JP5217425B2 - Thermoplastic resin composition, method for producing the same, and molded article comprising the same - Google Patents

Description

  The present invention is excellent in fluidity and hydrolysis resistance useful as electrical / electronic equipment parts, automobile parts, machine parts, etc., and in a preferred embodiment, it is excellent in mechanical properties or impact resistance, thermoplastic resin, 3 or more The present invention relates to a thermoplastic resin composition comprising a compound having a functional group and a terminal blocking agent having three or more reactive groups, a method for producing the same, and a molded article comprising the same.

  Polyester resins, polyamide resins, polycarbonate resins, and the like, 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 molded products.

  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 degrading mechanical properties. It is desired to improve the fluidity at the time of melting and to have hydrolysis resistance.

  Patent Document 1 describes a polyester resin having a melt tension of 0.8 to 5.0 g having a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol, but the resulting polyester resin is thickened. However, there is a problem that the fluidity is lowered, and no mention is made of hydrolysis resistance.

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, there is a tendency that mechanical properties are also lowered, and no mention is made of hydrolysis resistance.
JP 2001-200038 A (Claims) JP-A-7-304970 (Claims)

  The present invention is excellent in fluidity and hydrolysis resistance, and in a preferred embodiment, a thermoplastic resin, a compound having three or more functional groups, and three or more reactive groups having excellent mechanical properties or impact resistance. It is an object of the present invention to provide a thermoplastic resin composition formed by blending a terminal blocker having the same, a method for producing the same, and a molded product comprising the same.

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

That is, the present invention
(1) (A) 0.1 to 10 parts by weight of a compound having 3 or more functional groups and 2 or more types of compounds (C) other than the above (B) with respect to 100 parts by weight of the thermoplastic resin Is a thermoplastic resin composition comprising 0.01 to 10 parts by weight of a reactive endblocker , wherein (A) the thermoplastic resin is at least one selected from polyester resins and polycarbonate resins. (B) the compound having three or more functional groups is a polyfunctional compound having three or more hydroxyl groups and one or more propylene oxide units, wherein at least one of the terminal structures having the functional group is represented by the formula (C) is a compound having a structure represented by (1), and (C) a terminal blocking agent having three or more reactive groups is selected from carbodiimide compounds, epoxy compounds, oxazine compounds and compounds containing acid anhydride groups. The The thermoplastic resin composition is at least one that,
-(O-R) n-X (1)
(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.)
(2) terminus sequestrant has three or more reactive groups, the thermoplastic resin composition according to a compound having no structure represented by the above formula (1) (1),
(3) The thermoplastic resin composition according to (1) or (2), wherein (A) the thermoplastic resin is a polyester resin having a carboxyl end group amount of 30 eq / t or less,
( 4 ) The thermoplastic resin composition according to any one of (1) to ( 3 ), further comprising (D) a reaction catalyst,
( 5 ) The thermoplastic resin composition according to any one of (1) to ( 4 ), further comprising (E) an inorganic filler.
( 6 ) The thermoplastic resin composition according to any one of (1) to ( 5 ), further comprising (F) an impact resistance improver,
( 7 ) When producing the thermoplastic resin composition according to any one of (1) to ( 6 ), 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
( 8 ) A molded product formed by molding the thermoplastic resin composition according to any one of (1) to ( 6 ),
Is to provide.

  According to the present invention, it is excellent in fluidity and hydrolysis resistance, and in a preferred embodiment, it is excellent in mechanical properties or impact resistance, a thermoplastic resin, a compound having three or more functional groups, and three or more reactivity. It is possible to provide a thermoplastic resin composition comprising a terminal blocking agent having a group, a production method thereof, and a molded product comprising the same.

  The thermoplastic resin (A) used in the present invention may be any resin that can be melt-molded. For example, polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic olefin resin, acrylonitrile / butanediene / styrene (ABS) Resin, acrylonitrile / styrene (AS) resin, cellulose resin such as cellulose acetate, 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 (a) a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative, (b) a hydroxycarboxylic acid or its It is a polymer or copolymer having one or more selected from ester-forming derivatives and (c) lactone as the main structural unit.

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

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

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

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

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

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

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

  In the present invention, a liquid crystalline polyester capable of forming anisotropy at the time of melting 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. However, in the present invention, it is not preferable to use a non-liquid crystalline polyester and a liquid crystalline polyester resin in combination as the polyester resin because the fluidity may be lowered.

  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 more preferably 20 eq / t or less, particularly preferably 15 eq / t or less, and most 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, in terms 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 end group amount of (A) the thermoplastic resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The amount of hydroxyl terminal groups of the polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or more, more preferably 80 eq / t or more, 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. 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 in the range of 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 method for producing 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 preferred 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 the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, Dibutyltin oxide, Methylphenyltin oxide, Tetraethyltin, Hexaethylditin oxide, Cyclohexahexylditin oxide, Didodecyltin oxide, Triethyltin hydroxide, 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.

In the present invention, when (A) polycarbonate is used as the thermoplastic resin, the polycarbonate resin is bisphenol A, that is, 2,2′-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylalkane, It is a polycarbonate mainly composed of one or more dihydroxy compounds selected from 4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxydiphenyl ether.
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. Furthermore, 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.

  In the present invention, when a polyamide is used as the thermoplastic resin (A), the polyamide resin is a polyamide mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, pentamethylenediamine , Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosi Chlohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as 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 suitable to use these polyamide resins as a mixture depending on required 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 almost the temperature range in which the glass transition detected when measured with a differential scanning calorimeter (DSC) at a rate of temperature increase of 20 ° C./min. The midpoint value.

  In the present invention, (B) a compound having three or more functional groups is blended. 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 composition of the present invention. The component (B) is not particularly limited as long as it has three or more functional groups in the molecule, and may be a low molecular compound or a polymer. In addition, 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 is excellent in 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) is (B) a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having functional groups. Preferably, the compound is a compound having a structure represented by the formula (1), and the component (B) is a compound having (B) three or more functional groups, particularly in terms of excellent fluidity and mechanical properties. More preferably, the compound is a compound having two or more of the terminal structures having a functional group and having a structure represented by the formula (1), and the terminal structure having a functional group in the component (B). More preferably, three or more compounds are compounds having a structure represented by the formula (1), and all of the terminal structures having a functional group in the component (B) are structures represented by the formula (1). Most preferably.
-(O-R) n-X (1)

Here, 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 carboxyl group, a sulfo group, an amino group, a glycidyl group, an isocyanate. represents groups, OH Kisazorin group, oxazine group, at least one functional group selected or shea silanol group et al.
In the present invention, R represents an alkylene group, n represents an integer of 1 to 7, and X represents a hydroxyl group, a carboxyl group, in terms of excellent fluidity, recyclability, durability and mechanical properties. amino group, a glycidyl group, may represent at least one functional group selected or isocyanate groups, et al preferably, R represents an alkylene radical, n represents an integer of 1 to 5, X is a hydroxyl group, a carboxyl group, an amino group, is more preferably represents at least one functional group selected or glycidyl group et al, R represents an alkylene group, n represents an integer of 1 to 4, X represents a hydroxyl group, an amino group, more preferably representing at least one functional group selected or glycidyl group et al, R represents an alkylene radical, n represents an integer of 1 to 3, X is particularly be a hydroxyl group Like There. 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 component (B) is a hydroxyl group, aldehyde group, carboxyl group, sulfo group, amino group, glycidyl group, isocyanate group, carbodiimide group, oxazoline group, oxazine group, ester group, amide group, silanol. And at least one selected from a silyl ether group, and the functional group in component (B) preferably has three or more functional groups that are the same or different. . Moreover, in this invention, (B) component is a polyfunctional compound which has (B) 3 or more functional groups, Comprising: Two or more of the terminal structures which have a functional group are represented by 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, methyl glucoside, 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 preferable example of a compound having three or more functional groups, when the functional group is a carboxyl group, propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid 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 8-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 preferred 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, monomers such as triglycidyl triazolidine-3,5-dione, triglycidyl isocyanurate, poly ( And polymers such as ethylene / glycidyl methacrylate) -g-polymethyl methacrylate.

  (B) As a preferable example of the 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 carboxyl groups And ester derivatives of compounds having a group.

(B) As a preferable example of the compound having 3 or more functional groups, when the functional group is an amide group, an amide derivative of the compound having 3 or more carboxyl groups may be mentioned.
From the viewpoint of fluidity and mechanical properties, it is preferable that (B) the compound having 3 or more functional groups contains one or more alkylene oxide units. In the present invention, the component (B) is (B) a polyfunctional compound having 3 or more functional groups, and at least one terminal structure having a functional group is represented by the formula (1). When R in formula (1) is an alkylene group, the structure represented by formula (1) represents 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 3 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 the 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 from the viewpoint 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 3 or more functional groups is an alkylene oxide per functional group in terms of excellent fluidity and mechanical properties. The unit is preferably from 0.1 to 20, more preferably from 0.5 to 10, and even more preferably from 1 to 5.

  As a preferred example of the compound having three or more functional groups (B) containing at least one alkylene oxide unit, 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) oxymethylenetrimethylolpropane, (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) io 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 the 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 Hemellitic 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.

  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 amino group, 1,2,3-trimethyl containing (poly) methylene oxide units is used. 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 or the like can be cited, and trimethylolpropane tris [poly (propylene glycol) amine] ether is also suitable, such as.

  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 carboxyl groups containing the above alkylene oxide units.

In addition, as a preferred example of a compound having three or more functional groups (B) containing at least one alkylene oxide unit, when the functional group is an amide group, a compound having three or more carboxyl groups containing the alkylene oxide unit And amide derivatives thereof.
As a particularly preferred example of the compound having three or more functional groups (B) containing at least one alkylene oxide unit 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 a (poly) propylene oxide unit, trimethylolpropane tris [poly (propylene glycol) amine] ether.

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

  The viscosity of the compound (B) having 3 or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and more preferably 5000 m · Pa or less in terms of fluidity and mechanical properties. It is 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 during 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 weight average molecular weight (Mw) of the compound (B) having 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. More preferably, it is more preferably in the range of 200 to 3000. In the present invention, (B) Mw of the compound having 3 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 moisture content of the compound (B) having 3 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.

  (B) The compound having three or more functional groups used in the present invention may contain a metal component, and includes, for example, an alkali metal or an alkaline earth metal used for introducing an alkylene oxide unit. It may contain a catalyst or the like.

  In the present invention, the blending amount of the compound (B) having 3 or more functional groups is essential to be in the range of 0.1 to 10 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 5 parts by weight, more preferably in the range of 0.1 to 4 parts by weight, and 0.1 to 2 parts by weight. More preferably, it is blended in the range of 0.1 to 1 part by weight, and most preferably in the range of 0.2 to 0.7 part by weight.

  In the present invention, as a combination of (A) a thermoplastic resin and (B) a compound having 3 or more functional groups, when (A) component is a polyester resin, (B) component is at least one hydroxyl group, It preferably has a carboxyl group or an amino group from the viewpoint of fluidity, more preferably (B) component has 3 or more hydroxyl groups or amino groups, and (B) component has 3 or more. It is more preferable that all the functional groups of the component (B) are hydroxyl groups.

  The present invention is characterized in that (C) a compound other than the above (B) is blended with a terminal blocking agent having three or more reactive groups. The end-capping agent having 3 or more reactive groups is a necessary component for improving the hydrolysis resistance. The terminal blocking agent used in the present invention is (B) a compound other than a compound having three or more functional groups, and can block a terminal group of a polymer such as a carboxyl group, a hydroxyl group or an amino group by reaction. If it is a compound, there will be no restriction | limiting in particular, A well-known thing can be used as a terminal blocker of a polymer. In the present invention, the end-capping agent not only blocks the end of the thermoplastic resin but also a carboxyl group, a hydroxyl group or an amino group of a low molecular compound such as a decomposition product generated by thermal decomposition or hydrolysis of the thermoplastic resin. Reactive functional groups such as can also be blocked.

  The terminal blocking agent used here is preferably a compound having three or more reactive groups and not having the structure represented by the above formula (1). Moreover, the compounding quantity of terminal blocker is 0.1-10 weight part of (B) polyfunctional compound which has a 3 or more functional group with respect to 100 weight part of (A) thermoplastic resins, and (C) 3. It is preferable that it is 0.01-10 weight part of terminal blockers which have a 1 or more reactive group and do not have the structure represented by the said Formula (1).

  The end-capping agent having three or more reactive groups is at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, a carbodiimide compound, and a compound containing an acid anhydride group, Epoxy compounds and / or carbodiimide compounds are preferable, and carbodiimide compounds are more preferable in terms of excellent long-term durability such as mechanical properties, moldability, heat resistance, hydrolysis resistance, and dry heat resistance.

  In the present invention, examples of the epoxy compound that can be used as a terminal blocking agent include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, and alicyclic epoxy compounds. Mechanical properties, moldability, In view of excellent long-term durability such as heat resistance, hydrolysis resistance or dry heat resistance, it is preferably at least two selected from glycidyl ether compounds and glycidyl ester compounds, and at least one selected from glycidyl ether compounds. More preferably, it is at least one compound selected from one or more compounds and a glycidyl ester compound.

  In the present invention, the glycidyl ether compound is a compound having an etherified glycidyl group, and specifically includes glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, and the like. Can do. In the present invention, the blending amount of the glycidyl ether compound is 100 parts by weight of a thermoplastic resin in terms of excellent long-term durability such as mechanical properties, moldability, heat resistance, hydrolysis resistance, dry heat resistance, and melt viscosity stability. On the other hand, 0.1-5 weight part is preferable, 0.5-3 weight part is more preferable, 0.7-2.5 weight part is further more preferable. 1.0 to 2.0 parts by weight are particularly preferred.

  In the present invention, the glycidyl ester compound is a compound having an esterified glycidyl group, specifically, trimesic acid triglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, etc. Can be mentioned. In the present invention, the blending amount of the glycidyl ester compound is 100 parts by weight of a thermoplastic resin in terms of excellent long-term durability such as mechanical properties, moldability, heat resistance, hydrolysis resistance, and dry heat resistance, or melt viscosity stability. Is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2.5 parts by weight, still more preferably 0.15 to 2.0 parts by weight, and particularly preferably 0.3 to 1.5 parts by weight. preferable.

  In the present invention, specific examples of the glycidylamine compound include tetraglycidylaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, tetraglycidylmetaxylenediamine, tetraglycidylbisaminomethylcyclohexane, triglycidyl cyanurate or triglycidyl Examples thereof include glycidyl isocyanurate.

  As other epoxy compounds, polymers containing epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol novolac type epoxy resins, or glycidyl group-containing vinyl-based units A polymer containing a glycidyl group-containing vinyl-based unit is preferred from the viewpoint of excellent molding processability, melt viscosity stability, impact resistance or surface hardness.

  In the present invention, specific examples of the raw material monomer for forming the glycidyl group-containing vinyl unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate, maleic acid, itaconic acid Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acid such as, unsaturated glycidyl ether such as allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-4-glycidyl ether, and the like. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit preferably contains a vinyl-based unit other than the glycidyl group-containing vinyl-based unit as a copolymerization component. Depending on the selection, the melting point of the polymer, the glass transition temperature, etc. Can be adjusted. As vinyl units other than glycidyl group-containing vinyl units, acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic anhydride units, unsaturated dicarboxylic acid units, aliphatic types Examples thereof include vinyl units, maleimide units, and other vinyl units.

  Specific examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , Isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Roxypropyl, hydroxypropyl methacrylate, acrylic acid ester or methacrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, Acrylic vinyl units having an amino group such as acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. The raw material monomer etc. which form are mentioned, Especially, acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid Methyl, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Preferred are 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile, and acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylo Tolyl, methacrylonitrile is used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer that forms the vinyl carboxylate unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Monofunctional aliphatic vinyl carboxylates such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate and vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl cinnamate, etc. And polyfunctional vinyl carboxylates such as vinyl aromatic carboxylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonic acid and vinyl sorbate. Among them, vinyl acetate is preferably used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer for forming the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, 4 -Dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned, among which styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  Examples of the raw material monomer that forms the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, among which maleic anhydride is preferably used. . These may be used alone or in combination of two or more.

Examples of the raw material monomer for forming the unsaturated dicarboxylic acid-based unit include maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid and the like. Among these, maleic acid and itaconic acid are preferably used. These may be used alone or in combination of two or more.
Examples of raw material monomers for forming aliphatic vinyl units include ethylene, propylene, and butadiene. Examples of raw material monomers for forming maleimide units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- As other raw material monomers for forming vinyl units such as isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide, N-vinyldiethylamine, N- Acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene and the like can be mentioned, and these can be used alone or in combination of two or more.

  In the present invention, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited, but is in the range of 30 to 100 ° C. in that it is excellent in workability and molding processability during blending. It is preferable that it is, It is more preferable that it is the range of 40-70 degreeC, It is most preferable that it is the range of 50-65 degreeC. The glass transition temperature here is an intermediate point glass transition temperature measured by DSC at a temperature increase temperature of 20 ° C./min by the method of JIS K7121. In addition, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit can be controlled by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit usually contains a volatile component because unreacted raw material monomers and solvents remain. The amount of the non-volatile component that is the balance is not particularly limited, but it is preferable that the non-volatile component amount is large from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by weight or more, more preferably 97% by weight or more, further preferably 98% by weight or more, and most preferably 98.5% by weight or more. preferable. In addition, the non-volatile component here represents the remaining amount ratio when the sample 10g is heated at 110 degreeC for 1 hour in nitrogen atmosphere.

  In the present invention, a polymer containing a glycidyl group-containing vinyl-based unit may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. Contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, the method for producing a polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. When these methods are used, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used, but these remain as impurities in a polymer containing a vinyl unit containing a glycidyl group finally obtained. There are things to do. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, particularly 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  As a method for producing a polymer containing a glycidyl group-containing vinyl-based unit that satisfies the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, and the like as described above, a high temperature of 150 ° C. or higher is applied. A method of continuous bulk polymerization under a pressure condition (preferably 1 MPa or more) in a short time (preferably 5 to 30 minutes) is a high polymerization rate, a polymerization initiator or a chain transfer agent that causes impurities and sulfur content And more preferable in that no solvent is used. In the present invention, the amount of the polymer containing a glycidyl group-containing vinyl-based unit depends on mechanical properties, molding processability, heat resistance, hydrolysis resistance, dry heat resistance, long-term durability, melt viscosity stability, or surface hardness. In terms of superiority, it is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.2 to 3 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 2 parts by weight are particularly preferred.

  In the present invention, examples of commercially available polymers containing a glycidyl group-containing vinyl-based unit include “Marproof” manufactured by NOF Corporation, “Joncry” manufactured by BASF, and “ARUFON” manufactured by Toagosei Co., Ltd.

  In the present invention, specific examples of the oxazoline compound that can be used as a terminal blocking agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2- Poly having a monomer unit containing a compound containing an oxazoline group such as oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline An oxazoline can be mentioned, and among them, a polyoxazoline containing 2-isopropenyl-2-oxazoline as a monomer unit, which can impart hydrolysis resistance and is easily available industrially, is preferable.

  In the present invention, “Epocross” manufactured by Nippon Shokubai and the like can be mentioned as commercial products of oxazoline compounds.

  In the present invention, specific examples of the oxazine compound that can be used as a terminal blocking agent having three or more reactive groups include polyoxazine containing a compound containing an oxazine group as a monomer unit.

  In the present invention, the carbodiimide compound that can be used as an end-capping agent having three or more reactive groups refers to at least three carbodiimide groups represented by (—N═C═N—) in the molecule. For example, it can be produced by decarboxylation by heating an organic isocyanate in the presence of a suitable catalyst.

  Specific examples of the carbodiimide compound include poly (1,6-hexamethylenecarbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexene). Silenecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide) ), Poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (1,3,5) Examples include polycarbodiimides such as triisopropylbenzene) polycarbodiimide, poly (1,3,5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide, poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), and the like. Commercially available products include “Carbodilite” manufactured by Nisshinbo, “Stavaxol” manufactured by Rhein Chemie, and the like.

  In the present invention, examples of the compound containing an acid anhydride group include a polymer containing a compound containing an acid anhydride group as a monomer unit.

  In the present invention, the blending amount of the terminal blocking agent having 3 or more reactive groups is essential to be 0.01 to 10 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin. 05 to 5 parts by weight is more preferable, 0.1 to 3 parts by weight is further preferable, and 0.3 to 2 parts by weight is particularly preferable.

  In the present invention, the number of reactive groups in the end-capping agent having 3 or more reactive groups is preferably 3 to 100 in terms of excellent hydrolysis resistance, dry heat resistance or molding processability. 5 to 50 is more preferable, and 7 to 30 is more preferable. In the present invention, when the end-capping agent having 3 or more reactive groups is a polymer, the average number of reactive groups in one molecule is the ratio of monomers containing reactive groups contained in the polymer a When the weight percent is, the number average molecular weight of the polymer is b, and the molecular weight of the monomer containing the reactive group is c, the average number of reactive groups can be obtained as (a / 100) × b / c. .

  In the present invention, the end-capping agent (D) reaction catalyst is further added in that it has excellent long-term durability such as mechanical properties, moldability, heat resistance, hydrolysis resistance, and dry heat resistance, or excellent melt viscosity stability. Is preferred.

  In the present invention, (D) the reaction catalyst may be an alkali metal compound, alkaline earth metal compound, tertiary amine compound, imidazole compound, quaternary ammonium salt, phosphine compound, phosphonium salt, phosphate ester, organic acid or Lewis. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, acetic acid. Potassium, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate Alkali metal compounds such as dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt, cesium salt , Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, magnesium stearate, stearin Alkaline earth metal compounds such as strontium acid, triethylamine, tributylamine, trihexylamine, triamylamine, triethanolamine, dimethylaminoethanol, triethylenediamine , Tertiary amines such as dimethylphenylamine, dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, dimethylaniline, pyridine, picoline, 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole Imidazole compounds such as 2-ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, 4-phenyl-2-methylimidazole, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium Quaternary ammonium salts such as chloride, triethylbenzylammonium chloride, tripropylbenzylammonium chloride, N-methylpyridinium chloride Phosphine compounds such as trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, phosphonium salts such as tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, triphenylbenzylphosphonium bromide, trimethyl Phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (p-hydroxy) phenyl phosphate, tri (P-methoxy Phosphate esters such as phenyl phosphate, oxalic acid, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, organic acids such as dodecylbenzenesulfonic acid, boron trifluoride, aluminum tetrachloride, titanium tetrachloride, tin tetrachloride, etc. A Lewis acid etc. are mentioned, These can be used 1 type or 2 types or more. Among them, an alkali metal compound, an alkaline earth metal compound or a phosphate ester is preferable in terms of excellent hydrolysis resistance or melt viscosity stability, an alkali metal or an alkaline earth metal organic salt is more preferable, and an alkali metal. Alternatively, an organic salt of an alkaline earth metal having 6 or more carbon atoms is more preferable, and sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate or magnesium acetate is particularly preferable. It is most preferable to use any one or more of sodium stearate, potassium stearate, calcium stearate, magnesium stearate or sodium benzoate.

  (D) The compounding amount of the reaction catalyst is (A) 100 wt. 0.001-1 weight part is preferable with respect to part, 0.01-0.1 weight part is more preferable, 0.02-0.1 weight part is further more preferable.

  In the thermoplastic resin composition of the present invention, the end groups of the polymer and the low molecular weight compound may be appropriately blocked according to the use used as a molded product. In the case of terminal groups, the amount of carboxyl terminal groups in the resin composition is preferably 10 eq / t or less, more preferably 5 eq / t or less, in view of excellent hydrolysis resistance, more preferably 1 eq / t. More preferably, it is t or less. In the present invention, the amount of carboxyl end groups in the resin composition is measured by a method in which the resin composition is dissolved in a suitable solvent and then titrated with an alkali compound solution such as sodium hydroxide having a known concentration or measured by NMR. Any method can be used.

  In the present invention, it is preferable to blend (E) an inorganic filler in order to impart mechanical strength, surface hardness or other characteristics. (E) 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 (E) 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-based and pitch-based carbon fibers, stainless steel 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, zirconium silicate Bromide such as powdered, include granular or platy fillers, among them glass fibers are preferred. The type of glass fiber is not particularly limited as long as it is generally used for resin reinforcement. For example, it can be used by selecting from long fiber type or short fiber type chopped strand, cut fiber, milled fiber, etc. As for, any of round shape, rectangular shape, eyebrows shape and the like can be used. Moreover, said (E) inorganic filler can also be used in combination of 2 or more types. In addition, said (E) 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. 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 (E) inorganic filler 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 or the like.
In the present invention, in order to impart mechanical strength and other characteristics of the resin composition, it is preferable to blend (F) an impact resistance improver. (F) 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 (F) 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, crystal nucleating agents, plasticizers, ultraviolet absorbers, antibacterial agents, stabilizers, mold release agents, colorants including pigments and dyes, lubricants, antistatic agents and One or more additives selected from flame retardants can be added. In the present invention, the fluidity of branched polymers, low-molecular-weight linear polyesters, low-molecular-weight linear polycarbonates, aromatic low-molecular compounds, acrylic compounds, etc. is within the range not impairing the object of the present invention. An agent may be further 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, metal salts of phenylphosphonate, 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 mold release agent, any of those used for mold release agents 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 kind of flame retardant selected from brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants. It is preferable to use any two or more flame retardants selected from the above flame retardants in that a flame retardant can be used and the flame retardancy and mechanical properties are excellent.

  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 derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A-carbonate oligomer or polymer, 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 representative examples include organic phosphorus such as phosphate ester, condensed phosphate ester, and polyphosphate. In terms of excellent fluidity, mechanical properties and flame retardancy, one or more of condensed phosphate ester, polyphosphate and red phosphorus are preferable, and condensed phosphate ester is more preferable. Aromatic condensed phosphates are 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 terms 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. In addition, 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 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, alkyl group, cyclohexyl group, phenyl group, benzyl group, amino group, epoxy group, polyether Modified polysiloxane modified with at least one group selected from a group, carboxyl group, mercapto group, chloroalkyl group, alkyl higher alcohol ester group, alcohol group, aralkyl group, vinyl group, or trifluoromethyl group, or these Can be mentioned. In addition, silsesquioxane forming a cage-type or ladder-type structure and a silicone-based oligomer that is a derivative thereof can also be given as preferable examples.

  In the present invention, other inorganic flame retardants include 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 a 3 or more functional group (C) a terminal blocking agent having 3 or more reactive groups and, if necessary, other components above the melting point of the thermoplastic resin, a single-screw extruder, a twin-screw extruder, or a triaxial or more multi-screw extrusion A method of uniformly melting and kneading with a machine, a method of removing a solvent after mixing in a solution, and the like are preferably used. From the viewpoint of productivity, a method of uniformly melting and kneading with a single screw or twin screw extruder is preferable, and fluidity In view of obtaining a resin composition excellent in mechanical properties, a method of uniformly melt-kneading with a twin screw extruder is more 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 due to (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, when melt-kneading, a method for supplying each component is, for example, using an extruder having at least one input port, preferably two or more input ports, from a main input port installed on the screw root side ( A) A thermoplastic resin, (B) a compound having three or more functional groups, (C) a terminal blocker having three or more reactive groups, and other batches of other components as required. Kneading method, (A) thermoplastic resin, (C) end-capping agent having 3 or more reactive groups and other components are supplied from the main input port, and the secondary input is installed between the main input port and the extruder tip (B) a method in which a compound having three or more functional groups is supplied from the mouth and melt-mixed; (A) a compound having a thermoplastic resin and other components is supplied from the main input port; Is there a sub-inlet installed in between? (B) a compound having three or more functional groups, (C) a method of supplying and melting and mixing an end-blocking agent having three or more reactive groups, or (A) a thermoplastic resin from a main input port, (B) a compound having three or more functional groups, (C) a terminal blocker having three or more reactive groups, and a compound having other components from a sub-inlet installed between the main inlet and the extruder tip (A) A thermoplastic resin and a compound having other components are supplied from the main inlet in terms of excellent fluidity, mechanical properties, and production stability. Then, (B) a compound having 3 or more functional groups and (C) an end-capping agent having 3 or more reactive groups are supplied and melted from a sub-inlet installed between the main inlet and the front end of the extruder. A method of mixing is preferable, and the component (B) and / or Others it is more preferable to continuously feed the terminal blocking agent having a (C) 3 or more reactive groups. In addition, (A) a thermoplastic resin, (B) a compound having three or more functional groups, and a compound having other components are melt-kneaded into pellets, and then (C) an end-capped group having three or more reactive groups. A method of melt-kneading in multiple stages such as a two-stage kneading method in which a compound having an agent and other components is melt-kneaded is also preferred. Further, in the present invention, when (E) an inorganic filler is blended, a side feed method is a method of blending (E) an inorganic filler from a sub-feed port installed between the main feed port and the extruder tip. It is preferable that

  The melt kneading temperature at the time of producing the resin composition of the present invention 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. .

  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 , Vapor canister housing, air cleaner how , Timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, etc. Automotive underhood parts, torque control levers, safety belt parts, register blades, washers Lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various automotive interior parts such as motor housing, roof rail, fender, garnish, bumper, door mirror stay, spoiler, hood louver, wheel cover, wheel Automotive exterior parts such as caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, wire harnesses Connectors, SMJ connectors, PCB connectors, various connectors for automobiles such as door grommet connectors, electrical connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings, internal parts, printer housings And internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers and handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts, facsimiles And electrical / electronic parts such as 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, semiconductor parts, liquid crystal parts, FDD carriages, FDD chassis, Electric and electronic parts such as motor brush holders and transformers, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, heat insulation , Adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags , Curing sheet, Slope protection sheet, Fly ash holding sheet, Drain sheet, Water retention sheet, Sludge and sludge dehydration bag, Concrete formwork such as concrete formwork, Washing bowl (washbasin), Handwashing bowl (handwashing machine), Washing face 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 Shelf, bathroom ceiling, washbasin, shower faucet, bathroom components such as washroom chairs and handrails, toilet bowl, toilet lid, toilet seat, toilet counter, washing nozzle, toilet storage shelf Toilet components, kitchen counters, kitchen sinks, kitchen bags, kitchen top plates, storage shelves, storage shelf doors, 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, Seedling pots, Vegetation pile, seed string tape, germination sheet, house lining sheet, farm bi-fastener, slow-release fertilizer, root-proof sheet, garden net, insect net, infant tree net, print laminate, fertilizer bag, sample bag, Agricultural materials such as sandbags, beast damage prevention nets, incentive straps, windproof nets, sanitary products such as disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, Non-woven fabric for medical use (stitching part 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 and other medical supplies, calendar , Stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets and other containers, tableware, hot fill containers, microwave 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, egg packs , HDD packaging, compost bags, recording media packaging, shopping bags, wrapping films for electrical and electronic parts, etc. 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, carriers Hot melt binders such as 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, magnetic material, zinc sulfide , Electrode material powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage ditch Filter, clear file, coating agent, adhesive Useful as a 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, PCB It is useful as a connector for various automobiles such as a connector and a door grommet connector or a connector for electric / electronic parts.

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

  The raw materials used in the examples and the symbols in the table are shown below.

(A) Thermoplastic resin A-1: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 45 eq / t)
A-2: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 12 eq / t)
A-3: Polypropylene terephthalate (melting point: 228 ° C., “Cortera” CP509211, manufactured by Shell Chemicals)
A-4: Polyethylene terephthalate (melting point 260 ° C., Mitsui Chemicals J155)
A-5: Polycarbonate (“Taflon” A1900 manufactured by Idemitsu Kosan Co., Ltd.)

(B) Compound B-1 having three or more functional groups: Glycerin (molecular weight 92, number of alkylene oxide units 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, manufactured by Aldrich)
B-3: Pentaerythritol (molecular weight 136, alkylene oxide unit number 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: Trishydroxymethylaminomethane (molecular weight 121, alkylene oxide unit number 0 per functional group, manufactured by Wako Pure Chemical Industries, Ltd.)
B-5: Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, Sakamoto Yakuhin SC-E450)
B-6: Polyoxyethylene trimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, Nippon Emulsifier TMP-30)
B-7: Polyoxyethylene pentaerythritol (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-8: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750)
B-9: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, TMP-F32 manufactured by Nippon Emulsifier)
B-10: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)
B-11: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp)
B-12: trimethylolpropane tris [poly (propylene glycol) amine] ether (molecular weight 450, number of alkylene oxide (propylene oxide) units 1.8 per functional group, “Jeffamine” T-403 manufactured by Huntsman).

(B ′) Compound B′-1: 1,6-hexanediol having less than 3 functional groups (manufactured by Aldrich).

(C) Terminal blocker C-1 having 3 or more reactive groups: Aromatic polycarbodiimide (Production Example 1)
C-2: Aliphatic polycarbodiimide (Production Example 2)
C-3: Oxazoline group-containing polymer (Production Example 3)
C-4: Glycidyl group-containing styrene / acrylic polymer (Production Example 4).

(D) Reaction catalyst D-1: Sodium stearate (manufactured by Wako Pure Chemical Industries).

(E) Inorganic filler E-1: Chopped strand type glass fiber (fiber diameter 10 μm, Nippon Electric Glass T120H).

(F) Impact resistance improver F-1: Ethylene / ethyl acrylate copolymer (“EVAFLEX” EEA A-709 manufactured by Mitsui DuPont Polychemical)
F-2: Acrylic core shell elastomer ("PARALOID" EXL2314 manufactured by Rohm & Haas).

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

(H) Release agent H-1: Montanic acid partially saponified ester (“Licowax” OP manufactured by Clariant).

[Production Example 1] Aromatic polycarbodiimide In a 3 L flask, 500 g of 4,4′-diphenylmethane diisocyanate, 5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a carbodiimidization catalyst, and 1.3 L of triethylene glycol dimethyl ether And reacted at 100 ° C. for 3.5 hours to obtain poly (4,4′-diphenylmethanecarbodiimide) having 5 carbodiimide groups in one molecule.

[Production Example 2] Aliphatic polycarbodiimide 1 L flask was charged with 500 g of 4,4'-dicyclohexylmethane diisocyanate and 53 g of cyclohexyl isocyanate and 5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a carbodiimidization catalyst. The reaction was carried out at 180 ° C. for 50 hours to obtain poly (4,4′-dicyclohexylmethanecarbodiimide) having 10 carbodiimide groups in one molecule.

[Production Example 3] Oxazoline group-containing polymer 100 parts by weight of toluene as a solvent and 1 part by weight of α-methylstyrene dimer as a chain transfer agent are charged into a reaction vessel equipped with a reflux tube, a thermometer, a dropping device and a stirring device. After the temperature was raised to 100 ° C., with stirring, a mixture of 70 parts by weight of styrene, 25 parts by weight of acrylonitrile and 5 parts by weight of 2-isopropenyl-2-oxazoline and t-butylperoxy-2 as a polymerization initiator -2 parts by weight of ethylhexanoate was gradually added dropwise to the reaction solution over 4 hours from the dropping device. After completion of the dropwise addition, the mixture was further stirred for 3 hours to complete the reaction. By pelletizing the resulting polymer solution while removing the solvent under reduced pressure, an oxazoline group-containing polymer having a number average molecular weight (Mn) of 45,000 and an average of 20 oxazoline groups in the molecule was obtained.

[Production Example 4] Styrene / acrylic polymer containing glycidyl group 69 parts by weight of styrene as a monomer, 30 parts by weight of glycidyl methacrylate and 1 part by weight of methyl methacrylate, 15 parts by weight of xylene and di-peroxide as a polymerization initiator While continuously supplying a mixture of 0.5 parts by weight of t-butyl to a 1 L reaction vessel equipped with a thermometer, a dropping device and a stirring device, polymerization was carried out at 210 ° C. with a residence time of 15 minutes. After continuously removing the polymer from the reaction vessel, volatile components such as residual monomers are removed under the conditions of 250 ° C. and 30 kPa to obtain a number average molecular weight (Mn) of 10,000 and an average of 6 epoxy groups in the molecule. One glycidyl group-containing styrene / acrylic polymer was obtained.

  Moreover, the evaluation method used in an Example etc. is shown 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) the thermoplastic resin is polybutylene terephthalate, and (E) 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 (E) 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) Tensile strength According to ASTM D638, the tensile strength of the ASTM No. 1 dumbbell molded 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) Hydrolysis resistance When the thermoplastic resin is polybutylene terephthalate, polypropylene terephthalate, or polyethylene terephthalate, ASTM No. 1 dumbbell molded product is formed. When the thermoplastic resin is a polycarbonate resin, molding with a 3 mm thick notch is performed. After the product is treated in a pressure cooker test apparatus at a temperature of 121 ° C. and a relative humidity of 100% for 30 hours, the tensile strength is measured by the above method (2) or the Izod impact strength is measured by the above method (3). Strength retention = (strength after hydrolysis / strength before hydrolysis) × 100 (%).

[Examples 1 to 8 , Comparative Examples 1 to 23 ]
(A) a thermoplastic resin, (B) a compound having 3 or more functional groups, and (C) an end-capping agent having 3 or more reactive groups, etc., at the mixing ratios shown in Table 1 and Table 2, Using a twin screw extruder with L / D = 45, melt kneading was performed by a batch charging kneading method. The melt kneading conditions were a cylinder temperature of 250 ° C. and a rotation speed of 200 rpm, and a pellet-shaped resin composition was obtained.
The obtained resin composition was injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., thereby obtaining molded products for various evaluations. The evaluation results are shown in Tables 1 and 2.

(A) Thermoplastic resin A-1: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 45 eq / t)
A-2: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 12 eq / t)
(B) Compound B-1 having three or more functional groups: Glycerin (molecular weight 92, number of alkylene oxide units 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, manufactured by Aldrich)
B-3: Pentaerythritol (molecular weight 136, alkylene oxide unit number 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: Trishydroxymethylaminomethane (molecular weight 121, alkylene oxide unit number 0 per functional group, manufactured by Wako Pure Chemical Industries, Ltd.)
B-5: Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, Sakamoto Yakuhin SC-E450)
B-6: Polyoxyethylene trimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, Nippon Emulsifier TMP-30)
B-7: Polyoxyethylene pentaerythritol (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-8: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750)
B-9: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, TMP-F32 manufactured by Nippon Emulsifier)
B-10: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)
B-11: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp)
B-12: trimethylolpropane tris [poly (propylene glycol) amine] ether (molecular weight 450, number of alkylene oxide (propylene oxide) units 1.8 per functional group, “Jeffamine” T-403 manufactured by Huntsman)
(B ′) Compound B′-1: 1,6-hexanediol having less than 3 functional groups (manufactured by Aldrich)
(C) Terminal blocker C-1 having 3 or more reactive groups: Aromatic polycarbodiimide (Production Example 1)
C-2: Aliphatic polycarbodiimide (Production Example 2)
C-3: Oxazoline group-containing polymer (Production Example 3)
C-4: Glycidyl group-containing styrene / acrylic polymer (Production Example 4)

(A) Thermoplastic resin A-1: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 45 eq / t)
A-2: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 12 eq / t)
(B) Compound B-1 having three or more functional groups: Glycerin (molecular weight 92, number of alkylene oxide units 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, manufactured by Aldrich)
B-3: Pentaerythritol (molecular weight 136, alkylene oxide unit number 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: Trishydroxymethylaminomethane (molecular weight 121, alkylene oxide unit number 0 per functional group, manufactured by Wako Pure Chemical Industries, Ltd.)
B-5: Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, Sakamoto Yakuhin SC-E450)
B-6: Polyoxyethylene trimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, Nippon Emulsifier TMP-30)
B-7: Polyoxyethylene pentaerythritol (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-8: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750)
B-9: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, TMP-F32 manufactured by Nippon Emulsifier)
B-10: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)
B-11: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp)
B-12: trimethylolpropane tris [poly (propylene glycol) amine] ether (molecular weight 450, number of alkylene oxide (propylene oxide) units 1.8 per functional group, “Jeffamine” T-403 manufactured by Huntsman)
(B ′) Compound B′-1: 1,6-hexanediol having less than 3 functional groups (manufactured by Aldrich)
(C) Terminal blocker C-1 having 3 or more reactive groups: Aromatic polycarbodiimide (Production Example 1)
C-2: Aliphatic polycarbodiimide (Production Example 2)
C-3: Oxazoline group-containing polymer (Production Example 3)
C-4: Glycidyl group-containing styrene / acrylic polymer (Production Example 4)
(D) Reaction catalyst D-1: Sodium stearate (manufactured by Wako Pure Chemical Industries)

From a comparison between Examples 1 to 8 and Comparative Examples 1 to 23 , (A) 0.1 to 10 parts by weight of a compound having 3 or more functional groups with respect to 100 parts by weight of the thermoplastic resin ( C) It can be seen that the thermoplastic resin composition obtained by blending 0.01 to 10 parts by weight of the end-capping agent having 3 or more reactive groups is excellent in fluidity and hydrolysis resistance. In particular, when (B) 0.1 to 4 parts by weight of a compound having 3 or more functional groups is blended and / or (B) the compound having 3 or more functional groups contains an alkylene oxide unit, fluidity It can be seen that it is excellent in hydrolysis resistance and mechanical properties.

[Examples 9 to 16 , Comparative Examples 24 to 41 ]
(A) a thermoplastic resin, (B) a compound having 3 or more functional groups, and (C) an end-capping agent having 3 or more reactive groups, etc., at the blending ratio shown in Table 3, L / D = 45 using a twin screw extruder, melt kneading was performed by a batch charging kneading method. The melt kneading conditions are as follows: (A) When the thermoplastic resin is polypropylene terephthalate, the cylinder temperature is 265 ° C. and the rotation speed is 200 rpm. When the thermoplastic resin is polyethylene terephthalate, the cylinder temperature is 280 ° C. and the rotation speed is 200 rpm. It was.

  Using the obtained resin composition, an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. (A) When the thermoplastic resin is polypropylene terephthalate, the cylinder temperature is 265 ° C., the mold temperature is 40 ° C., and the polyethylene terephthalate is cylinder. Injection molding was performed at a temperature of 280 ° C. and a mold temperature of 40 ° C. to obtain various molded articles for evaluation. The evaluation results are shown in Table 3.

(A) Thermoplastic resin A-3: Polypropylene terephthalate (melting point: 228 ° C., “Cortera” CP509211, manufactured by Shell Chemicals)
A-4: Polyethylene terephthalate (melting point 260 ° C., Mitsui Chemicals J155)
(B) Compound B-1 having three or more functional groups: Glycerin (molecular weight 92, number of alkylene oxide units 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, manufactured by Aldrich)
B-3: Pentaerythritol (molecular weight 136, alkylene oxide unit number 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: Trishydroxymethylaminomethane (molecular weight 121, alkylene oxide unit number 0 per functional group, manufactured by Wako Pure Chemical Industries, Ltd.)
B-5: Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, Sakamoto Yakuhin SC-E450)
B-6: Polyoxyethylene trimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, Nippon Emulsifier TMP-30)
B-7: Polyoxyethylene pentaerythritol (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-8: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750)
B-9: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, TMP-F32 manufactured by Nippon Emulsifier)
B-10: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)
B-11: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp)
B-12: trimethylolpropane tris [poly (propylene glycol) amine] ether (molecular weight 450, number of alkylene oxide (propylene oxide) units 1.8 per functional group, “Jeffamine” T-403 manufactured by Huntsman)
(B ′) Compound B′-1: 1,6-hexanediol having less than 3 functional groups (manufactured by Aldrich)
(C) Terminal blocker C-1 having 3 or more reactive groups: Aromatic polycarbodiimide (Production Example 1)
C-2: Aliphatic polycarbodiimide (Production Example 2)
C-3: Oxazoline group-containing polymer (Production Example 3)
C-4: Glycidyl group-containing styrene / acrylic polymer (Production Example 4)
(D) Reaction catalyst D-1: Sodium stearate (manufactured by Wako Pure Chemical Industries)

From a comparison between Examples 9 to 16 and Comparative Examples 24 to 41 , (B) 0.1 to 10 parts by weight of a compound having 3 or more functional groups with respect to 100 parts by weight of the thermoplastic resin ( C) It can be seen that the thermoplastic resin composition obtained by blending 0.01 to 10 parts by weight of the end-capping agent having 3 or more reactive groups is excellent in fluidity and hydrolysis resistance. In particular, when (B) 0.1 to 4 parts by weight of a compound having 3 or more functional groups is blended and / or (B) the compound having 3 or more functional groups contains an alkylene oxide unit, fluidity It can be seen that it is excellent in hydrolysis resistance and mechanical properties.

[Examples 17 to 22 , Comparative Examples 42 to 51 ]
(A) a thermoplastic resin, (B) a compound having 3 or more functional groups, and (C) an end-capping agent having 3 or more reactive groups, etc., at the blending ratio shown in Table 4, L / D = 45 using a twin screw extruder, melt kneading was performed by a batch charging kneading method. The melt kneading conditions were a cylinder temperature of 260 ° C. and a rotation speed of 200 rpm, and a pellet-shaped resin composition was obtained.

  The obtained resin composition was injection-molded at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., thereby obtaining molded products for various evaluations. The evaluation results are shown in Table 4.

(A) Thermoplastic resin A-5: Polycarbonate (“Taflon” A1900 manufactured by Idemitsu Kosan Co., Ltd.).
(B) Compound B-1 having three or more functional groups: Glycerin (molecular weight 92, number of alkylene oxide units 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, manufactured by Aldrich)
B-3: Pentaerythritol (molecular weight 136, alkylene oxide unit number 0 per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: Trishydroxymethylaminomethane (molecular weight 121, alkylene oxide unit number 0 per functional group, manufactured by Wako Pure Chemical Industries, Ltd.)
B-5: Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, Sakamoto Yakuhin SC-E450)
B-6: Polyoxyethylene trimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, Nippon Emulsifier TMP-30)
B-7: Polyoxyethylene pentaerythritol (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-8: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750)
B-9: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, TMP-F32 manufactured by Nippon Emulsifier)
B-10: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)
B-11: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp)
B-12: trimethylolpropane tris [poly (propylene glycol) amine] ether (molecular weight 450, number of alkylene oxide (propylene oxide) units 1.8 per functional group, “Jeffamine” T-403 manufactured by Huntsman)
(B ′) Compound B′-1: 1,6-hexanediol having less than 3 functional groups (manufactured by Aldrich)
(C) Terminal blocker C-1 having 3 or more reactive groups: Aromatic polycarbodiimide (Production Example 1)
C-2: Aliphatic polycarbodiimide (Production Example 2)
C-3: Oxazoline group-containing polymer (Production Example 3)
C-4: Glycidyl group-containing styrene / acrylic polymer (Production Example 4)

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

From a comparison between Examples 17 to 22 and Comparative Examples 42 to 51 , (A) 0.1 to 10 parts by weight of a compound having 3 or more functional groups with respect to 100 parts by weight of the thermoplastic resin ( C) It can be seen that the thermoplastic resin composition obtained by blending 0.01 to 10 parts by weight of the end-capping agent having 3 or more reactive groups is excellent in fluidity and hydrolysis resistance. In particular, when (B) 0.1 to 4 parts by weight of a compound having 3 or more functional groups is blended and / or (B) the compound having 3 or more functional groups contains an alkylene oxide unit, fluidity It can be seen that it is excellent in hydrolysis resistance and impact resistance.

[Examples 23 to 29 , Comparative Examples 52 to 60 ]
(A) a thermoplastic resin, (B) a compound having 3 or more functional groups, and (C) an end-capping agent having 3 or more reactive groups, etc., at the blending ratio shown in Table 5, L / D = 45 was used for melt kneading. (A) A thermoplastic resin and (C) a terminal blocker are blended, supplied from the main input port (hopper) at the root of the extruder screw, and from a sub input port installed between the main input port and the end of the extruder ( B) An individual charging kneading method for supplying a compound having three or more functional groups, and (E) a side feed method in which an inorganic filler is fed into the extruder from a side feeder, the melt kneading conditions are set at a cylinder temperature of 250. A pellet-shaped resin composition was obtained at a temperature of 120 ° C. and a rotation speed of 120 rpm.

  The obtained resin composition was injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., thereby obtaining molded products for various evaluations. The evaluation results are shown in Table 5.

(A) Thermoplastic resin A-1: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 45 eq / t)
A-2: Polybutylene terephthalate resin (melting point 223 ° C., intrinsic viscosity 0.86 dl / g, COOH concentration 12 eq / t)
(B) Compound B-7 having three or more functional groups: polyoxyethylene pentaerythritol (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, PNT-60U manufactured by Nippon Emulsifier)
B-9: Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, TMP-F32 manufactured by Nippon Emulsifier)
B-10: Polyoxypropylene pentaerythritol (molecular weight 452, number of alkylene oxide (propylene oxide) units per functional group, PNT-F40 manufactured by Nippon Emulsifier)
B-11: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp)
(C) Terminal blocker C-1 having 3 or more reactive groups: Aromatic polycarbodiimide (Production Example 1)
C-4: Glycidyl group-containing styrene / acrylic polymer (Production Example 4)
(D) Reaction catalyst D-1: Sodium stearate (manufactured by Wako Pure Chemical Industries)
(E) Inorganic filler E-1: Chopped strand type glass fiber (fiber diameter 10 μm, Nippon Electric Glass T120H).
(F) Impact resistance improver F-1: Ethylene / ethyl acrylate copolymer (“EVAFLEX” EEA A-709 manufactured by Mitsui DuPont Polychemical)
F-2: Acrylic core shell elastomer (Rohm & Haas "PARALOID" EXL2314)
(G) Stabilizer G-1: Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane (“IRGANOX” 1010 manufactured by Ciba Specialty Chemicals)
(H) Release agent H-1: Partially saponified ester of montanic acid ("Licowax" OP manufactured by Clariant)

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

From a comparison between Examples 23 to 29 and Comparative Examples 52 to 60 , (A) 0.1 to 10 parts by weight of a compound having 3 or more functional groups with respect to 100 parts by weight of the thermoplastic resin ( C) A thermoplastic resin composition comprising 0.01 to 10 parts by weight of an end-capping agent having 3 or more reactive groups and (E) an inorganic filler is excellent in fluidity and hydrolysis resistance. I understand that. Furthermore, it can be seen that when (B) the compound having 3 or more functional groups contains an alkylene oxide unit and (D) a reaction catalyst is blended, the hydrolysis resistance is particularly excellent. Moreover, when blended with (F) impact resistance improver, it is understood that the fluidity, mechanical properties, impact resistance, and hydrolysis resistance are excellent.

Claims (8)

(A) 0.1 to 10 parts by weight of a compound having 3 or more functional groups and (C) a compound other than (B), and 3 or more to 100 parts by weight of the thermoplastic resin A thermoplastic resin composition comprising 0.01 to 10 parts by weight of a terminal blocker having a reactive group of (A), wherein the thermoplastic resin is one or more selected from polyester resins and polycarbonate resins (B) the compound having three or more functional groups is a polyfunctional compound having three or more hydroxyl groups and one or more propylene oxide units, and at least one terminal structure having a functional group Is a compound having a structure represented by the formula (1), and (C) a compound in which the end-capping agent having 3 or more reactive groups contains a carbodiimide compound, an epoxy compound, an oxazine compound and an acid anhydride group Or The thermoplastic resin composition is at least one selected.
-(O-R) n-X (1)
(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.) The thermoplastic resin composition according to claim 1, wherein the terminal blocking agent is a compound having 3 or more reactive groups and not having the structure represented by the formula (1). (A) The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin is a polyester resin having a carboxyl end group amount of 30 eq / t or less. The thermoplastic resin composition according to any one of claims 1 to 3, further comprising (D) a reaction catalyst. Furthermore, (E) The thermoplastic resin composition in any one of Claims 1-4 formed by mix | blending an inorganic filler. Furthermore, the thermoplastic resin composition in any one of Claims 1-5 formed by mix | blending (F) impact resistance improving agent. When producing the thermoplastic resin composition according to any one of claims 1 to 6, assuming that the screw length of the twin screw extruder is L and the screw diameter is D, the twin screw extruder of L / D> 30. A method for producing a thermoplastic resin composition that is melt-kneaded using a resin. A molded article formed by molding the thermoplastic resin composition according to claim 1.