamide resin, polyacetal resin and polycarbonate resin are preferable in terms of heat resistance, moldability, fluidity and mechanical properties, polyester resin, polyamide resin and polycarbonate resin are more preferable, and selected from polyester resin and polycarbonate resin. More preferably, at least one selected from the above. These may be used alone or in combination of two or more, and may be used as a polymer alloy. However, two or more of them are used in combination in that various properties such as durability, appearance, hardness and mechanical properties are excellent. It is preferable.

  In the present invention, a polymer alloy (strictly a resin composition) composed of two or more kinds of resins as described above is also referred to as “resin”.

  When a polyester resin is used as the thermoplastic resin (A) used in the present invention, the polyester resin means (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or the An ester-forming derivative, (c) a polymer or copolymer having at least one selected from lactone as a main structural unit.

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

  Examples of the diol or ester-forming derivative 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, 1,5-oxepan-2-one, and the polymer or copolymer having these as structural units includes polycaprolactone. , Polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Of these, polymers or copolymers having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative are preferred, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol. Or, 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 them, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate , Aromatic polyester resins such as polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate Is particularly preferred, and polybutylene terephthalate is most preferred.

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

  In the present invention, a liquid crystalline polyester capable of forming anisotropy when melted may be used as the polyester resin. Examples of the structural unit of the liquid crystalline polyester include an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, and an aromatic iminooxy unit.

  Moreover, in this invention, it is preferable to use 2 or more types of polyester resin at the point of fluidity | liquidity and mechanical property, and the combination of non-liquid crystalline polyester and liquid crystalline polyester is especially preferable.

  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, and preferably 30 eq / t or less in terms of fluidity, hydrolysis resistance, and heat resistance. More preferably, it is 20 eq / t or less, more preferably 10 eq / t or less. The lower limit is 0 eq / t. In the present invention, the carboxyl end group amount of (A) thermoplastic resin is a value measured by dissolving in 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, from the viewpoint of color tone and fluidity, and 5 eq / t. More preferably, it is as follows. The lower limit is 0 eq / t. In the present invention, the vinyl terminal group amount of (A) the thermoplastic resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The amount of hydroxyl end 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, in terms of moldability and fluidity, and 100 eq / t is more preferably t or more, and particularly preferably 120 eq / t or more. The upper limit is not particularly limited, but is 180 eq / t. In the present invention, the hydroxyl terminal group amount of (A) the thermoplastic resin is 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 as long as it can be melt-kneaded. However, in terms of moldability, the intrinsic viscosity when the o-chlorophenol solution is measured at 25 ° C. is 0.36 to 1. The range is preferably 60 dl / g, more preferably 0.50 to 1.50 dl / g.

  The molecular weight of the polyester resin used in the present invention is preferably in the range of more than 8,000 to 500,000, more preferably in the range of more than 8,000 to 300,000 in terms of heat resistance. More preferably, it is more than 8000 and not more than 250,000. In the present invention, Mw of the polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  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 an exchange reaction or a reaction by direct polymerization can be applied, but continuous polymerization is preferable in terms of cost because the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. Direct polymerization is preferred.

  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, the dicarboxylic acid or The ester-forming derivative and the diol or the ester-forming derivative thereof can be produced by an esterification reaction or a transesterification reaction and then a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and 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, Triphenyl Hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Tin compounds such as alkylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, etc. Among these, organic titanium compounds and tin compounds are preferred, Furthermore, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are preferred, and titanic acid is preferred. Tetra -n- butyl ester is particularly 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.

When polycarbonate is used as the thermoplastic resin (A) used in the present invention, the polycarbonate resin is bisphenol A, that is, 2,2′-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylalkane or 4 , 4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxydiphenyl ether are polycarbonates mainly composed of one or more kinds of dihydroxy compounds.
Among these, bisphenol A, that is, a product produced using 2,2′-bis (4-hydroxyphenyl) propane as a main raw material is preferable.

  The manufacturing method of the polycarbonate resin used by this invention is not specifically limited, It can manufacture by well-known transesterification and the phosgene method. Specifically, polycarbonate obtained by the transesterification method or the phosgene method using the above bisphenol A or the like as a dihydroxy component is preferable. Further, the bisphenol A may be used in combination with other dihydroxy compounds copolymerizable therewith, such as 4,4′-dihydroxydiphenylalkane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl ether, and the like. The amount of other dihydroxy compounds used is preferably 10 mol% or less based on the total amount of dihydroxy compounds.

  The degree of polymerization of these polycarbonate resins is not particularly limited, but the specific viscosity is 0.1 to 2.0, particularly 0.5 to 1 when 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride and measured at 20 ° C. Those in the range of 0.5 are preferred, and those in the range of 0.8 to 1.5 are most preferred.

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

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

  Among these, preferable polyamide resins include nylon 6, nylon 66, nylon 12, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 12, and nylon 6T / 6 copolymer. 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 a relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is preferably in the range of 1.5 to 7.0. In particular, a polyamide resin in the range of 2.0 to 6.0 is preferable.

  The melting point of the thermoplastic resin (A) used in the present invention is not particularly limited, but is preferably 120 ° C. or higher, more preferably 180 ° C. or higher, and 200 ° C. or higher in terms of heat resistance. Is more preferable, and it is particularly preferable that the temperature is 220 ° C. or higher. Although an upper limit is not specifically limited, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less. In the present invention, the melting point of the thermoplastic resin (A) is a peak top value detected when measured by a differential scanning calorimeter (DSC) at a temperature rising rate of 20 ° C./min.

  The glass transition point of the thermoplastic resin (A) used in the present invention is not particularly limited, but is preferably 80 ° C or higher, more preferably 100 ° C or higher, and 120 ° C or higher in terms of heat resistance. More preferably, it is particularly preferably 140 ° C. or higher. Although an upper limit is not specifically limited, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less. In the present invention, (A) the glass transition point of the thermoplastic resin is approximately the temperature range in which the glass transition detected when measured by a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min is performed. The midpoint value.

  The compound (B) having three or more functional groups used in the present invention is a component necessary for improving the fluidity of the thermoplastic resin of the present invention. The component (B) is not limited as long as it has three or more functional groups in the molecule, and may be a low molecular compound or a polymer. The component (B) may be any compound as long as it has three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound, but has excellent fluidity and mechanical properties. In this respect, a trifunctional compound or a tetrafunctional compound is more preferable, and a tetrafunctional compound is further preferable.

  In the present invention, in terms of excellent fluidity and mechanical properties, the component (B) includes (B) a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having functional groups. Is preferably a compound having a structure represented by the formula (1), and particularly in terms of excellent fluidity and mechanical properties, the component (B) is a polyfunctional compound having (B) three or more functional groups. More preferably, the compound is a compound in which two or more of the terminal structures having a functional group are structures represented by the formula (1), and the terminal structure having a functional group in the component (B) More preferably, at least one compound is a compound represented by the formula (1), and all of the terminal structures having a functional group in the component (B) are compounds represented by the formula (1). Most preferably it is.

  Here, R represents a hydrocarbon group having 1 to 15 carbon atoms, n represents an integer of 1 to 10, X represents a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, It represents at least one functional group selected from an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group.

  In the present invention, R represents an alkylene group, n represents an integer of 1 to 7, and X represents a hydroxyl group or a carboxylic acid group in terms of excellent fluidity, recyclability, durability and mechanical properties. , Preferably represents at least one functional group selected from an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group, R represents an alkylene group, and n represents an integer of 1 to 5, More preferably, X represents at least one functional group selected from a hydroxyl group, a carboxylic acid group, an amino group, a glycidyl group, and an ester group, R represents an alkylene group, and n is an integer of 1 to 4. X is more preferably at least one functional group selected from a hydroxyl group, an amino group, a glycidyl group, and an ester group, R represents an alkylene group, and n is an integer of 1 to 3. The stands, X is particularly preferably a hydroxyl group. In the present invention, when R is an alkylene group, the structure represented by the formula (1) indicates a structure containing an alkylene oxide unit.

  In the present invention, the functional group in the component (B) is a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, Preferably, at least one selected from silanol groups and silyl ether groups is used, and the functional group in component (B) may have three or more functional groups that are the same or different from these. preferable. In the present invention, the component (B) is (B) a polyfunctional compound having three or more functional groups, and two or more terminal structures having functional groups are represented by the formula (1). In the case of a compound having a structure, the functional group may be the same or different from the above, but in terms of fluidity, mechanical properties, durability, heat resistance and productivity, It is preferable that they are the same.

  (B) As a preferred example of a compound having three or more functional groups, when the functional group is a hydroxyl group, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6- Xanthriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tritrimethylol Propane, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, mannitol, sucrose, 1,3,5-trihydroxybenzene , Include polymers such as polyhydric alcohol or a polyvinyl alcohol having a carbon number of 3 to 24 such as 2,4-trihydroxybenzene. Of these, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol having a branched structure are preferable from the viewpoint of fluidity and mechanical properties.

  (B) As a preferred example of a compound having three or more functional groups, when the functional group is a carboxylic acid group, propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-tris Carboxylic acid, butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, cyclohexane 1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene-2,5 , 7-tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid, naphthalene-1,4,5, - polycarboxylic acid or acrylic acid, such as tetracarboxylic acid, include polymers such as methacrylic acid, it may be used acid anhydrides thereof. Of these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides having a branched structure are preferable from the viewpoint of fluidity.

(B) When the functional group of a compound having three or more functional groups is an amino group, at least one of the three or more substituents is preferably a primary or secondary amine, both of which are primary Or it is more preferable that it is a secondary amine, and it is especially preferable that all are primary amines. (B) As a preferable example of the compound having three or more functional groups, when the functional group is an amino group, 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, , 2,4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetramino Benzene, 1,2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, 1,4,5,8 -Te La Mino naphthalene, and the like. Of these, 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane and 1,3,5-triaminobenzene having a branched structure are preferable from the viewpoint of fluidity.
(B) As a preferred example of a compound having three or more functional groups, when the functional group is a glycidyl group, a monomer such as triglycidyl triazolidine-3,5-dione, triglycidyl isocyanurate, poly Examples include (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, glycidyl group-containing acrylic / styrene polymer, and the like.

  (B) As a preferred example of a compound having three or more functional groups, when the functional group is an isocyanate group, nonane triisocyanate (for example, 4-isocyanatomethyl-1,8-octane diisocyanate (TIN)), decantrie Examples thereof include isocyanate, undecane triisocyanate, and dodecane triisocyanate.

  (B) As a preferable example of the compound having three or more functional groups, when the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of the compound having three or more hydroxyl groups, or the three or more groups described above And ester derivatives of compounds having a carboxylic acid group.

  (B) As a preferable example of the compound having three or more functional groups, when the functional group is an amide group, an amide derivative of the compound having three or more carboxylic acid groups may be mentioned.

  From the viewpoint of fluidity and mechanical properties, it is preferable that (B) the compound having three or more functional groups contains one or more alkylene oxide units. In the present invention, the component (B) is (B) a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having a functional group is represented by the formula (1) In the case where R in the formula (1) is an alkylene group, the structure represented by the formula (1) indicates a structure containing an alkylene oxide unit and is particularly excellent in fluidity. In this respect, the component (B) is most preferably (B) a polyfunctional compound having three or more functional groups, and a polyfunctional compound containing an alkylene oxide unit. In the present invention, an aliphatic alkylene oxide unit having 1 to 4 carbon atoms is effective as a preferred example of an alkylene oxide unit. Specific examples include a methylene oxide unit, an ethylene oxide unit, a trimethylene oxide unit, a propylene oxide unit, Examples include tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units, and isobutylene oxide units. In the present invention, in particular, fluidity, recyclability, durability, heat resistance and From the viewpoint of excellent mechanical properties, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit, and in terms of excellent hydrolysis resistance and toughness (tensile elongation at break), a propylene oxide unit. Contains It is particularly preferred to use that compound.

  In the component (B) used in the present invention, (B) the number of alkylene oxide units contained in the compound having three or more functional groups is alkylene oxide per functional group in terms of excellent fluidity and mechanical properties. The unit is preferably 0.1 to 20, more preferably 0.5 to 10, and further preferably 1 to 5.

  As a preferred example of a compound having three or more functional groups (B) containing one or more alkylene oxide units, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, (poly) oxyethylene glycerin, (poly) Oxytrimethylene glycerol, (poly) oxypropylene glycerol, (poly) oxyethylene- (poly) oxypropylene glycerol, (poly) oxytetramethylene glycerol, (poly) oxymethylene diglycerol, (poly) oxyethylene diglycerol, ( Poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylene trimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) oxyp Pyrenetrimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane, (poly ) Oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (Poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol, (poly) o Simethylenedipentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose, (poly) oxyethylene glucose, (poly ) Oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, (poly) oxytetramethylene glucose and the like.

  In addition, as a preferred example of a compound having three or more functional groups (B) containing one or more alkylene oxide units, when the functional group is a carboxylic acid, propane-1,2,2 containing a (poly) methylene oxide unit 3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) trimethylene oxide units, (poly) propylene oxide units Propane-1,2,3-tricarboxylic acid containing, propane-1,2,3-tricarboxylic acid containing (poly) tetramethylene oxide units, 2-methylpropane-1,2,3 containing (poly) methylene oxide units -Triscarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) ethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing poly) trimethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) propylene oxide units, (poly) tetra 2-methylpropane-1,2,3-triscarboxylic acid containing methylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) methylene oxide units, butane-1 containing (poly) ethylene oxide units, 2,4-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, (poly) tetra Butane-1,2,4-tricarboxylic acid containing methylene oxide units, butane containing (poly) methylene oxide units 1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) ethylene oxide units, butane-1,2,3 containing (poly) trimethylene oxide units 4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly) tetramethylene oxide units , Trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) trimethylene oxide units, trimellitic acid containing (poly) propylene oxide units, ( Trimellitic acid containing poly) tetramethylene oxide units, trimesic acid containing (poly) methylene oxide units, (poly ) Trimesic acid containing ethylene oxide units, trimesic acid containing (poly) trimethylene oxide units, trimesic acid containing (poly) propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide units Hemimellitic acid containing, Hemimellitic acid containing (poly) ethylene oxide units, Hemimellitic acid containing (poly) trimethylene oxide units, Hemimellitic acid containing (poly) propylene oxide units, (Poly) tetramethylene oxide units included Hemimellitic acid, pyromellitic acid containing (poly) methylene oxide units, pyromellitic acid containing (poly) ethylene oxide units, pyromellitic acid containing (poly) trimethylene oxide units, pyromellitic acid containing (poly) propylene oxide units acid, Pyromellitic acid containing poly) tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) methylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, Cyclohexane-1,3,5-tricarboxylic acid containing poly) trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units, cyclohexane-1 containing (poly) tetramethylene oxide units , 3,5-tricarboxylic acid and the like.

  Further, as a preferred example of the compound (B) having three or more functional groups containing at least one alkylene oxide unit, when the functional group is an amino group, 1,2,3-trimethyl containing a (poly) methylene oxide unit is preferred. Aminopropane, 1,2,3-triaminopropane containing (poly) ethylene oxide units, 1,2,3-triaminopropane containing (poly) trimethylene oxide units, 1,2 containing (poly) propylene oxide units , 3-triaminopropane, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) methylene oxide units, (poly) 1,2,3-triamino-2-methylpropane containing ethylene oxide units, 1,2, containing (poly) trimethylene oxide units -Triamino-2-methylpropane, 1,2,3-triamino-2-methylpropane containing (poly) propylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) tetramethylene oxide units 1,2,4-triaminobutane containing (poly) methylene oxide units, 1,2,4-triaminobutane containing (poly) ethylene oxide units, 1,2,4 containing (poly) trimethylene oxide units -Triaminobutane, 1,2,4-triaminobutane containing (poly) propylene oxide units, 1,2,4-triaminobutane containing (poly) tetramethylene oxide units, containing (poly) methylene oxide units 1,2,3,4-tetraminobutane, 1,2,3,4-tetraminobutane containing (poly) ethylene oxide units 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) propylene oxide units, 1,1,4 containing (poly) tetramethylene oxide units 2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane containing (poly) methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, (poly) trimethylene oxide 1,3,5-triaminocyclohexane containing units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) methylene oxide units, (poly ) 1,2,4-triaminocyclohexane containing ethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) trimethylene oxide units, 1,2,4-triamino containing (poly) propylene oxide units Cyclohexane, 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) methylene oxide units, 1,2 containing (poly) ethylene oxide units , 4,5-tetraminocyclohexane, 1,2,4,5-tetraminocyclohexane containing (poly) trimethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units, (poly) 1,2,4,5-Tetra containing tetramethylene oxide units Nocyclohexane, 1,3,5-triaminobenzene containing (poly) methylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, 1,3 containing (poly) trimethylene oxide units , 5-triaminobenzene, 1,3,5-triaminobenzene containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, (poly) methylene oxide units 1,2,4-triaminobenzene containing 1,2,4-triaminobenzene containing (poly) ethylene oxide units, 1,2,4-triaminobenzene containing (poly) trimethylene oxide units, (poly ) 1,2,4-triaminobenzene containing propylene oxide units, (poly) tetramethylene oxide units Including 1,2,4-aminobenzene, and the like.

  In addition, as a preferred example of the compound having three or more functional groups (B) containing one or more alkylene oxide units, when the functional group is an ester group, the compound having three or more hydroxyl groups containing the alkylene oxide units is used. Examples thereof include aliphatic acid esters or aromatic acid esters, and ester derivatives of compounds having three or more carboxylic acid groups containing the alkylene oxide unit.

  In addition, as a preferred example of a compound having three or more functional groups (B) containing one or more alkylene oxide units, when the functional group is an amide group, it has three or more carboxylic acid groups containing the alkylene oxide units. Examples include amide derivatives of compounds.

  As a particularly preferable example of the compound having three or more functional groups (B) containing one or more alkylene oxide units from the viewpoint of fluidity, when the functional group is a hydroxyl group, (poly) oxyethylene glycerin, (poly) oxy Propylene glycerin, (poly) oxyethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly) oxyethylene ditrimethylolpropane, (poly) oxy Propylene ditrimethylolpropane, (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol When the group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide units, (poly) ethylene oxide units Containing trimellitic acid, trimellitic acid containing (poly) propylene oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, cyclohexane-1 containing (poly) ethylene oxide units, Examples include 3,5-tricarboxylic acid and cyclohexane-1,3,5-tricarboxylic acid containing a (poly) propylene oxide unit. When the functional group is an amino group, 1,2,3-containing a (poly) ethylene oxide unit Triaminopropane, containing (poly) propylene oxide units , 2,3-triaminopropane, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, (poly) ethylene oxide units 1,3,5-triaminobenzene containing, 1,3,5-triaminobenzene containing (poly) propylene oxide units.

  (B) The compound having three or more functional groups used in the present invention may react with the thermoplastic resin (A) and be introduced into the main chain and side chain of the component (A). The structure at the time of mixing may be maintained without reacting with.

  The viscosity of the compound (B) having three or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and 5000 m · Pa or less from the viewpoint of fluidity and mechanical properties. More preferably, it is particularly preferably 2000 m · Pa or less. Although there is no particular lower limit, it is preferably 100 m · Pa or more from the viewpoint of bleeding property at the time of molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  The molecular weight or the weight average molecular weight (Mw) of the compound having (B) three or more functional groups used in the present invention is preferably in the range of 50 to 10,000, and in the range of 150 to 8,000 in terms of fluidity. It is more preferable that it is in the range of 200 to 3000. In the present invention, (B) Mw of the compound having three or more functional groups is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. .

  The water content of the compound (B) having three or more functional groups used in the present invention is preferably 1% or less. More preferably, the moisture content is 0.5% or less, and further preferably 0.1% or less. There is no particular lower limit on the moisture content of the component (B). A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

  In the present invention, the blending amount of the compound (B) having three or more functional groups is essential to be in the range of 0.1 to 4 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). In view of fluidity and mechanical properties, it is preferably blended in the range of 0.1 to 2 parts by weight, more preferably in the range of 0.1 to 1 part by weight, and 0.2 to 0. More preferably, it is blended in the range of 7 parts by weight.

  In the present invention, as a combination of (A) a thermoplastic resin and (B) a compound having three or more functional groups, when (A) component is a polyester resin, (B) component is at least one hydroxyl group, Or it is preferable from a fluid point that it has a carboxylic acid group, and it is more preferable that (B) component has 3 or more hydroxyl groups or a carboxylic acid group, and (B) component is 3 or more. It is more preferable to have a hydroxyl group, and it is particularly preferable that all functional groups of the component (B) are hydroxyl groups.

  In the present invention, it is preferable to blend (C) an end-capping agent having less than 3 functional groups in terms of improving fluidity and hydrolysis resistance, and (A) 100 parts by weight of the thermoplastic resin. On the other hand, it is preferable that (C) a terminal blocking agent having less than 3 functional groups is blended in the range of 0.01 to 50 parts by weight in terms of fluidity and hydrolysis resistance, and 0.01 to 30 parts by weight. It is more preferable to mix | blend in the range of 0.05-20 weight part, It is further more preferable to mix | blend in the range of 0.1-10 weight part, It is especially preferable to mix | blend in the range of 0.5-3 weight part It is most preferable to blend in the range of parts.

  In the present invention, (C) the functional group of the end-capping agent having less than three functional groups is at least one selected from a glycidyl group, an acid anhydride group, a carbodiimide group, and an oxazoline group. It is preferable that it is a reactive compound containing a glycidyl group in terms of fluidity and hydrolysis resistance. One kind of these reactive compounds may be used, but it is preferable to use two or more kinds in combination in view of hydrolysis resistance. As such a glycidyl compound, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, and an alicyclic epoxy compound can be preferably used. In terms of hydrolysis resistance, a glycidyl ether compound and a glycidyl compound can be used. An ester compound is more preferable.

  Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as sidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone; Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable. In the present invention, the addition amount of the glycidyl ether compound is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and more preferably 1 to 100 parts by weight of the (A) thermoplastic resin. 0.0 to 2.5 parts by weight is most preferred.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexane dicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable. In the present invention, the addition amount of the glycidyl ester compound is preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and more preferably 0 to 100 parts by weight of the (A) thermoplastic resin. Most preferred is 3 to 1.5 parts by weight.

  In the present invention, when (A) a polyester resin is used as the thermoplastic resin, it is preferable to further blend (D) a transesterification catalyst because the effect of improving fluidity is increased. (D) As a compounding quantity of a transesterification catalyst, it is preferable from a fluidity point to mix | blend in 0.0005-1 weight part with respect to 100 weight part of (A) thermoplastic resins, and 0.001-0. More preferably, it is blended in the range of 1 part by weight.

  In the present invention, the (D) transesterification catalyst includes lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, cerium, manganese, and the like. A metal compound such as a metal, an organic metal compound thereof, a metal alkoxide, a metal oxide, and a metal halide can be used, and there is no limitation as long as it is usually used as a catalyst for transesterification. Specific examples of particularly preferred (D) transesterification catalysts include dibutyltin oxide, antimony trioxide, antimony acetate, and tetra-n-butyl ester of titanic acid. Moreover, these transesterification catalysts may be used individually by 1 type, or may use 2 or more types together.

  In the present invention, when (A) a polyester resin is used as the thermoplastic resin, the fluidity is greatly improved by further blending (E) a polyester having a weight average molecular weight (Mw) of 100 to 8000 (hereinafter, low molecular weight polyester). Is done. (E) As a compounding quantity of low molecular weight polyester, it is preferable at the point of fluidity | liquidity to mix | blend in the range of 0.1-10 weight part with respect to 100 weight part of (A) thermoplastic resins, 0.2-5 It is more preferable to blend in the range of parts by weight.

  (E) In the low molecular weight polyester, Mw is more preferably in the range of 300 to 7000, and more preferably in the range of 500 to 5000 in terms of fluidity, mechanical properties, and bleed out. In the present invention, Mw of the low molecular weight polyester is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  In addition, (E) low molecular weight polyester used in the present invention includes (a) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, (b) hydroxycarboxylic acid or its ester-forming derivative, (c) ) A polymer or copolymer having at least one selected from lactone as a main structural unit, and (i) a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming property in terms of fluidity and mechanical properties. A derivative is preferred. The low molecular weight polyester may be any of aromatic polyester, aliphatic polyester, and alicyclic polyester.

  In the present invention, it is preferable to blend (F) an inorganic filler in order to impart mechanical strength and other characteristics of the resin composition. (F) The blending amount of the inorganic filler is preferably 0.1 to 120 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) in terms of fluidity and mechanical properties, and preferably 1 to 70 parts by weight. More preferably, it is mix | blended in the range of 1 part by weight, and it is still more preferable to mix | blend in the range of 1-50 weight part.

  In the present invention, as the type of (F) inorganic filler, any filler such as a fibrous shape, a plate shape, a powder shape, and a granular shape can be used. Specifically, glass fibers, PAN and pitch carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers , Alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc., whisker-like filler, mica, talc, Kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, barium sulfate, etc. Or include a plate-like filler, among others glass fibers are preferred. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said (F) inorganic filler can also be used in combination of 2 or more types. In addition, said (F) inorganic filler used for this invention treats the surface with a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent, etc.) and other surface treatment agents. It can also be used. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The inorganic filler (F) used in the present invention may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, such as aminosilane or epoxysilane. It may be treated with a coupling agent.

  In the present invention, it is preferable to blend (G) an impact resistance improver in order to impart mechanical strength and other characteristics of the resin composition. (G) The blending amount of the impact modifier is preferably from 0.1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) from the viewpoint of fluidity and mechanical properties. It is more preferable to mix in the range of 70 parts by weight, and further preferable to mix in the range of 1 to 50 parts by weight.

  In the present invention, as the (G) impact resistance improver, those known for thermoplastic resins can be used. Specifically, natural rubber, polyethylene such as low density polyethylene and high density polyethylene, Polypropylene, impact modified polystyrene, polybutadiene, styrene / butadiene copolymer, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / Polyester elastomers such as glycidyl methacrylate copolymer, polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, MB Include butadiene-based core shell elastomers or acrylic core shell elastomers such as these may be used alone or in combination. Examples of the butadiene-based or acrylic-based core-shell elastomer include “Metablene” manufactured by Mitsubishi Rayon, “Kaneace” manufactured by Kaneka, “Paralloid” manufactured by Rohm & Haas, and the like.

  In the present invention, a crystal nucleating agent, a plasticizer, an ultraviolet absorber, an antibacterial agent, a stabilizer, a mold release agent, a colorant including a pigment and a dye, a lubricant, an antistatic agent, and the like, as long as the effects of the present invention are not impaired. One or more additives selected from flame retardants can be added.

  In the present invention, the crystal nucleating agent may be either an inorganic crystal nucleating agent or an organic crystal nucleating agent. Examples of inorganic crystal nucleating agents include synthetic mica, clay, zeolite, magnesium oxide, calcium sulfide, boron nitride, neodymium oxide, etc., which are modified with organic matter to increase dispersibility in the composition. Preferably it is. As organic crystal nucleating agents, sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, sodium toluate, Organic carboxylic acid metal salts such as sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, sodium p-toluenesulfonate, sodium sulfoisophthalate, etc. Organic sulfonates, sorbitol compounds, phenylphosphonate metal salts, sodium-2,2′-methylenebis (4,6-di-t-butylphenol) , And the like phosphorus compound metal salts such as Le) phosphate. By blending these crystal nucleating agents, a thermoplastic resin composition and a molded product excellent in mechanical properties, moldability, heat resistance and durability can be obtained.

  In the present invention, any stabilizer that is used as a stabilizer for thermoplastic resins can be used. Specific examples include antioxidants and light stabilizers. By blending these stabilizers, a thermoplastic resin composition and a molded product excellent in mechanical properties, moldability, heat resistance and durability can be obtained.

  In the present invention, as the release agent, any of those used as a release agent for thermoplastic resins can be used. Specific examples include fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partially saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, and modified silicones. By blending these release agents, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  In the present invention, the flame retardant is at least one flame retardant selected from a brominated flame retardant, a chlorine flame retardant, a phosphorus flame retardant, a nitrogen compound flame retardant, a silicone flame retardant, and other inorganic flame retardants. It is preferable to use any two or more kinds of flame retardants selected from the above flame retardants in that a flame retardant can be used and excellent in flame retardancy and mechanical properties.

  In the present invention, specific examples of brominated flame retardants include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy). ) Ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisph Nord-A, tetrabromobisphenol-A derivatives, tetrabromobisphenol-A-epoxy oligomers or polymers, brominated epoxy resins such as brominated phenol novolac epoxy, tetrabromobisphenol-A-carbonate oligomers or polymers, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneopene Glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo terephthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  In the present invention, specific examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.

  In the present invention, as a specific example of the phosphorus-based flame retardant, a generally used phosphorus-based flame retardant can be used, and typically, an organic phosphorus compound such as a phosphate ester, a condensed phosphate ester, or a polyphosphate. In addition, at least one of condensed phosphate ester, polyphosphate, and red phosphorus is preferable, and condensed phosphate ester is more preferable in view of excellent fluidity, mechanical properties, and flame retardancy. An aromatic condensed phosphate ester is more preferable. Examples of the aromatic condensed phosphate ester include resorcinol polyphenyl phosphate and resorcinol poly (di-2,6-xylyl) phosphate.

  In the present invention, examples of the nitrogen compound flame retardant include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea, etc. In view of excellent flame retardancy and mechanical properties, nitrogen-containing heterocyclic compounds are preferable, triazine compounds are preferable, melamine cyanurate or melamine isocyanurate is more preferable, and addition of cyanuric acid or isocyanuric acid and triazine compound is particularly preferable. An adduct having a composition of usually 1 to 1 (molar ratio) and optionally 1 to 2 (molar ratio) can be mentioned. When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate, a known surface treatment agent, or the like may be used in combination.

  Examples of the silicone-based flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of RSiO3 / 2, R2SiO, and R3SiO1 / 2. Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group in the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

In the present invention, as other inorganic flame retardants, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, tin oxide Salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, metal salt of tungstic acid, tungsten and metalloid And complex oxide acids, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, swellable graphite, and the like. In the present invention, magnesium hydroxide, a fluorine-based compound, and swellable graphite are preferable, and a fluorine-based compound is more preferable in terms of excellent flame retardancy and mechanical properties. Fluorine compounds include polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoro Propylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer and the like are preferable, and polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is also preferable.
In the present invention, the flame retardant content is preferably 0.5 to 150 parts by weight, more preferably 1 to 150 parts by weight, and 1.2 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Is more preferable, 1.2 to 100 parts by weight is particularly preferable, and 2 to 80 parts by weight is most preferable. Although the manufacturing method of the resin composition of this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, For example, (A) thermoplastic resin, (B) The compound which has three or more functional groups In addition, a method of uniformly melting and kneading other components with a single-screw or twin-screw extruder at a melting point or higher, if necessary, or a method of removing the solvent after mixing in a solution is preferably used. In view of this, a method of uniformly melt-kneading with a single-screw or twin-screw extruder is preferable, and a method of uniformly melt-kneading with a twin-screw extruder is more preferable in that a resin composition excellent in fluidity and mechanical properties can be obtained. preferable. In particular, when the screw length is L and the screw diameter is D, a melt kneading method using a twin screw extruder with L / D> 30 is particularly preferable. The screw length here refers to the length from the position where the screw base material is supplied to the tip of the screw. The greater the L / D, the greater the fluidity improving effect of (B) the compound having three or more functional groups. The upper limit of the L / D of the twin screw extruder is 150, and preferably the L / D exceeds 30 and 100 or less.

  In the present invention, the screw structure used in the twin-screw extruder is a combination of full flight and kneading disk, but uniform kneading with a screw is required to obtain the composition of the present invention. is there. Therefore, the ratio of the total length of the kneading disk (kneading zone) to the total length of the screw is preferably in the range of 5 to 50%, and more preferably in the range of 10 to 40%.

  In the present invention, in the case of melt kneading, for example, a method of charging each component is performed by using an extruder having two charging ports and using (A) a thermoplastic resin from a main charging port installed on the screw base side, (B ) A method of supplying a compound having three or more functional groups and other components as required, or (A) a thermoplastic resin and other components are supplied from the main input port, and between the main input port and the tip of the extruder (B) A method in which a compound having three or more functional groups is supplied and melt-mixed from the installed sub-inlet, and the fluidity, mechanical properties, and production stability are excellent. A) A method in which a thermoplastic resin and other components are supplied, and (B) a compound having three or more functional groups is supplied and melt-kneaded from a sub-inlet installed between the main inlet and the front end of the extruder is preferable. (B) component continuously It is more preferable to feed.

  In the production of the resin composition of the present invention, the melt kneading temperature is preferably 110 to 360 ° C, more preferably 210 ° C to 320 ° C, and particularly preferably 240 to 280 ° C in terms of excellent fluidity and mechanical properties. preferable.

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

  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. It is suitable as a connector for electronic equipment.

  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. Automotive exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, and other automotive connectors, electrical connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop 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, housings and internal parts of recording media (CD, DVD, PD, FDD, etc.) drives, copiers And electrical / electronic components such as facsimile housings and internal components, 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 brushes Electric and electronic parts such as holders, 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 Thermal insulation 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, weed bags Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dewatering bag, concrete formwork and other civil engineering related parts, wash bowl (wash basin), hand wash bowl (hand wash basin) , Vanity counters, hand-washing counters, storage cases, storage shelves, mirror frames, faucet members, floor and wall toilet components, bathtubs, bath lids, bathroom washrooms, bathroom walls, bathroom counters, bathroom floors, waterproof pans, Bathroom storage shelves, bathroom ceilings, washbasins, shower faucets, bathroom components such as washing chairs and handrails, toilet bowls, toilet lids, toilet seats, toilet counters, washing nozzles, toilets Toilet and other toilet components, kitchen counter, kitchen sink, kitchen back, kitchen top plate, storage shelf and storage shelf door and other kitchen components, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers , Water supply parts, Toy parts, Fans, Tegs, Pipes, Cleaning jigs, Motor parts, Microscopes, Binoculars, Cameras, Watches and other mechanical parts, Multi films, Tunnel films, Bird-proof sheets, Non-vegetation protection nonwovens Pots, vegetation piles, seed tape, germination sheets, house lining sheets, farm-bi fasteners, slow-release fertilizers, root-proof sheets, garden nets, insect nets, young tree nets, printed laminates, fertilizer bags, Sanitary items such as sample bags, sandbags, beast damage prevention nets, incentive straps, windproof nets, agricultural materials such as paper diapers, sanitary wrapping materials, cotton swabs, towels, and toilet seat wipes Medical supplies such as medical supplies, non-woven fabric for medical use (stitching reinforcing material, anti-adhesion film, prosthetic repair material), wound dressing material, wound tape bandage, sticking material base fabric, surgical suture, fracture reinforcing material, medical film, etc. , Calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets, etc., hot-fill containers, microwave ovens Cooking containers Cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lid materials, window envelopes, fruit baskets, hand-cut tape, easy peel packaging, eggs Packing films for packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical and electronic parts, etc. Various containers and 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, sulfide Zinc, electrode material powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, drainer net, body towel, hand towel, tea pack, drainage Groove filter, clear file, coating agent, contact Useful as agent, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc., wire harness connector, SMJ connector It is useful as a connector for various automobiles such as a PCB connector and a door grommet connector or a connector for electric / electronic parts. Among them, it is particularly useful to use as a connector whose thinnest part is 1 mm or less.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention.

Production Example 1
754 g of terephthalic acid and 491 g of 1,4-butanediol were charged into a reaction vessel equipped with a stirring blade, a distillation tube and a cooling tube, and a transesterification reaction was performed under the following reaction conditions.

  After removing water at 120 ° C. for 0.5 hours in a nitrogen gas atmosphere, 0.45 ml of tetrabutoxytitanium was added as a catalyst to start the esterification reaction. The temperature was gradually raised from 135 ° C. to 240 ° C., and the pressure reduction condition was 650 mmHg. After 230 minutes from the start of the reaction, it was confirmed that the temperature at the upper part of the rectifying column had decreased, and when the reaction was stopped, a theoretical amount of water was distilled off to obtain a low molecular weight polyester (E-1).

  The obtained low molecular weight polyester (E-1) had a melting point of 222 ° C. and a weight average molecular weight of 880.

  Abbreviations and main contents of main raw materials used in Examples and the like are summarized below.

(A) Thermoplastic polyester A-1: Polybutylene terephthalate (melting point: 223 ° C., “Toraycon” 1100S manufactured by Toray)
A-2: Polypropylene terephthalate (melting point: 228 ° C., “Corterra” CP509211, manufactured by Shell Chemicals)
A-3: Polyethylene terephthalate (melting point 260 ° C., Mitsui Chemicals J155)
A-4: Polycarbonate (“Taflon” A1900 manufactured by Idemitsu Kosan)

(B) Compound B-1 having three or more functional groups: Glycerin (molecular weight 92, alkylene oxide units 0 per functional group, Tokyo Kasei)
B-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, ARDRICH)
B-3: Pentaerythritol (molecular weight 136, number of alkylene oxide units 0 per functional group, Tokyo Kasei)
B-4: Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, SC-E450 manufactured by Sakamoto Yakuhin)
B-5: Oxyethylenetrimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, manufactured by Nippon Emulsifier TMP-30U)
B-6: Polyoxyethylene pentaerythritol (molecular weight 400, number of alkylene oxide (ethylene oxide) units 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-7: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750)
B-8: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, Nippon Emulsifier TMP-F32)
B-9: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)

(B ′) Compound B′-1: 1,6-hexanediol (ARDRICH) having less than three functional groups
B'-2: 4,4'-dihydroxybiphenyl (Honshu Chemical)

(C) End-capping agent C-1 having less than 3 functional groups C-1: Versatic acid glycidyl ester (epoxy content 4.06 mol / kg, “Curjur” E10P manufactured by Japan Epoxy Resin)

(D) Transesterification catalyst D-1: Dibutyltin oxide (Tokyo Kasei)

  (E) Low molecular weight polyester

(F) Inorganic filler F-1: Chopped strand type glass fiber (fiber diameter 10 μm, cut length 3 mm, Nittobo CS3J948) F-2: Talc (Nihon Talc P-6)

(G) Impact resistance improver G-1: Ethylene / ethyl acrylate copolymer (“EVAFLEX” EEA A-709 manufactured by Mitsui DuPont Polychemical)
G-2: Ethylene / glycidyl methacrylate copolymer (“BONDAST” 2C manufactured by Sumitomo Chemical)
G-3: Acrylic core-shell elastomer (Rohm & Haas “PARALOID” EXL2314)
G-4: Butadiene-based core-shell elastomer ("PARALOID" EXL2603 manufactured by Rohm & Haas)

(H) Stabilizer H-1: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (“IRGANOX” 1010 manufactured by Ciba Geigy)

(I) Release agent I-1: Partially saponified ester of montanic acid ("Licowax" OP manufactured by Clariant)
I-2: Ethylene bis-stearic acid amide (“SLIPAX” E manufactured by Nippon Kasei)
Moreover, the evaluation methods used in Examples and the like are summarized below.

(1) Fluidity Using a strip-shaped molded product having a thickness of 1 mm and a width of 10 mm, the fluidity was judged. The injection conditions are (A) when the thermoplastic resin is polybutylene terephthalate, and (F) when no inorganic filler is included, the cylinder temperature is 250 ° C., the mold temperature is 80 ° C., and the injection pressure is 30 MPa. (A) When the thermoplastic resin is polybutylene terephthalate and (F) contains an inorganic filler, the cylinder temperature is 250 ° C., the mold temperature is 80 ° C., and the injection pressure is 70 MPa. (A) When the thermoplastic resin is polypropylene terephthalate, the cylinder temperature is 265 ° C., the mold temperature is 40 ° C., and the injection pressure is 30 MPa. (A) When the thermoplastic resin is polyethylene terephthalate, the cylinder temperature is 280 ° C., the mold temperature is 40 ° C., and the injection pressure is 30 MPa. (A) When the thermoplastic resin is polycarbonate, the cylinder temperature is 260 ° C., the mold temperature is 40 ° C., and the injection pressure is 80 MPa.

(2) Heat resistance (DTUL)
According to ASTM D648, the deflection temperature under load (load 1.82 MPa) of a 12.7 mm × 127 mm × 3 mm strip-shaped product was measured.

(3) Impact resistance According to ASTM D256, the Izod impact strength of a molded product having a 3 mm thickness notch was measured.

(4) Flexural Modulus According to ASTM D790, the flexural modulus of the 12.7 mm × 127 mm × 3 mm strip-shaped product was measured.

(5) Tensile Strength and Tensile Breaking Elongation According to ASTM D-638, tensile yield strength and tensile breaking elongation were measured for ASTM No. 1 dumbbell test pieces.

(6) Hydrolysis resistance The ASTM No. 1 dumbbell specimen was left in a pressure cooker test apparatus at a temperature of 121 ° C. and a relative humidity of 100% for 50 hours. Then, it took out from the apparatus and measured the tensile yield strength by said method (5), and calculated | required tensile strength retention = (strength after a hydrolysis process / strength before a hydrolysis process) x100 (%).

[Examples 1-20, Comparative Examples 1-10]
(A) A thermoplastic resin and (B) a compound having three or more functional groups, etc., are batch-blended at the blending ratios shown in Tables 1 and 2, and using a twin screw extruder with L / D = 45 (A) When the thermoplastic resin is polybutylene terephthalate, the cylinder temperature is 250 ° C. and the rotation speed is 200 rpm. When the thermoplastic resin is polypropylene terephthalate, the cylinder temperature is 265 ° C. Melt-kneading was performed under the condition of a rotational speed of 200 rpm to obtain a pellet-shaped resin composition.
The mixture was melt-kneaded under the above conditions to obtain a pellet-shaped resin composition.

  Using the obtained resin composition, an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. (A) When the thermoplastic resin is polybutylene terephthalate, the cylinder temperature is 250 ° C., the mold temperature is 80 ° C., and (A) the thermoplastic resin. When polypropylene terephthalate was used, various evaluation molded articles were injection molded at a cylinder temperature of 265 ° C. and a mold temperature of 40 ° C., and when polypropylene terephthalate was used, the cylinder temperature was 280 ° C. and the mold temperature was 40 ° C.

  The evaluation results are shown in Tables 1 and 2.

  From the results of Tables 1 and 2, the following is clear.

From comparison between Examples 1 to 5, 11 to 20, and Comparative Examples 1 to 10, (A) 100 parts by weight of the thermoplastic resin (B) 0.1 to 4 compounds having three or more functional groups It can be seen that the thermoplastic resin composition blended in parts by weight is excellent in fluidity, mechanical properties, and heat resistance. In particular, it can be seen that (B) when the compound having three or more functional groups contains an alkylene oxide unit, the effect of improving fluidity is great. Further, from comparison between Examples 5 to 10 and Comparative Example 1, (C) an end-capping agent having less than 3 functional groups, (D) a transesterification catalyst, and (E) a low molecular weight polyester are further blended. It can be seen that the fluidity is improved.
[Examples 21-30, Comparative Examples 11-13]
(A) a thermoplastic resin and (B) a compound having three or more functional groups and the like are collectively blended at a blending ratio shown in Table 3, using a twin screw extruder with L / D = 45, a cylinder temperature of 250 ° C., Melt kneading was performed at a rotational speed of 200 rpm to obtain a pellet-shaped resin composition.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries, Ltd. injection molding machine SG75H-MIV at a cylinder temperature of 250 ° C and a mold temperature of 80 ° C.

  The evaluation results are shown in Table 3.

  From the results in Table 3, the following is clear.

  From a comparison between Examples 21-30 and Comparative Examples 11-13, (A) 0.1-4 parts by weight of a compound having three or more functional groups is blended with respect to 100 parts by weight of the thermoplastic resin. It can be seen that the thermoplastic resin composition is excellent in fluidity, mechanical properties, and heat resistance. In particular, it can be seen that (B) when the compound having three or more functional groups contains a propylene oxide unit, it is excellent in toughness and hydrolysis resistance.

[Examples 31 to 35, Comparative Examples 14 to 16]
(A) a thermoplastic resin and (B) a compound having three or more functional groups and the like are collectively blended at a blending ratio shown in Table 4, using a twin screw extruder of L / D = 45, a cylinder temperature of 260 ° C., Melt-kneading was performed under the condition of a rotational speed of 200 rpm to obtain a pellet-shaped resin composition.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries, Ltd. injection molding machine SG75H-MIV at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C.

  The evaluation results are shown in Table 4.

  From the results in Table 4, the following is clear.

  From a comparison between Examples 31 to 35 and Comparative Examples 14 to 16, (A) 0.1 to 4 parts by weight of a compound having three or more functional groups is blended with respect to 100 parts by weight of the thermoplastic resin. It can be seen that the thermoplastic resin composition obtained is excellent in fluidity and mechanical properties.

[Examples 36 to 48, Comparative Examples 17 to 19]
(A) a thermoplastic resin and (B) a compound having three or more functional groups are batch-blended at the blending ratio shown in Table 5 and supplied to the root of a twin screw extruder with L / D = 45. ) The inorganic filler was fed into the extruder from the side feeder. Melt kneading was performed under the conditions of a cylinder temperature of 250 ° C. and a rotation speed of 200 rpm to obtain a pellet-shaped resin composition.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries, Ltd. injection molding machine SG75H-MIV at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C.

  The evaluation results are shown in Table 5.

  From the results of Table 5, the following is clear.

From a comparison between Examples 36 to 48 and Comparative Examples 17 to 19, a resin composition comprising (A) a thermoplastic resin, (B) a compound having three or more functional groups, and (F) an inorganic filler. Is excellent in fluidity, mechanical properties, and heat resistance. In particular, it can be seen that (B) when the compound having three or more functional groups contains an alkylene oxide unit, the effect of improving fluidity is great. Further, from comparison between Examples 40 to 43 and Comparative Example 17, (C) an end-capping agent having less than 3 functional groups, (D) a transesterification catalyst, and (E) a low molecular weight polyester are further blended. It can be seen that the fluidity is improved.
[Examples 49 to 63, Comparative Examples 20 to 21]
In the blending ratio shown in Table 6, (A) thermoplastic resin and other components other than (B) component and (F) component are batch-blended, and used as the main input port of the screw of the twin screw extruder with L / D = 45. (B) A compound having three or more functional groups is continuously supplied from a sub-inlet installed between the main input and the extruder tip, and (F) an inorganic filler is fed into the extruder from the side feeder. And melt-kneaded under the conditions of a cylinder temperature of 250 ° C. and a rotation speed of 200 rpm to obtain a pellet-shaped resin composition.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries, Ltd. injection molding machine SG75H-MIV at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C.

  The evaluation results are shown in Table 6.

  From the results of Table 6, the following is clear.

  From a comparison between Examples 49 to 63 and Comparative Examples 20 to 21, 0.1 to 4 parts by weight of (B) a compound having three or more functional groups is blended with 100 parts by weight of the thermoplastic resin. It can be seen that the thermoplastic resin composition is excellent in fluidity, mechanical properties and heat resistance. Further, from Examples 50 and 53, when (C) a terminal blocking agent having less than 3 functional groups is blended, or from Examples 54 to 61, (B) a compound having 3 or more functional groups is obtained. When the propylene oxide unit is contained, it can be seen that the hydrolysis resistance is further excellent.

Claims (12)

(A) A thermoplastic resin composition obtained by blending 0.1 to 4 parts by weight of a compound having three or more functional groups with respect to 100 parts by weight of a thermoplastic resin. (B) The compound having three or more functional groups is a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having a functional group is a structure represented by the formula (1) The thermoplastic resin composition according to claim 1, which is a certain compound.

(R represents a hydrocarbon group having 1 to 15 carbon atoms, n represents an integer of 1 to 10, and X represents a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, or an isocyanate group. And represents at least one functional group selected from a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group.) (B) The thermoplastic resin composition according to claim 1, wherein the compound having three or more functional groups contains one or more alkylene oxide units. (A) The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition is at least one selected from a polyester resin, a polycarbonate resin, and a polyamide resin. (B) The functional group of the compound having three or more functional groups is at least one group selected from a hydroxyl group, a carboxylic acid group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. The thermoplastic resin composition in any one of -4. Furthermore, (C) The thermoplastic resin composition in any one of Claims 1-5 formed by mix | blending the terminal blocker which has a functional group less than three. The thermoplastic resin composition according to any one of claims 1 to 6, wherein (A) at least one kind of thermoplastic resin is polyester, and (D) a transesterification catalyst is further blended. The thermoplastic resin composition according to any one of claims 1 to 7, wherein (A) at least one of the thermoplastic resins is polyester, and (E) a polyester having a weight average molecular weight of 100 to 8000 is blended. Furthermore, the thermoplastic resin composition in any one of Claims 1-8 formed by mix | blending (F) inorganic filler. Furthermore, the thermoplastic resin composition in any one of Claims 1-9 formed by mix | blending (G) impact resistance improving agent. 11. When producing the thermoplastic resin composition according to claim 1, assuming that the screw length of the twin screw extruder is L and the screw diameter is D, a twin screw extruder of L / D> 30. A method for producing a thermoplastic resin composition that is melt-kneaded using a resin. The molded article formed by shape | molding the thermoplastic resin composition in any one of Claims 1-10.