JP2007234260A - Resin composition for connector and connector consisting of it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a connector including thermoplastic resin excellent in fluidity and mechanical characteristics and a connector consisting of it. <P>SOLUTION: Resin composition for the connector is made up by blending (B) 0.01 to 50 parts by weight of a fluidity improving agent to (A) 100 parts by weight of thermoplastic resin. (B) the fluidity improving agent is preferred to include at least one selected from a branched polymer, liquid crystal polymer, low-molecular-weight straight-chain polyester, low-molecular-weight straight-chain polycarbonate, aromatic low-molecular-weight compound, and acrylic compound, and (A) the thermoplastic resin is preferred to be polybutylene terephthalate. Further, the connector consists of the resin composition for a connector. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition for connectors and a connector comprising the same, and more particularly to a resin composition for connectors containing a thermoplastic resin excellent in fluidity and mechanical properties and a connector comprising the same.

  Thermoplastic resins, especially polybutylene terephthalate (hereinafter referred to as PBT), which is a type of polyester, are excellent in moldability, heat resistance, mechanical properties, chemical resistance, etc., and are therefore connectors for automobiles and electrical / electronic devices. It is widely used as a material for industrial molded products such as relays and switches.

  However, in recent years, various types of industrial molded products, especially automobile wire harness connectors, have been increasing in number of circuits due to the diversification and multi-functionalization of electrical equipment, so that multipolarization and high density have been promoted. As a result, it is necessary to reduce the size and weight of molded products. Specifically, there is a need to reduce the thickness of molded products as the size of terminals is reduced. Improvement is demanded.

  Various methods have been studied for this, and Patent Documents 1 and 2 describe resin compositions using hyperbranched polymers, which are branched polymers, but for use in molded products such as connectors. There is no disclosure at all, and there is no suggestion of a solution for obtaining a resin composition for connectors.

Patent Document 3 describes a resin composition using a liquid crystal polymer, and Patent Document 4 describes a resin composition using a both-end-capped oligobutylene terephthalate which is a low molecular weight linear polyester, Patent Document 5 describes a resin composition using a low-molecular-weight linear polycarbonate, and Patent Document 6 describes a resin composition using an aromatic polybasic acid ester which is an aromatic low-molecular compound. Patent Document 7 describes a resin composition using an acrylic acid polymer that is an acrylic compound. However, in any case, the effect of improving fluidity is insufficient, and further improvement of fluidity is required, and there is no disclosure about using it for molded products such as connectors, and the resin composition for connectors There is no suggestion of a solution to get things.
International Patent Publication No. 2005/75563 (page 1-2) International Patent Publication No. 2005/75565 (page 1-2) Japanese Patent Laying-Open No. 2003-213105 (page 1-2) JP-A-4-120163 (page 1-2) JP-A-5-186676 (page 1-3) JP 61-85467 (page 1-2) JP 2003-113316 A (page 1-2)

  An object of the present invention is to provide a resin composition for a connector containing a thermoplastic resin excellent in fluidity and mechanical properties, and a connector comprising the same.

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

That is, the present invention
(1) (B) Fluidity improver with respect to 100 parts by weight of (A) thermoplastic resin. 01-50 parts by weight of a resin composition for connectors,
(2) (B) The fluidity improver is any one selected from a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound, and an acrylic compound. The connector resin composition according to (1), comprising
(3) The resin composition for connectors according to any one of (1) to (2), wherein (C) 1 to 100 parts by weight of a filler is blended with 100 parts by weight of a thermoplastic resin.
(4) The resin composition for a connector according to any one of (1) to (3), wherein (D) 1 to 100 parts by weight of an impact resistance improver is blended with 100 parts by weight of (A) thermoplastic resin. object,
(5) The resin composition for a connector according to any one of (1) to (4), wherein 0.01 to 50 parts by weight of the reactive compound (E) is blended with 100 parts by weight of the thermoplastic resin (A). object,
(6) The resin composition for connectors according to any one of (1) to (5), wherein (A) the thermoplastic resin is polybutylene terephthalate,
(7) The resin composition for a connector according to any one of (1) to (6), wherein the carboxyl end group concentration in the resin composition is 30 eq / t or less,
(8) A connector with a tab width of a terminal made of the resin composition for connectors according to any one of (1) to (7), of 0.8 mm or less,
It is.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for connectors containing the thermoplastic resin which is excellent in fluidity | liquidity and a mechanical characteristic, and a connector consisting thereof can be provided.

  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, Polyamide resin, Polyacetal resin, Polyester resin, Polycarbonate resin, Polyphenylene ether resin, Polyarylate resin, Polysulfone resin, Polyphenylene sulfide resin, Polyether ether ketone Resins, polyimide resins and polyetherimide resins may be mentioned, and one or more may be used in combination. Of these, polyamide resins, polyacetal resins, polyester resins, and polycarbonate resins are preferable, and polyester resins are more preferable in terms of heat resistance, moldability, fluidity, and mechanical properties. These may be used alone or in combination of two or more as a polymer alloy.

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

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

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

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

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

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

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

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

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

  When the thermoplastic resin (A) used in the present invention is a polyester resin, the amount of carboxyl end groups of the polyester resin is not particularly limited, but is 50 eq / t or less in terms of fluidity, hydrolysis resistance and heat resistance. Preferably, it is 30 eq / t or less, more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. The lower limit is 0 eq / t. In the present invention, the 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.

  When the thermoplastic resin (A) used in the present invention is a polyester resin, the amount of vinyl end groups of the polyester resin is not particularly limited, but is preferably 15 eq / t or less in terms of color tone and fluidity. / T or less is more preferable, and 5 eq / t or less is more preferable. 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.

  When the thermoplastic resin (A) used in the present invention is a polyester resin, the amount of hydroxyl terminal groups of the polyester resin is not particularly limited, but is preferably 50 eq / t or more in terms of moldability and fluidity, It is more preferably 80 eq / t or more, further preferably 100 eq / 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.

  When the thermoplastic resin (A) used in the present invention is a polyester resin, the viscosity of the polyester resin is not particularly limited as long as it can be melt-kneaded. However, in terms of moldability, the o-chlorophenol solution is 25 ° C. The intrinsic viscosity when measured is preferably in the range of 0.36 to 1.60 dl / g, more preferably in the range of 0.50 to 1.25 dl / g.

  When the thermoplastic resin (A) used in the present invention is a polyester resin, the method for producing the polyester resin is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization may be used, and both ester exchange reaction and direct polymerization reaction can be applied, but the amount of carboxyl end groups can be reduced, and fluidity and hydrolysis resistance can be reduced. Continuous polymerization is preferable in that the effect of improving the property is increased, and direct polymerization is preferable in terms of cost.

  When (A) the thermoplastic 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 Can be produced by subjecting a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative to an esterification reaction or a transesterification reaction, followed by 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, Trif Enyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid And 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 preferable. Tetra -n- butyl ester of titanic acid is especially preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) in terms of mechanical properties, moldability and color tone, A range of 0.2 parts by weight is more preferable.

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

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

  Particularly preferred 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 necessary properties such as impact resistance and molding processability.

  The degree of polymerization of these polyamide resins is not particularly limited, but a relative viscosity measured in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml at 25 ° C. 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 preferably 220 ° C. or higher. Although an upper limit is not specifically limited, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less. In the present invention, the melting point of the thermoplastic resin (A) is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  The (B) fluidity improver used in the present invention has a function of greatly reducing the melt viscosity of the thermoplastic resin by blending with the (A) thermoplastic resin. Specifically, It includes any one selected from a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound, and an acrylic compound. These may be used alone or in combination of two or more. However, in terms of improving fluidity more effectively and improving mechanical properties, hydrolysis resistance, etc. It is preferable to use the above in combination.

  In the present invention, the branched polymer refers to a polymer having a branched structure, and specifically refers to a polymer having a multi-branched structure. The branched structure includes a plurality of linear segments radially from a central core. A star polymer having a branched chain, a graft polymer having a structure in which a polymer having a plurality of branch points and a branch chain is introduced into the main linear polymer chain, and having a branch in three dimensions, Examples include hyperbranched polymers having a branched structure in the repeating unit, and dendrimers having a precisely controlled molecular weight distribution and degree of branching, and star polymers and hyperbranched polymers are preferred because they are easy to produce industrially. In this respect, a hyperbranched polymer is more preferable. The branched polymer of the present invention is preferably a polymer having a branched structure that does not have a crosslinked structure due to a chemical bond such as a covalent bond, in that the effect of improving fluidity is great.

  In the present invention, the branched polymer is not particularly limited as long as it is a polymer having a branched structure, but in terms of fluidity, polyamide, polyester, polyesteramide, polycarbonate, polyester polycarbonate, polyether, polystyrene, polyphenylene, polyimide, It is preferable that it contains any one selected from polyphenylene sulfide and polyurethane, and polyester and polycarbonate are more preferable in terms of heat resistance, mechanical properties, hydrolysis resistance, and recyclability, and an aromatic system having an aromatic ring A polymer is more preferable, and an alkylene terephthalate structure is particularly preferable.

  In the present invention, the method for producing the branched polymer is not particularly limited. In the case of a star polymer, after synthesizing a linear segment that becomes a branched chain, an arm-first method of grafting to the core and a multifunctional initiator as a component that becomes the core, and then a branched chain Any of the co-first methods for synthesizing a linear segment may be used. In the case of a dendrimer, either the Divergent method in which a stepwise reaction is repeated from the core to increase branching, or the Convergent method in which the outer shell components are repeatedly stepped and finally bonded to the core may be used. In the case of a hyperbranched polymer, a method of self-polycondensation using a compound having a total of 3 or more of two types of substituents in one molecule, a sequential reaction using a bifunctional compound and a trifunctional compound May be any one of a method of conducting polycondensation, a method of chain-reacting self-polycondensation using a vinyl monomer having an initiator site, and a method of chain-reacting ring-opening polymerization using a cyclic monomer. Preferred are a method of sequential self-polycondensation using a compound having a total of 3 or more of two kinds of substituents in the molecule and a method of successive reactive polycondensation using a bifunctional compound and a compound having a functionality of three or more. .

  In the present invention, when the branched polymer is a hyperbranched polymer, the raw material monomer is not particularly limited as long as the above production method can be carried out. As a specific example, the compound having a total of 3 or more of two kinds of substituents in one molecule includes diphenolic acid, 5- (2-hydroxyethoxy) isophthalic acid, 5-acetoxyisophthalic acid, 5-phenoxyisophthalic acid, 3,5-hydroxybenzoic acid, 3,5-acetoxybenzoic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid, methyl 3,5-bis (2-hydroxyethoxy) benzoate, 3,5-bis (Trimethylsiloxy) benzoic acid chloride, 4,4- (4′-hydroxyphenyl) pentanoic acid, 4,4- (4′-hydroxyphenyl) pentanoic acid methyl, 3,5-dibromophenol, 5- (bromomethyl)- 1,3-dihydroxybenzene, 3,5-diaminobenzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 5-aminoi Phthalic acid, phenol-3,5-diglycidyl ether, (3,5-dibromophenyl) boronic acid, 6-bromo-1- (4-hydroxy-4'-biphenylyl) -2- (4-hydroxyphenyl) Hexane, 13-bromo-1- (4-hydroxyphenyl) -2- (4-hydroxy-4 ″ -p-terphenylyl) tridecane, 13-bromo-1- (4-hydroxyphenyl) -2- [ 4- (6-Hydroxy-2-naphthalenylyl) phenyl] tridecane and the like, and in terms of fluidity, recyclability, mechanical properties and hydrolysis resistance, 5- (2-hydroxyethoxy) isophthalic acid, 5-acetoxy Isophthalic acid, 3,5-acetoxybenzoic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid, 3,5-bis (2-hydroxyethyl) Xyl) methyl benzoate, 3,5-bis (trimethylsiloxy) benzoic acid chloride, 4,4- (4′-hydroxyphenyl) pentanoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 13-bromo -1- (4-Hydroxyphenyl) -2- (4-hydroxy-4 ″ -p-terphenylyl) tridecane is preferred. Examples of the bifunctional compound include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, Dicarboxylic acid components such as aliphatic dicarboxylic acids such as dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, ethylene glycol, propylene glycol, 1, 4 Butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-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, Diol components such as poly-1,3-propylene glycol, polytetramethylene glycol, 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and their ester-forming derivatives, Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenedia Diamine components such as min, p-phenylenediamine, and p-xylylenediamine, and trifunctional or higher functional compounds include trimesic acid, trimellitic acid, pyromellitic acid, mellitic acid, glycerin, trimethylolpropane, pentaerythritol, 1,3 , 5-benzenetriol, tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenoxy) benzene, etc., and at least one compound having an aromatic ring may be used. , Terephthalic acid and ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-in terms of heat resistance, mechanical properties, hydrolysis resistance, and recyclability Use one or more diol components selected from hexanediol Rukoto are preferred, in which case, it is possible to obtain those having a alkylene terephthalate structure branched polymers. Examples of the vinyl monomer having an initiator site include 3- (1-chloroethyl) styrene and 4-chloromethylstyrene. Examples of the cyclic monomer include 2- (3,5-dihydroxyphenyl) -1,3-oxazoline.

  The molecular weight of the branched polymer used in the present invention is not particularly limited, but in terms of fluidity, the number average molecular weight (Mn) is preferably in the range of 300 to 30,000, more preferably in the range of 500 to 10,000. Preferably, the range is from 800 to 5000, more preferably from 1000 to 3000, the weight average molecular weight (Mw) is preferably from 300 to 150,000, and from 500 to 50,000. More preferably, it is more preferably in the range of 800-30000, and particularly preferably in the range of 1000-10000.

  The molecular weight distribution (Mw / Mn) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of 1 to 5 and more preferably in the range of 1 to 4 in terms of fluidity. 1 to 3 is more preferable.

  In the present invention, Mn, Mw and Mw / Mn of the branched polymer are values in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The degree of branching (DB) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of 0.1 to 1.0 and in the range of 0.2 to 0.9 in terms of fluidity. It is more preferable that it is in the range of 0.3 to 0.9. In the present invention, DB can be obtained from the following equation, and the number of each unit can be obtained from measurement by nuclear magnetic resonance (NMR).

DB = (D + T) / (D + L + T)
D: Number of dendritic units L: Number of linear units T: Number of terminal units The glass transition temperature (Tg) of the branched polymer used in the present invention is not particularly limited, but is in the range of −60 to 200 ° C. in terms of fluidity. It is preferable that it is, It is more preferable that it is the range of 0-150 degreeC, It is further more preferable that it is the range of 50-120 degreeC. In the present invention, Tg can be determined from measurement by a differential scanning calorimeter (DSC).

  The melting point (Tm) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of 0 to 300 ° C, more preferably in the range of 30 to 250 ° C, from the viewpoint of heat resistance. More preferably, it is in the range of 50 to 200 ° C. In the present invention, Tm can be determined from measurement by a differential scanning calorimeter (DSC).

  In the present invention, the liquid crystal polymer is a resin capable of forming an anisotropic molten phase, and preferably has an ester bond. For example, a liquid crystalline polyester comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, etc., and forming an anisotropic melt phase Or, a liquid crystalline polyester amide that is composed of a structural unit selected from the above structural unit and an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like, and that forms an anisotropic melt phase, etc. Specifically, a liquid crystalline polyester comprising a structural unit produced from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit produced from p-hydroxybenzoic acid, and 6-hydroxy-2-naphthoic acid. Generated structural units, aromatic dihydroxy compounds and / or aliphatic dicarboxylic acids Liquid crystalline polyester comprising a structural unit produced from the above, structural unit produced from p-hydroxybenzoic acid, structural unit produced from 4,4′-dihydroxybiphenyl, aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and / or adipine Liquid crystalline polyester comprising a structural unit produced from an aliphatic dicarboxylic acid such as acid or sebacic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, or a structural unit produced from terephthalic acid Polyester, structural unit generated from p-hydroxybenzoic acid, structural unit generated from ethylene glycol, liquid crystalline polyester composed of structural units generated from terephthalic acid and isophthalic acid, structural unit generated from p-hydroxybenzoic acid, ethylene Glico A liquid crystalline polyester comprising a structural unit formed from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid or sebacic acid, p-hydroxybenzoic acid, a structural unit formed from 4,4′-dihydroxybiphenyl, A structural unit generated from an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, a structural unit generated from ethylene glycol, a structural unit generated from ethylene glycol, a structural unit generated from an aromatic dihydroxy compound As the liquid crystalline polyester, and the liquid crystalline polyester amide resin, in addition to structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, etc. P-aminopheno Polyester amides that form an anisotropic melt phase containing p-iminophenoxy units produced from alcohol. Further, from the viewpoint of fluidity, the liquid crystal polymer preferably has a branched structure. Examples of the polymer having such characteristics can be obtained by the methods described in JP-T-8-503503, US Pat. No. 4,410,683, and the like.

  Of these liquid crystal polymers, liquid crystalline polyesters are preferable from the viewpoint of fluidity and mechanical properties. Among them, liquid crystalline polyesters composed of structural units formed from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, p- Structural units generated from hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from 4,4′-dihydroxybiphenyl, structural units generated from aliphatic dicarboxylic such as terephthalic acid and / or adipic acid, sebacic acid, etc. Liquid crystalline polyester comprising, structural unit generated from p-hydroxybenzoic acid, structural unit generated from ethylene glycol, structural unit generated from aromatic dihydroxy compound, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc. Is it an aromatic dicarboxylic acid? A liquid crystalline polyester composed of the generated structural unit is more preferable. Among them, a liquid crystalline polyester composed of a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, From structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, structural units generated from aromatic dicarboxylic acids such as terephthalic acid, structural units generated from p-hydroxybenzoic acid, from ethylene glycol A liquid crystalline polyester having a structural unit generated from an aromatic dicarboxylic acid such as terephthalic acid is more preferable.

  The method for producing a liquid crystal polymer such as liquid crystalline polyester or liquid crystalline polyester amide used in the present invention is not particularly limited and can be produced by a known polycondensation method.

For example, the following production method is preferably exemplified as the production of the liquid crystalline polyester.
(1) Diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by deacetic acid condensation polymerization reaction.
(2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid with acetic anhydride. Then, after acylating a phenolic hydroxyl group, a method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction.
(3) From p-hydroxybenzoic acid phenyl ester and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by dephenol polycondensation reaction.
(4) After reacting p-hydroxybenzoic acid and aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and the like with a predetermined amount of diphenyl carbonate to obtain diphenyl ester, 4,4 ′ A method for producing a liquid crystalline polyester by dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone.
(5) Polyester polymer such as polyethylene terephthalate, oligomer or liquid crystal by the method of (1) or (2) in the presence of bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate For producing a conductive polyester.

  The liquid crystal starting temperature (TN) of the liquid crystal polymer used in the present invention is not particularly limited, but is preferably in the range of 0 to 300 ° C., more preferably in the range of 100 to 250 ° C. in terms of fluidity. More preferably, the temperature is in the range of 150 to 230 ° C. In the present invention, TN refers to the temperature at which the entire field of view starts to flow as measured by a shear stress heating device (CSS-450) at a shear rate of 1000 / s, a heating rate of 5 ° C./min, and an objective lens 60 times. .

  The melting point (Tm) of the liquid crystal polymer used in the present invention is not particularly limited, but is preferably 0 to 350 ° C. or less, more preferably 100 to 300 ° C. or less in terms of fluidity and heat resistance. More preferably, it is 180-250 degrees C or less. In the present invention, Tm can be obtained from measurement by a differential scanning calorimeter (DSC), and is a value measured under a temperature rising rate of 20 ° C./min.

  The melt viscosity of the liquid crystal polymer used in the present invention is not particularly limited, but is preferably in the range of 0.5 to 200 Pa · s, more preferably in the range of 1 to 100 Pa · s in terms of fluidity. 1 to 50 Pa · s is more preferable. In the present invention, the melt viscosity of the liquid crystal polymer can be determined from the measurement by a capillograph, and is a value measured under the condition of Tm + 10 to 50 ° C. of the liquid crystal polymer and the shear rate of 1000 / s.

  The low molecular weight linear polyester used in the present invention is a linear polyester having a weight average molecular weight (Mw) in the range of 500 to 30,000. In terms of fluidity, mechanical properties, and bleed out, Mw is preferably in the range of 1000 to 25000, more preferably in the range of 1500 to 10,000, and even more preferably in the range of 3000 to 5000. In the present invention, Mw of the low molecular weight linear polyester is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

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

  The low molecular weight linear polycarbonate used in the present invention is a linear polycarbonate having a weight average molecular weight (Mw) in the range of 500 to 30,000. In terms of fluidity, mechanical properties and bleed out, Mw is preferably in the range of 1000 to 25000, more preferably in the range of 5000 to 20000, and still more preferably in the range of 7000 to 10,000. In the present invention, Mw of the low molecular weight linear polyester is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The low-molecular-weight linear polycarbonate used in the present invention is a polymer or copolymer having a carbonate bond obtained by reacting a diol with a carbonic acid diester. From the viewpoint of fluidity, both ends are hydroxyl groups. A certain polycarbonate diol is preferable. In the present invention, the diol may be an aromatic diol, an aliphatic diol, or an alicyclic diol, and the carbonic acid diester may be any of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. The raw material diol is preferably used in a range of 0.5 to 5.0 times the mole of the carbonic acid diester so that both ends of the resulting polycarbonate are hydroxyl groups, and 0.8 to 2.0 times. Mole is more preferable, and 0.9 to 1.5 times mol is more preferable.

  The aromatic low molecular weight compound used in the present invention is a compound having an aromatic ring and having a number average molecular weight (Mn) in the range of 50 to 1,000. In the present invention, in terms of fluidity, it is preferably a compound having a carboxylic acid having an aromatic ring or an ester bond, and Mn is preferably in the range of 100 to 900, and in the range of 300 to 800. It is more preferable.

  The acrylic compound used in the present invention is one in which 30 mol% or more of the constituent components are composed of a (meth) acrylic acid monomer. In the present invention, in terms of fluidity, the (meth) acrylic acid monomer is preferably 50 mol% or more, and more preferably 70 mol% or more. In the present invention, specific examples of the (meth) acrylic acid monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) allylate, (meth) acrylic. Examples include isopropyl acid, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and the like.

  The weight average molecular weight (Mw) of the acrylic compound used in the present invention is not particularly limited, but Mw is preferably in the range of 3000 to 300,000 in terms of fluidity, mechanical properties, and bleedout, More preferably, it is in the range of 10,000, more preferably in the range of 10,000 to 30,000.

  As a method for producing the acrylic compound used in the present invention, a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like can be used. Although the temperature conditions at the time of superposition | polymerization are not specifically limited, -30-100 degreeC is preferable at a heat resistant point, 0-90 degreeC is more preferable, and 30-80 degreeC is further more preferable.

  Although it does not specifically limit about the terminal group of (B) fluidity improver used by this invention, The terminal group which can suppress exchange reaction with a thermoplastic resin from the point of fluidity | liquidity and hydrolysis resistance (A). It is considered that the structure is effective, and specific methods for achieving the structure include (B) a method in which a monofunctional compound is added during the production of the fluidity improver, and (B) the fluidity improver. Examples thereof include a method in which the end group is blocked with a reactive compound. The terminal group structure may be any structure as long as it is not a reactive functional group structure such as carboxylic acid or hydroxyl terminal. For example, stearic acid ester terminal, benzoic acid terminal, o-benzoylbenzoic acid terminal, phenyl Examples include carbonate ends. Further, the amount of such a terminal group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 90 mol% or more in terms of fluidity and hydrolysis resistance. preferable. The terminal group structure can be determined by observing the corresponding chemical shift and its integrated value in NMR measurement. Another effective method is (A) a method of adding a stabilizer that deactivates a polymerization reaction catalyst for promoting polymerization added during the production of a thermoplastic resin.

  (B) Monofunctional compounds used in the method of adding a monofunctional compound during the production of a fluidity improver include monocarboxylic acids, alcohols, monoamines, etc., and in terms of fluidity, monocarboxylic acids are Preferable examples include benzoic acid, methylbenzoic acid, tert-butylbenzoic acid, naphthoic acid, stearic acid and the like. In addition, a monofunctional compound may be 1 type and may use 2 or more types together.

  (B) The reactive compound used in the method of end-capping the terminal group of the fluidity improver with a reactive compound is at least one selected from a glycidyl group, an acid anhydride group, a carbodiimide group, and an oxazoline group. The reactive compound etc. which contain a functional group more than a seed | species are mentioned, It is preferable that it is a reactive compound containing a glycidyl group from the point of fluidity | liquidity and recyclability. In addition, the reactive compound may be 1 type and may use 2 or more types together.

(A) As a stabilizer used in a method of adding a stabilizer for deactivating a catalyst for promoting polymerization added at the time of producing a thermoplastic resin, phosphorus compounds, hindered phenol compounds, thioether compounds , Vitamin compounds, triazole compounds, polyamine compounds, hydrazine derivative compounds, and the like. From the viewpoint of fluidity and recyclability, phosphorus compounds are preferable, and phosphate compounds are particularly preferable. More preferred. In addition, a stabilizer may be 1 type and may use 2 or more types together.
In the present invention, the blending amount of the (B) fluidity improver is 0.01 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin, and the fluidity, mechanical properties, heat resistance, and hydrolysis resistance. From the viewpoint of property and recyclability, 0.1 to 30 parts by weight is preferable, 0.5 to 20 parts by weight is more preferable, and 1 to 10 parts by weight is further preferable.

  In the present invention, in order to impart mechanical strength and other properties of the resin composition, it is preferable to blend 0.1 to 100 parts by weight of (C) filler with respect to 100 parts by weight of (A) thermoplastic resin, In terms of fluidity, the amount of the filler (C) is preferably 1 to 70 parts by weight, and more preferably 1 to 50 parts by weight. When the blending amount of the filler (C) is less than 0.1 parts by weight, the effect of improving the mechanical strength tends to be insufficient, and when it exceeds 100 parts by weight, the fluidity may be lowered or the weight may be increased. is there.

  In the present invention, as the type of (C) 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, etc. Fillers, and among others, glass fibers are preferred. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said (C) filler can also be used in combination of 2 or more types. The (C) filler used in the present invention is used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. You can also. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin.

  In the present invention, a layered silicate is preferably added, and an organically modified layered silicate is more preferable in terms of fluidity, mechanical properties, hydrolysis resistance, and the like.

  In the present invention, the organically modified layered silicate is a layered silicate in which an exchangeable cation or anion existing between layers is exchanged with an organic onium ion or an organic anion, and in particular, the exchangeable cation is an organic onium ion. Exchanged layered silicates are preferred.

  A layered silicate having exchangeable ions between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 Å are laminated, and exchangeable ions are provided between the layers of the plate-like materials. have. The ion exchange capacity is 0.2 to 3 meq / g, and preferably the ion exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li type Fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, swellable mica such as Li-type tetrasilicon fluorine mica, hydrotalcite, etc., which may be natural or synthesized Good. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. The ammonium ion may be any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium.

  Examples of primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium. Alkyltrimethylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldialkylammonium ions such as dimethyldioctadecylammonium, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, benzene Such as benzethonium ion having two thereof.

  Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These may be used alone or in combination of two or more. In the present invention, those having reactive functional groups and those having high affinity are preferred, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferred.

  Examples of the organic anion include a long-chain carboxylic acid, and examples thereof include lauric acid, decanoic acid, stearic acid, dodecadicarboxylic acid, and dimer acid.

  In the present invention, the organically modified layered silicate can be produced by reacting a layered silicate having an exchangeable cation or anion between layers, an organic onium ion or an organic anion by a known method. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a liquid or molten organic salt with a layered silicate can be used.

  In the present invention, the amount of organic ions relative to the layered silicate is the cation exchange capacity of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. In general, it is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents.

  In addition, it is preferable to use the organically modified layered silicate after pretreatment with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the organically modified layered silicate is preferably uniformly dispersed in the resin composition. Here, uniform dispersion means that the layered silicate is dispersed in a laminated state of 5 layers or less without having a local mass.

  In the present invention, the amount of the layered silicate is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). Part is particularly preferred.

  In the present invention, in order to impart mechanical strength and other properties of the resin composition, (D) 0.1 to 100 parts by weight of an impact resistance improver is blended with 100 parts by weight of the thermoplastic resin. From the viewpoint of fluidity, the blending amount of the (D) impact resistance improver is preferably 1 to 70 parts by weight, more preferably 1 to 50 parts by weight. (D) If the blending amount of the impact resistance improver is less than 0.1 parts by weight, the mechanical strength improving effect tends to be insufficient. There is a risk of lowering.

  In the present invention, as the (D) 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 Or an acrylic core-shell elastomer and the like, which may be used alone or in combination.

  In the present invention, it is preferable to blend 0.01 to 50 parts by weight of the reactive compound (E) with respect to 100 parts by weight of the thermoplastic resin (A) in terms of improving hydrolysis resistance and toughness. In terms of fluidity, the amount of the reactive compound (E) is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight, and 5 to 3 parts by weight is particularly preferred. (E) When the compounding amount of the reactive compound is less than 0.01 parts by weight, the hydrolysis resistance and toughness improving effect of the resin composition tends to be insufficient, and when it exceeds 50 parts by weight, gelation occurs. There is a risk that the fluidity will be lowered.

  In the present invention, the reactive compound (E) is preferably a reactive compound containing at least one functional group selected from a glycidyl group, an acid anhydride group, a carbodiimide group, and an oxazoline group. From the viewpoint of hydrolyzability, it is more preferably a reactive compound containing a glycidyl group. One kind of these reactive compounds may be used, but it is preferable to use two or more kinds in combination in view of hydrolysis resistance.

  In the present invention, as the reactive compound containing a glycidyl group, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, an alicyclic epoxy compound can be preferably used, and the hydrolysis resistance point Thus, a glycidyl ether compound and a glycidyl ester compound are more preferable, and a glycidyl ether compound and a glycidyl ester compound are more preferably used in combination.

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

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

  Furthermore, in the present invention, in terms of hydrolysis resistance, the reaction between the glycidyl group and the carboxyl terminal group of the thermoplastic resin (A) and the effect of improving the affinity between the thermoplastic resin and the branched polymer are achieved. As a compound, it is preferable to add (F) catalyst, and specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate. , Lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate , Lithium benzoate, disodium hydrogen phosphate, phosphoric acid Alkali metal compounds such as dipotassium dihydrogen, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt, cesium salt, water Calcium oxide, 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, strontium stearate Alkaline earth metal compounds such as triethylamine, tributylamine, trihexylamine, triamylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, dimethyl ether Tertiary amines such as ruphenylamine, 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 chloride Quaternary ammonium salts such as triethylbenzylammonium chloride, tripropylbenzylammonium chloride, N-methylpyridinium chloride, Phosphine compounds such as tilphosphine, triethylphosphine, tributylphosphine and trioctylphosphine, phosphonium salts such as tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide and 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) pheny Phosphate esters such as phosphate, oxalic acid, p-toluenesulfonic acid, dinonyl naphthalene disulfonic acid, organic acids such as dodecylbenzenesulfonic acid, Lewis such as boron trifluoride, aluminum tetrachloride, titanium tetrachloride, tin tetrachloride An acid etc. are mentioned, These can use 1 type (s) or 2 or more types. Among these, it is preferable to use an alkali metal compound, an alkaline earth metal compound, and a phosphate ester, and particularly an alkali metal or an organic salt of an alkaline earth metal can be preferably used. Particularly preferred compounds are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and magnesium acetate. Further, an organic salt of an alkali metal or alkaline earth metal having 6 or more carbon atoms is preferable, and it is preferable to use one or more of sodium stearate, potassium stearate, calcium stearate, magnesium stearate, and sodium benzoate. In the present invention, the addition amount of the catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight, and 0.01 to 0.1 part per 100 parts by weight of the thermoplastic resin (A). Part by weight is more preferred, with 0.03 to 0.1 part by weight being most preferred. If the amount of the catalyst is less than 0.001 part by weight, the improvement of the hydrolyzability is insufficient. On the other hand, if the amount exceeds 1 part by weight, a decrease in physical properties due to side reactions cannot be ignored.

  In the resin composition of the present invention, stabilizers (antioxidants, ultraviolet absorbers, etc.), lubricants, mold release agents, flame retardants, colorants including dyes and pigments, crystals, and the like are not impaired. A nucleating agent, a plasticizer, an antistatic agent, and the like can be added, and a release agent is preferably blended from the viewpoint of fluidity. Any release agent may be used as long as it is a generally known release agent used for thermoplastic resins, but from the viewpoint of mechanical properties, aliphatic ester type is preferable, and glycerin fatty acid ester and pentaerythritol fatty acid ester are more preferable. preferable.

  The method for producing the resin composition for a connector of the present invention is not particularly limited. For example, (A) a thermoplastic resin, (B) a fluidity improver, and other additives as necessary are blended in advance. Then, a method of uniformly melting and kneading with a single screw or twin screw extruder above the melting point, a method of removing the solvent after mixing in a solution, etc. are used, but in terms of productivity, with a single screw or twin screw extruder A method of uniformly melt-kneading is preferable, and a method of uniformly melt-kneading with a twin screw extruder is more preferable in that a resin composition excellent in fluidity and mechanical properties can be obtained.

  In the resin composition of the present invention, from the viewpoint of fluidity and toughness, the dispersed particle size of the (B) fluidity improver in the resin composition is preferably 200 nm or less, and more preferably 170 nm or less. 150 nm or less is more preferable, and 140 nm or less is particularly preferable. The lower limit is not particularly limited, but is preferably 10 nm or more and more preferably 30 nm or more in terms of fluidity. In the present invention, the dispersed particle size of (B) fluidity improver in the resin composition can be observed with a transmission electron microscope (TEM).

  In the resin composition of the present invention, in terms of hydrolysis resistance, the carboxyl end group concentration in the resin composition after melt-kneading is preferably as low as possible, preferably 40 eq / t or less, and 30 eq / It is more preferably t or less, further preferably 20 eq / t or less, particularly preferably 10 eq / t or less, and most preferably 5 eq / t or less. In the present invention, the carboxyl end group concentration in the resin composition can be determined by a method of titrating after dissolving the polymer in a solvent or a method of quantifying by NMR.

  In the resin composition of the present invention, in terms of fluidity, (A) the melting point of the thermoplastic resin + 20 to 100 ° C., and the melt viscosity at a shear rate of 100 / s is preferably in the range of 1 to 200 MPa · s. 10 to 150 MPa · s, more preferably 30 to 100 MPa · s, and particularly preferably 50 to 90 MPa · s. In the present invention, the melt viscosity of the resin composition can be measured by a capillograph.

  In addition, the obtained resin composition for connectors can be used as a connector by a conventionally known molding method, for example, any molding method such as injection molding, extrusion molding, blow molding, or vacuum molding. In particular, in the present invention, taking advantage of excellent fluidity, a thin portion having a thickness of 0.01 to 1.0 mm, preferably 0.05 to 0.7 mm, more preferably 0.1 to 0.4 mm is used. Specifically, the connector may have a terminal tab width of 0.8 mm or less, preferably 0.6 mm or less, more preferably 0.4 mm or less.

  The resin composition for a connector of the present invention and a connector comprising the same are excellent in fluidity and mechanical properties, and are also excellent in stagnation stability and recyclability. In a preferred embodiment, they are excellent in hydrolysis resistance, color tone, and the like. Therefore, it is particularly suitable as a connector for automobiles and a connector for electric / electronic devices.

  EXAMPLES Hereinafter, although an Example demonstrates the structure and effect of this invention further in detail, this invention is not limited to these. Here, the number of parts in the examples represents parts by weight. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A) Thermoplastic resin A-1: Polybutylene terephthalate resin (Tm 223 ° C., carboxyl end group amount 37 eq / t, vinyl end group amount 5 eq / t, intrinsic viscosity 1.00 dl / g)
A-2: Polybutylene terephthalate resin (Tm 223 ° C., carboxyl end group amount 14 eq / t, vinyl end group amount 1 eq / t, intrinsic viscosity 1.00 dl / g)
A-3: Polypropylene terephthalate resin (Tm 235 ° C., carboxyl end group amount 30 eq / t, vinyl end group amount 7 eq / t, intrinsic viscosity 1.00 dl / g)
A-4: Nylon 66 resin (Tm 262 ° C., “Amilan” CM3001-N manufactured by Toray)
(B) Fluidity improver B-1: Production Example 1 (Branched polymer: Hyperbranched aliphatic polyester)
B-2: Production Example 2 (Branched polymer: Hyperbranched aromatic polyester carbonate)
B-3: Production Example 3 (Liquid Crystal Polymer: Liquid Crystalline Polyester)
B-4: Production Example 4 (Liquid Crystal Polymer: Liquid Crystalline Polyester)
B-5: Production Example 5 (low molecular weight linear polyester: aliphatic polyester)
B-6: Production Example 6 (low molecular weight linear polyester: aromatic polyester)
B-7: Production Example 7 (low molecular weight linear polycarbonate: aliphatic polycarbonate)
B-8: Production Example 8 (low molecular weight linear polycarbonate: aromatic polycarbonate)
B-9: Tri-2-ethylhexyl trimellitic acid (TOTM, Daihachi Chemical Industry, Mn547, Tm-30 ° C.) (aromatic low molecular weight compound)
B-10: Production Example 9 (aromatic low molecular weight compound)
B-11: Polybutyl acrylate (“Act Flow” UMB-1001, Mw 1500, manufactured by Soken Chemical)
B-12: Production Example 10 (acrylic compound)
(C) Filler C-1: Glass fiber (Nittobo CS3J948)
C-2: Glass fiber (T-289 manufactured by Nippon Electric Glass)
C-3: Production Example 11 (Organic Modified Layered Silicate)
(D) Impact resistance improver D-1: Ethylene / ethyl acrylate copolymer ("Evaflex" A709, manufactured by Mitsui DuPont Chemical)
D-2: Polyester elastomer ("Hytrel" 4047 manufactured by Toray DuPont)
(E) Reactive compound E-1: Versatic acid glycidyl ester (Japan Epoxy Resin “Cardura” E10P)
E-2: Bisphenol A diglycidyl ether type epoxy resin (“Epicoat” 828 made by Japan Epoxy Resin)
(F) Catalyst F-1: Sodium stearate (manufactured by Nacalai Tesque)
[Production Example 1] (Production Example of B-1)
The reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then 5 parts of trimethylolpropane, 50 parts of 2,2′-bis (hydroxymethyl) heptanoic acid, 7 parts of stearic acid, and 0.2 of p-toluenesulfonic acid The mixture was reacted for 2 hours while stirring at 140 ° C. under a nitrogen stream, and further reacted at 140 ° C. and 67 Pa for 1 hour to obtain a hyperbranched aliphatic polyester (B-1) as a branched polymer. As a result of analyzing B-1, it was Mn1900, Mw2850, Mw / Mn1.5, Tg32 degreeC.
[Production Example 2] (Production Example of B-2)
After replacing the reaction vessel equipped with a stirring blade and a cooler with nitrogen, 50 parts of 1,6-hexanediol-based polycarbonate diol (Mn600) and 20 parts of trimesic acid were charged and stirred at 120 ° C. under a nitrogen stream. After holding for 1 minute, 0.1 part of dibutyltin oxide was added and polycondensed at 150 ° C. and 10 kPa for 3 hours. After returning to normal pressure, 5 parts of versatic acid glycidyl ester was added and reacted at 230 ° C. for 0.5 hour to obtain a hyperbranched aromatic polyester carbonate (B-3) as a branched polymer. As a result of analyzing B-3, it was Mn6700, Mw15000, Mw / Mn2.2, Tg45 degreeC.
[Production Example 3] (Production Example of B-3)
Polyethylene terephthalate 73 having 62 parts of p-hydroxybenzoic acid, 16 parts of 4,4′-dihydroxybiphenyl, 14 parts of terephthalic acid, and intrinsic viscosity of 0.6 dl / g in a reaction vessel equipped with a stirring blade and a distillation pipe And 68 parts of acetic anhydride were charged and reacted at 100 to 250 ° C. for 2 hours under a nitrogen stream, followed by polycondensation at 290 ° C. and 67 kPa for 3 hours to obtain a liquid crystalline polyester (B-3) as a liquid crystal polymer. . As a result of analyzing B-3, the liquid crystal starting temperature was 210 ° C., the melting point was 236 ° C., and the melt viscosity was 36 Pa · s (temperature 250 ° C., shear rate 1000 / s, orifice diameter 0.5 mm).
[Production Example 4] (Production Example of B-4)
A reaction vessel equipped with a stirring blade and a distillation tube was charged with 90 parts of p-acetoxybenzoic acid and 110 parts of polyethylene terephthalate having an intrinsic viscosity of 0.6 dl / g and reacted at 280 ° C. for 1 hour in a nitrogen stream. After that, polycondensation was performed at 290 ° C. and 67 kPa for 2 hours to obtain a liquid crystalline polyester (B-4) as a liquid crystal polymer. As a result of analyzing B-4, the liquid crystal starting temperature was 170 ° C., the melting point was 200 ° C., and the melt viscosity was 13 Pa · s (temperature 250 ° C., shear rate 1000 / s, orifice diameter 0.5 mm).
[Production Example 5] (Production Example of B-5)
A reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then 65 parts of adipic acid, 20 parts of 1,4-cyclohexanedimethanol, 20 parts of 1,4-butanediol and 10 parts of ethylene glycol were charged under a nitrogen stream. The mixture was reacted at 200 ° C. and 150 kPa for 1 hour, and further reacted at 220 ° C. and 40 kPa for 3 hours to obtain an aliphatic polyester (B-5) as a low molecular weight linear polyester. As a result of analyzing B-5, they were Mn2500, Mw5750, and Mw / Mn2.3.
[Production Example 6] (Production Example of B-6)
After the reaction vessel equipped with a stirring blade and a cooler was purged with nitrogen, 60 parts of terephthalic acid, 25 parts of 1,4-butanediol and 15 parts of ethylene glycol were charged and reacted at 180 ° C. for 1 hour in a nitrogen stream. , 220 ° C. and 40 kPa for 3 hours. After returning to normal pressure, 15 parts of methyl o-benzoylbenzoate was added and reacted at 220 ° C. and 67 Pa for 1 hour to obtain an aromatic polyester (B-6) as a low molecular weight linear polyester. As a result of analysis of B-6, Mn 1600, Mw 3100, Mw / Mn 1.9, hydroxyl end group amount 5 mol%, o-benzoylbenzoate ester end group amount 90 mol%.
[Production Example 7] (Production Example of B-7)
The reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then charged with 56 parts of 1,6-hexanediol and 43 parts of dimethyl carbonate, held at 120 ° C. for 15 minutes in a nitrogen stream, and then tetrabutoxy 0.1 g of titanium was added, reacted at 190 ° C. and 10 kPa for 5 hours under a nitrogen stream, and further reacted at 200 ° C. and 67 Pa for 5 hours to obtain an aliphatic polycarbonate (B-7) as a low molecular weight linear polycarbonate. . As a result of analyzing B-7, it was Mn1800, Mw2850, Mw / Mn1.5, hydroxyl end group amount 95 mol%, methyl carbonate endgroup amount 5 mol%.
[Production Example 8] (Production Example of B-8)
The reaction vessel equipped with a stirring blade and a cooler was purged with nitrogen, and then charged with 68 parts of 2,2′-bis (4-hydroxyphenyl) propane and 77 parts of diphenyl carbonate, and stirred at 180 ° C. under a nitrogen stream. After being kept for 1 minute, the mixture was reacted at 230 ° C. for 1 hour, and further reacted at 230 ° C. and 67 Pa to obtain an aromatic polycarbonate (B-8) as a low molecular weight linear polycarbonate. As a result of analyzing B-7, it was Mn3200, Mw6150, Mw / Mn1.9, hydroxyl end group amount 25 mol%, phenyl carbonate endgroup amount 75 mol%.
[Production Example 9] (Production Example of B-10)
The reaction vessel equipped with a stirring blade and a cooler was purged with nitrogen, then charged with 30 parts of 4,4′-diacetoxybiphenyl and 25 parts of benzoic acid, and allowed to react for 1 hour with stirring at 200 ° C. in a nitrogen stream. The reaction was carried out at 3 ° C for 3 hours. Acetone was removed with a Soxhlet extractor to obtain 4,4′-dibenzoyloxybiphenyl (B-10) as an aromatic low-molecular compound. As a result of analyzing B-10, it was Mn450 and Tm252 degreeC.
[Production Example 10] (Production Example of B-12)
After replacing the reaction vessel equipped with a stirring blade, a reflux device and a dropping device with nitrogen, 30 parts of methyl methacrylate, 30 parts of acrylic acid, 30 parts of styrene, 20 parts of α-methylstyrene, benzene as a solvent, polymerization initiator Azobisisobutyronitrile as a chain transfer agent and n-lauryl mercaptan as a chain transfer agent, followed by solution polymerization in a nitrogen stream at 80 ° C. for 1 hour. After completion of the polymerization reaction, the solvent and residual monomers were removed under a reduced pressure of 130 Pa. After removal, methyl methacrylate / acrylic acid / styrene / α-methylstyrene copolymer (B-12) was obtained as an acrylic compound. As a result of analyzing B-12, it was Mw19000 and Tg50 degreeC.
[Production Example 11] (Production Example of C-2)
100 parts of swellable fluorinated mica (Coop Chemical, “Somasif” ME-100, cation exchange capacity: 120 meq / 100 g) was stirred and dispersed in 10 L of warm water, and 150 parts of polyoxypropylene methyl diethylammonium chloride was dissolved therein. 2 L was added and stirred for 2 hours. The resulting precipitate was filtered off and washed with warm water. This washing and filtering operation was performed three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a swellable fluoromica (C-2) organized with polyoxypropylenemethyldiethylammonium ions.

The measurement method and determination method used in the present invention are shown below.
(1) Mn, Mw and Mw / Mn
It is the value of standard PMMA conversion measured by GPC. The GPC measurement uses a WATERS differential refractometer WATERS410 as a detector, a MODEL510 high performance liquid chromatography as a pump, and a column with Shodex GPC K-806M and Shodex GPC K-G connected in series as a solvent. Hexafluoroisopropanol was used, the flow rate was 0.5 mL / min, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected and measured.
(2) Intrinsic viscosity A solution with a sample concentration of 5 mg / mL using an o-chlorophenol solvent was measured at 25 ° C.
(3) Glass transition temperature (Tg), liquid crystal onset temperature (TN) and melting point (Tm)
It measured with the differential scanning calorimeter (Seiko Electronics RDC220). The measurement conditions are a sample 10 mg, a nitrogen atmosphere, and a temperature increase rate of 20 ° C./min.
(4) Amount of carboxyl end group 1.5 g of a sample was dissolved in o-cresol / chloroform solvent, and then titrated with ethanolic potassium hydroxide.
(5) Other end group amounts These are values measured by 1H-NMR measurement. 1H-NMR measurement was performed using JNM-AL400 manufactured by JEOL Ltd., using deuterated hexafluoroisopropanol as a solvent and a sample concentration of 20 mg / mL.
(6) Flowability A bar flow molded product having a thickness of 0.5 mm and a width of 10 mm was used, and the flow length was judged. The injection conditions are a cylinder temperature of 240 ° C., a mold temperature of 80 ° C., an injection pressure of 60 MPa, and an injection speed of 100 mm / s.
(7) Heat resistance (DTUL)
In accordance with ASTM D648, the deflection temperature under load (load 1.82 MPa) of the 12.7 mm × 127 mm × 3 mm strip-shaped product was measured.
(8) Impact resistance According to ASTM D256, the Izod impact strength of a 3 mm thick notched molded product was measured.
(9) Flexural Modulus According to ASTM D790, the flexural modulus of the 12.7 mm × 127 mm × 3 mm strip-shaped product was measured.
GPa).
(10) Tensile strength Tensile yield strength was measured for ASTM No. 1 dumbbell test pieces according to ASTM D-638.
(11) Hydrolysis resistance ASTM No. 1 dumbbell specimens were left in a pressure cooker test apparatus at a temperature of 121 ° C. and a relative humidity of 100% for 50 hours. Then, it took out from the apparatus, measured the tensile yield strength by said method (2), and calculated | required tensile strength retention = (strength after a hydrolysis process / strength before a hydrolysis process) x100 (%).
(12) Connector moldability (thin wall moldability)
A wire harness connector for automobiles having a terminal tab width of 0.5 mm (thickness 0.2 mm) was formed and judged according to the following criteria.

  A: A connector can be obtained without any problem.

  ○: A connector with a slight burr or unfilled can be obtained.

X: A burr | flash or unfilling is large and a connector cannot be obtained.
[Examples 1-18, Comparative Examples 1-3]
As shown in Table 1, (A) a thermoplastic resin and (B) a fluidity improver are blended, and a 30 mm diameter twin screw extruder is used for melt kneading under conditions of a cylinder temperature of 250 ° C. and a rotation speed of 200 rpm, and pellets A resin composition was obtained.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries injection molding machine SG75H-MIV at a cylinder temperature of 240 ° C and a mold temperature of 80 ° C.

  The evaluation results are shown in Table 1.

  From the results in Table 1, the following is clear.

From the comparison between Examples 1 to 18 and Comparative Examples 1 to 3, the resin composition formed by blending (A) a thermoplastic resin and (B) a fluidity improver has fluidity, mechanical properties, and connector moldability. It turns out that it is excellent. In particular, (A) the thermoplastic resin is polybutylene terephthalate, and (B) the fluidity improver is a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, and an aromatic low molecule. It can be seen that it is preferably one of the compounds, and the amount of carboxyl end groups of the resin composition is preferably 30 eq / t or less.
[Examples 19 to 34, Comparative Examples 4 and 5]
As shown in Table 2, (A) a thermoplastic resin, (B) a fluidity improver and (C) a filler were blended, a 30 mm diameter twin screw extruder was used, a cylinder temperature of 250 ° C., and a rotation speed of 200 rpm. The mixture was melt kneaded to obtain a pellet-shaped resin composition.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries injection molding machine SG75H-MIV at a cylinder temperature of 240 ° C and a mold temperature of 80 ° C.

  The evaluation results are shown in Table 2.

  From the results in Table 2, the following is clear.

From a comparison between Examples 19 to 34 and Comparative Examples 4 and 5, the resin composition comprising (A) a thermoplastic resin, (B) a fluidity improver, and (C) a filler is fluid and heat resistant. It can be seen that it has excellent properties, mechanical properties, and connector moldability. In particular, the (B) fluidity improver is preferably any one of a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, and an aromatic low molecular weight compound. It can be seen that the carboxyl end group amount is preferably 30 eq / t or less.
[Examples 35 to 46, Comparative Example 6]
As shown in Table 3, (A) a thermoplastic resin, (B) a fluidity improver and (C) a filler were blended, a 30 mm diameter twin screw extruder was used, a cylinder temperature of 250 ° C., and a rotational speed of 200 rpm. The mixture was melt kneaded to obtain a pellet-shaped resin composition.

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

  The evaluation results are shown in Table 3.

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

From a comparison between Examples 35 to 46 and Comparative Example 6, a resin composition comprising (A) a thermoplastic resin, (B) a fluidity improver, and (C) a filler has fluidity, mechanical properties, It can be seen that the connector moldability is excellent. In particular, (A) the thermoplastic resin is nylon 66 resin, and (B) the fluidity improver is a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, and an aromatic low molecule. It can be seen that any of the compounds is preferred.
[Examples 47 to 60, Comparative Examples 7 and 8]
As shown in Table 4, in addition to (A) thermoplastic resin, (B) fluidity improver, (C) filler, (D) impact modifier, (E) reactive compound, (F) catalyst Using a 30 mm diameter twin screw extruder, the mixture was melt kneaded under conditions of a cylinder temperature of 250 ° C. and a rotation speed of 200 rpm to obtain a pellet-shaped resin composition.

  The obtained resin composition was injection molded using a Sumitomo Heavy Industries injection molding machine SG75H-MIV at a cylinder temperature of 240 ° C and a mold temperature of 80 ° C.

  The evaluation results are shown in Table 4.

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

  From a comparison between Examples 47 to 60 and Comparative Examples 7 and 8, (A) a thermoplastic resin, (B) a fluidity improver, (C) a filler, and (D) an impact resistance improver are blended. It can be seen that the resin composition is excellent in fluidity, impact resistance, mechanical properties, and connector moldability. Furthermore, it turns out that the resin composition formed by mix | blending (E) a reactive compound and / or (F) catalyst is excellent also in hydrolysis resistance.

Claims (8)

(A) A resin composition for a connector obtained by blending 0.01 to 50 parts by weight of a fluidity improver with respect to 100 parts by weight of a thermoplastic resin. (B) The fluidity improver includes any one selected from a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound, and an acrylic compound. The resin composition for a connector according to claim 1, which is a waste product. The resin composition for a connector according to any one of claims 1 to 2, wherein (A) 1 to 100 parts by weight of the filler (C) is blended with 100 parts by weight of the thermoplastic resin. The resin composition for connectors according to any one of claims 1 to 3, wherein (A) 1 to 100 parts by weight of an impact resistance improver is blended with 100 parts by weight of the thermoplastic resin. The resin composition for a connector according to any one of claims 1 to 4, wherein (A) 0.01 to 50 parts by weight of the reactive compound is blended with 100 parts by weight of the thermoplastic resin. (A) The thermoplastic resin is polybutylene terephthalate, The resin composition for connectors according to any one of claims 1 to 5. The resin composition for a connector according to any one of claims 1 to 6, wherein a carboxyl end group concentration in the resin composition is 30 eq / t or less. The connector whose tab width of the terminal which consists of the resin composition for connectors in any one of Claims 1-7 is 0.8 mm or less.