JP2009132851A - Thermoplastic resin composition as well as molded article and composite molded body therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in the flowability and mechanical characteristics and also which is, in a preferable mode, excellent in the laser permeability and laser weldability and to provide a molded article and a composite molded body therefrom. <P>SOLUTION: The thermoplastic resin composition comprises a blend of 100 parts by weight of the sum total of (A) a polyester resin and (B) an amorphous resin, 0.01-10 parts by weight of (C) a flow improver and (F) 0.01-1 part by weight of a stabilizer, (C) the flow improver being a compound which has three or more functional groups and preferably contains one or more alkylene-oxide units, and furthermore comprises more preferably (D) a filler blended additionally thereto. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition excellent in fluidity and mechanical properties, and in a preferred embodiment, excellent in laser permeability and laser weldability, and a molded article and a composite molded body comprising the same.

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

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

Patent Document 1 describes a polyester resin having a melt tension of 0.8 to 5.0 g having a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol, and a polyfunctional compound is added during polymerization of the polyester. Therefore, the obtained polyester resin has a problem that the viscosity is increased and the fluidity is lowered. Further, Patent Document 2 includes a combination of a specific thermoplastic resin and a compound having at least three specific functional groups. Although a fluidity improving method for melting and mixing is described, the fluidity improving effect is insufficient and the mechanical properties tend to decrease.

  On the other hand, conventionally, in joining parts due to the complexity of product shape, joining with an adhesive, mechanical joining with a bolt or the like has been performed. However, adhesives have problems of adhesive strength, and mechanical joining by bolts has a problem of cost, time and effort of fastening. In hot plate welding, the problem of stringing, vibration welding, and ultrasonic welding required the treatment of burrs generated near the joint. On the other hand, laser welding of the resin molded body is a method of irradiating laser light to the superimposed resin molded product, allowing the irradiated one to pass through, absorbing the other, melting, and fusing, enabling three-dimensional bonding. This method is rapidly spreading to a wide range of fields, taking advantage of non-contact processing and the absence of burrs.

  However, polyester resin, especially polybutylene terephthalate resin, has a very low laser beam transmittance compared to thermoplastic resins such as nylon resin, and the laser welding method is applied with polybutylene terephthalate resin as a molded product on the laser beam transmission side. In this case, the laser beam transmittance is low, so that the thickness is strictly limited. In order to improve the laser beam transmittance, it is necessary to cope with the thinning, and the degree of freedom in product design is very small.

Patent Document 3 discloses a polybutylene terephthalate resin or a polybutylene terephthalate resin comprising a polybutylene terephthalate and a polybutylene terephthalate copolymer and a polycarbonate resin, an acrylonitrile / styrene copolymer, a polyphenylene oxide, a styrene resin, an acrylic resin, and a polyether. An example in which laser beam transmittance is improved by blending one or more resins of sulfone, polyarylate, and polyethylene terephthalate and laser welding is performed is disclosed in Patent Document 4 as polybutylene terephthalate resin, polycarbonate resin, and styrene resin. An example of improving the laser beam transmittance with a resin composition comprising at least one polyethylene terephthalate resin and performing laser welding is described. Can greatly improve the laser transmittance compared to polybutylene terephthalate resin alone, there is the fluidity is not always sufficient and can not be molded is large molded article size, there can be a problem.
JP 2001-200038 A (Claims) JP-A-7-304970 (Claims) Japanese Patent Laying-Open No. 2003-292752 (Claims) WO2003 / 085046 (Claims)

  An object of the present invention is to provide a thermoplastic resin composition excellent in fluidity and mechanical properties, and in a preferred embodiment, excellent in laser permeability, laser weldability or low warpage, and a molded article and a composite molded body comprising the same. There is.

  The inventors of the present invention have reached the present invention as a result of intensive studies and examinations in order to solve such problems.

That is, the present invention
(1) 0.01 to 10 parts by weight of (C) fluidity improver and 0.01 to 10 parts of (F) stabilizer for a total of 100 parts by weight of (A) polyester resin and (B) amorphous resin. 1 part by weight of a thermoplastic resin composition,
(2) The thermoplastic resin composition according to (1), wherein the fluidity improver (C) is a compound having three or more functional groups, and includes one or more alkylene oxide units.
(3) (C) The fluidity improver is a compound having three or more functional groups, and the functional groups are selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group or an amide group. The thermoplastic resin composition according to (1) or (2), characterized in that it is at least one kind of group
(4) (A) The polyester resin is at least one selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polybutylene terephthalate resin composed of polybutylene terephthalate and polybutylene terephthalate copolymer. The thermoplastic resin composition according to any one of (1) to (3),
(5) (B) The amorphous resin is one or more selected from polycarbonate resin, styrene resin, acrylic resin, polyarylate resin, and polyphenylene ether resin (1) to (4) The thermoplastic resin composition according to any one of
(6) The thermoplastic resin composition according to any one of (1) to (5), further comprising (D) a filler.
(7) The filler (D) is talc or glass fiber, and is blended in an amount of 0.01 to 120 parts by weight with respect to a total of 100 parts by weight of (A) and (B) (6 ) Thermoplastic resin composition,
(8) The thermoplastic resin composition according to any one of (1) to (7), further comprising (E) an impact resistance improver,
(9) (E) The impact resistance improver is a styrene elastomer which is a copolymer of styrene and butadiene, and the styrene elastomer is added in an amount of 1 to 100 weights per 100 weight parts of (A) and (B). Part of the thermoplastic resin composition according to (8),
(10) The thermoplastic resin composition according to any one of (1) to (9), wherein the (F) stabilizer is a phosphite compound or / and a phosphate compound,
(11) The thermoplastic resin composition for laser welding according to any one of (1) to (10),
(12) A laser welding molded article comprising the laser welding thermoplastic resin composition according to (11),
(13) A composite molded body obtained by laser welding the molded product according to (12) is provided.

  According to the present invention, there are provided a thermoplastic resin composition excellent in fluidity and mechanical properties, and in a preferred embodiment, excellent in laser permeability, laser weldability or low warpage, and a molded article and a composite molded body comprising the same. be able to.

  The (A) polyester resin 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, and (c) a lactone. It is a polymer or copolymer having one or more selected main structural units.

  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, diphenic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedione And aliphatic dicarboxylic acids such as acid, malonic acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof. .

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

  (A) Polymers or copolymers having dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polypropylene isophthalate. , Polybutylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene Terephthalate / naphthalate, polybutylene terf Rate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfoisophthalate, 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 / isof Rate / 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, polybutylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate Aromatic polyester resins such as pete, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate Nate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentylglycol adipate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / Adipate, polybutylene succinate / adipate What aliphatic polyester resins.

  In addition, (b) the hydroxycarboxylic acid or ester-forming derivative thereof includes glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6- Examples thereof include hydroxy-2-naphthoic acid and ester-forming derivatives thereof. Polymers or copolymers having these as structural units include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / Examples include aliphatic polyester resins such as β-hydroxybutyric acid / β-hydroxyvaleric acid.

  Examples of the (c) lactone include ε-caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one, γ-butyrolactone, and the like. Examples of the copolymer include polycaprolactone, polyvalerolactone, polypropiolactone, poly-γ-butyrolactone, polycaprolactone / valerolactone, and the like.

  Among these, (a) a polymer or copolymer having a main structural unit of a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof is preferable, and an aromatic dicarboxylic acid or an ester-forming derivative thereof A polymer or copolymer having an aliphatic diol or an ester-forming derivative thereof 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 the like. A polymer or copolymer having an ester-forming derivative as a main structural unit is more preferred, and among them, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene. Aromatic polyester resins such as lennaphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate are preferred, polyethylene terephthalate, polypropylene Particularly preferred are terephthalate and polybutylene terephthalate, and particularly preferred is polybutylene terephthalate.

  In the present invention, terephthalic acid or its ester-forming derivative with respect to all the dicarboxylic acids in the polymer or copolymer having (i) the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit. Is preferably 30 mol% or more, and more preferably 40 mol% or more.

  The viscosity of the (A) polyester resin used in the present invention is not particularly limited as long as it can be melt-kneaded. It is preferably in the range of ˜1.60 dl / g, and more preferably in the range of 0.50 to 1.50 dl / g.

  The amount of the carboxyl end group of the (A) polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or less, 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) the thermoplastic resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The amount of the vinyl terminal group of the (A) polyester resin used in the present invention is not particularly limited, but is preferably 15 eq / t or less, more preferably 10 eq / t or less in terms of color tone and fluidity, More preferably, it is 5 eq / t or less. The lower limit is 0 eq / t. In the present invention, the vinyl terminal 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 (A) polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or more, more preferably 80 eq / t or more in terms of moldability and fluidity. 100 eq / t or more is more preferable, and 120 eq / t or more is particularly preferable. The upper limit is not particularly limited, but is 180 eq / t. In the present invention, the hydroxyl terminal group amount of (A) the thermoplastic resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The method for producing the (A) polyester resin used in the present invention is not particularly limited, and can be produced by a normal polycondensation method or ring-opening polymerization method, and may be either batch polymerization or continuous polymerization. In addition, both the transesterification reaction and the reaction by direct polymerization can be applied, but continuous polymerization is preferable in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased, and the cost is reduced. In this respect, direct polymerization is preferable.

  When (A) the polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof Can be prepared by subjecting (i) a dicarboxylic acid or an ester-forming derivative thereof to a diol or an ester-forming derivative thereof 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 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, Cyclohexahexyldistin 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.

  The (A) polyester resin of the present invention can be used alone or in combination. However, in the present invention, it is not preferable to use a non-liquid crystalline polyester and a liquid crystalline polyester in combination as the polyester resin because the fluidity may be lowered.

  The (B) amorphous resin used in the present invention is at least one selected from polycarbonate resins, styrene resins, acrylic resins, polyarylate resins, and polyphenylene ether resins. The polycarbonate resin is bisphenol A, that is, 2,2′-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylalkane or 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl ether, 2 1,2′-bis (3,5-dimethyl-4-hydroxydenyl) propane, a polycarbonate mainly composed of one or more dihydroxy compounds selected from 1,1′-bis (4-hydroxyphenyl) cyclohexane is there. Among these, bisphenol A, that is, a product produced using 2,2'-bis (4-hydroxyphenyl) propane as a main raw material is preferable.

  The production method of the polycarbonate resin is not particularly limited, and can be produced by a normal transesterification reaction and a 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. It is possible, and it is preferable that the usage-amount of another dihydroxy compound is 10 mol% or less with respect to the total amount of a dihydroxy compound. The degree of polymerization of these polycarbonate resins is not particularly limited, but the specific viscosity is 1.1 to 2.5, particularly 1.2 to 2.0 when 1 g of polycarbonate resin is dissolved in 90 ml of tetrachloroethane and measured at 25 ° C. Those in the range are preferable, and those in the range of 1.2 to 1.9 are most preferable.

  The styrenic resin is arbitrary as long as it is a polymer containing a styrene structural unit, that is, an aromatic vinyl unit. For example, (a) styrene resin, α-methylstyrene resin, (ii) conjugated diene rubber such as polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, styrene, α-methylstyrene, dimethylstyrene, Aromatic vinyl such as vinyl toluene and vinyl cyanide such as acrylonitrile, methacrylonitrile, and other polymerizable monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate as required ABS resin obtained by graft polymerization, (iii) AS resin in which aromatic vinyl and vinyl cyanide exemplified above are copolymerized, and (e) Conjugated diene rubber and aromatic vinyl exemplified above are co-polymerized. Polymerized high impact poly Styrene resin, (o) a block copolymer of the above aromatic vinyl and diene.

  The (o) block copolymer may be either hydrogenated or non-hydrogenated as a constituent unit of diene. Examples of such dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc., and these do not necessarily need to be used in one type. The block copolymer can be used in combination with SBS resin (styrene / butadiene / styrene triblock copolymer), SIS resin (styrene / isoprene / styrene triblock copolymer), and the like. Can be mentioned.

  Among these exemplified (B) amorphous resins, those that can be suitably used include polycarbonate resins, polyarylate resins, polyphenylene ether resins, ABS resins, and AS resins, and more preferably polycarbonate resins. Examples thereof include resins, polyarylate resins, and AS resins. Among them, polycarbonate resins and AS resins are particularly preferable.

  The thermoplastic resin composition of the present invention is characterized by blending (A) a polyester resin and (B) an amorphous resin, and is excellent in fluidity, mechanical properties or laser weldability. A) 50 to 95% by weight of a polyester resin and (B) 50 to 5% by weight of an amorphous resin are preferably blended. More preferably, (A) the polyester resin is 50 to 92% by weight and (B) the amorphous resin is 50 to 8% by weight. Particularly preferably, (A) the polyester resin is 50 to 90% by weight and (B) the amorphous resin is 50 to 10% by weight.

  (B) When the blending amount of the amorphous resin is less than 5% by weight, there is no problem in the high fluidity and mechanical properties which are the subject of the present invention, but the low warpage and laser transmission are insufficient. This is not preferable. On the other hand, when the blending amount of the (B) amorphous resin exceeds 50% by weight, the low warpage property is outstanding, but the high heat resistance and excellent chemical resistance inherent in the polyester resin tend to decrease. The applicable products may be limited, which is not preferable.

  The resin component of the thermoplastic resin composition used in the present invention is composed of (A) a polyester resin and (B) an amorphous resin, but is not limited to these resins, and the thermoplastic resin of the present invention. Resins other than those described above can be mixed as long as the properties of the resin composition are not impaired. The resin that can be mixed may be any resin that can be melt-molded. For example, a polyethylene resin, a polypropylene resin, a polymethylpentene resin, a cyclic olefin resin, a cellulose resin such as cellulose acetate, a polyamide resin, a polyacetal resin, Polysulfone resin, polyphenylene sulfide resin, polyetheretherketone resin, polyimide resin, polyetherimide resin and the like can be mentioned. The resin to be mixed is not necessarily one type, and two or more types may be used in combination.

  The thermoplastic resin composition of the present invention is characterized by comprising (C) a fluidity improver. (C) By blending a fluidity improver, the melt viscosity of the thermoplastic resin can be greatly reduced, such as mechanical properties, laser permeability, laser weldability, recyclability, hydrolysis resistance or dry heat resistance, etc. Moreover, you may use together 2 or more types of (C) component at the point that can also improve together.

  In the present invention, the blending amount of the (C) fluidity improver must be in the range of 0.01 to 10 parts by weight of the component (C) with respect to 100 parts by weight of the total of (A) and (B). However, in terms of fluidity, mechanical properties, hydrolysis resistance, and bleed-out resistance, 0.01 to 5 parts by weight is preferable, 0.01 to 3 parts by weight is more preferable, and 0.05 to 1 part by weight Is more preferable.

  In the present invention, as the fluidity improver (C), a branched polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound, an acrylic compound, or three or more functional groups are used. Preferably, the compound has at least one functional group in that it is excellent in mechanical properties, laser transmission properties, laser welding properties, recyclability, hydrolysis resistance or dry heat resistance. More preferably, it comprises a compound.

  In the present invention, the (C) 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 structures radially from a central core. A star polymer having a chain segment as a branched chain, a graft polymer having a structure in which a polymer having a number of branch points in the main linear polymer chain and a branch chain is introduced therefrom, and branching in three dimensions And a hyperbranched polymer having a branched structure in the repeating unit and a dendrimer having a precisely controlled molecular weight distribution and degree of branching, and a star polymer and a hyperbranched polymer are preferable in terms of easy industrial production, From the viewpoint of fluidity, 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 (C) branched polymer is not particularly limited as long as it is a polymer having a branched structure, but in terms of fluidity, polyamide, polyester, polyester amide, polycarbonate, polyester polycarbonate, It is preferable to include any one structure selected from polyether, polystyrene, polyphenylene, polyimide, polyphenylene sulfide, and polyurethane. From the viewpoint of heat resistance, mechanical properties, hydrolysis resistance, or recyclability, the polyester structure and More preferably, it has a polycarbonate structure, more preferably an aromatic polymer having an aromatic ring, and particularly preferably an alkylene terephthalate structure.

  The molecular weight of the (C) 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. More preferably, the range is from 800 to 5000, still more preferably from 1000 to 3000, and the weight average molecular weight (Mw) is preferably from 300 to 150,000, and from 500 to 50,000. Is more preferable, it is more preferable that it is the range of 800-30000, and it is especially preferable that it is the range of 1000-10000.

  The molecular weight distribution (Mw / Mn) of the (C) branched polymer used in the present invention is not particularly limited, but is preferably in the range of 1 to 5 and in the range of 1 to 4 in terms of fluidity. Is more preferable, and the range of 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 (C) branched polymer used in the present invention is not particularly limited, but is preferably in the range of 0.1 to 1.0 in terms of fluidity, and is preferably 0.2 to 0.00. A range of 9 is more preferable, and a range of 0.3 to 0.9 is even more preferable. 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 (C) used in the present invention is not particularly limited, but is preferably in the range of −60 to 200 ° C. and in the range of 0 to 150 ° C. in terms of fluidity. More preferably, it is more preferably in the range of 50 to 120 ° C. In the present invention, Tg can be determined from measurement by a differential scanning calorimeter (DSC).

  The melting point (Tm) of the branched polymer (C) used in the present invention is not particularly limited. More preferably, it is more preferable that it is the range of 50-200 degreeC. In the present invention, Tm can be determined from measurement by a differential scanning calorimeter (DSC).

  The (C) 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 8,000. In terms of fluidity, mechanical properties and bleed out, Mw is preferably in the range of 1000 to 7000, more preferably in the range of 1500 to 6000, 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 (C) low molecular weight linear polyester used in the present invention is (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, or (b) a hydroxycarboxylic acid or an ester-forming derivative thereof. (C) a polymer or copolymer having at least one selected from lactone as a main structural unit, and (i) a dicarboxylic acid or its ester-forming derivative and a diol or its An ester-forming derivative is preferred. Moreover, as polyester, any of aromatic polyester, aliphatic polyester, and alicyclic polyester may be sufficient.

  The (C) 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 10,000. In terms of fluidity, mechanical properties, and bleed out, Mw is preferably in the range of 1000 to 9000, more preferably in the range of 2000 to 8000, and even more preferably in the range of 3000 to 7000. 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 (C) low-molecular-weight linear polycarbonate used in the present invention is a polymer or copolymer having a carbonate bond obtained by reacting a diol and a carbonic acid diester. Is preferably a polycarbonate diol having a hydroxyl group. 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 (C) aromatic low molecular 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, from the viewpoint 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 (C) acrylic compound used in the present invention is one in which 30 mol% or more of the constituent components is 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 1000 to 300,000 in terms of fluidity, mechanical properties, and bleed-out. More preferably, it is in the range of 10,000, more preferably in the range of 5,000 to 30,000.

  The compound (C) having three or more functional groups used in the present invention is a component necessary for improving the fluidity of the thermoplastic resin of the present invention. The component (C) is not limited as long as it is a polyfunctional compound having three or more functional groups in the molecule, and may be a low molecular compound or a high molecular weight polymer. . Such a functional group of component (C) is preferably at least one selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. Among these, it is preferable to have three or more functional groups that are the same or different. In addition, as the component (C), any compound may be used as long as it has three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound, but fluidity and mechanical properties are excellent. In that respect, a trifunctional compound or a tetrafunctional compound is more preferable.

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

  (C) As a preferred 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 preferable from the viewpoint of fluidity.

  (C) 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.

  (C) As a preferred example of a 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.

  (C) As a preferred example of a compound having three or more functional groups, when the functional group is a glycidyl group, a monomer such as triglycidyl triazolidine-3,5-dione, triglycidyl isocyanurate, poly Examples include (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, glycidyl group-containing acrylic / styrene polymer, and the like.

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

  (C) As a preferable example of a compound having three or more functional groups, when the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of the compound having three or more hydroxyl groups, or the three or more groups described above Examples thereof include ester derivatives of compounds having a carboxyl group.

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

  From the viewpoint of fluidity and mechanical properties, it is preferable that the compound (C) having three or more functional groups contains one or more alkylene oxide units. As preferred examples of the alkylene oxide unit, aliphatic alkylene oxide units having 1 to 4 carbon atoms are effective. Specific examples include a methylene oxide unit, an ethylene oxide unit, a trimethylene oxide unit, a propylene oxide unit, a tetramethylene oxide unit, 1,2-butylene oxide units, 2,3-butylene oxide units or isobutylene oxide units. In the present invention, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit in terms of excellent fluidity, mechanical properties, recyclability or productivity, and is resistant to hydrolysis and bleed. It is particularly preferable to use a compound containing a propylene oxide unit in terms of excellent out-out properties.

  The number of alkylene oxide units contained in the compound (C) having three or more functional groups used in the present invention is preferably 0.1 to 20 alkylene oxide units per functional group, 0.5 to 10 is more preferable, and 1 to 5 is more preferable.

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

  When the functional group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing a (poly) methylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly) ethylene oxide unit, (poly) tricarboxylic acid Propane-1,2,3-tricarboxylic acid containing methylene oxide units, Propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide units, Propane-1,2, containing (poly) tetramethylene oxide units 3-tricarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) methylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) ethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) trimethylene oxide units, (poly) propyl 2-methylpropane-1,2,3-triscarboxylic acid containing pyrene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide units -1,2,4-tricarboxylic acid containing, butane-1,2,4-tricarboxylic acid containing (poly) ethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units , Butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) tetramethylene oxide units, butane containing (poly) methylene oxide units 1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-teto containing (poly) ethylene oxide units Carboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, (poly ) Butane-1,2,3,4-tetracarboxylic acid containing tetramethylene oxide units, trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, (poly) trimethylene oxide Includes trimellitic acid containing units, trimellitic acid containing (poly) propylene oxide units, trimellitic acid containing (poly) tetramethylene oxide units, trimesic acid containing (poly) methylene oxide units, and (poly) ethylene oxide units Trimesic acid, trimesic acid containing (poly) trimethylene oxide units, (I) trimesic acid containing propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, hemimellitic acid containing (poly) methylene oxide units, hemimellitic acid containing (poly) ethylene oxide units, (poly) trimethylene Hemimellitic acid containing oxide units, Hemimellitic acid containing (poly) propylene oxide units, Hemimellitic acid containing (poly) tetramethylene oxide units, Pyromellitic acid containing (poly) methylene oxide units, (Poly) ethylene oxide units Containing pyromellitic acid, pyromellitic acid containing (poly) trimethylene oxide units, pyromellitic acid containing (poly) propylene oxide units, pyromellitic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide units Containing cyclohe Sun-1,3,5-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) trimethylene oxide units, Examples include cyclohexane-1,3,5-tricarboxylic acid containing a poly) propylene oxide unit, cyclohexane-1,3,5-tricarboxylic acid containing a (poly) tetramethylene oxide unit, and the like.

  When the functional group is an amino group, 1,2,3-triaminopropane containing (poly) methylene oxide units, 1,2,3-triaminopropane containing (poly) ethylene oxide units, (poly) trimethylene oxide units 1,2,3-triaminopropane containing 1,2,3-triaminopropane containing (poly) propylene oxide units, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, ( 1,2,3-triamino-2-methylpropane containing poly) methylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) ethylene oxide units, 1 containing (poly) trimethylene oxide units 1,2,3-triamino-2-methylpropane, 1,2,3-triamino-2 containing (poly) propylene oxide units Contains methylpropane, 1,2,3-triamino-2-methylpropane containing (poly) tetramethylene oxide units, 1,2,4-triaminobutane containing (poly) methylene oxide units, (poly) ethylene oxide units 1,2,4-triaminobutane, 1,2,4-triaminobutane containing (poly) trimethylene oxide units, 1,2,4-triaminobutane containing (poly) propylene oxide units, (poly) 1,2,4-triaminobutane containing tetramethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) methylene oxide units, 1,2,3,4-containing (poly) ethylene oxide units Tetraminobutane, 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, (poly) propyleneoxy 1,2,3,4-tetraminobutane containing units, 1,2,3,4-tetraminobutane containing (poly) tetramethylene oxide units, 1,3,5-triamino containing (poly) methylene oxide units Cyclohexane, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) trimethylene oxide units, 1,3 containing (poly) propylene oxide units 5-triaminocyclohexane, 1,3,5-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) methylene oxide units, (poly) ethylene oxide units included 1,2,4-triaminocyclohexane, (poly) trimethylene oxide unit 1,2,4-triaminocyclohexane containing, 1,2,4-triaminocyclohexane containing (poly) propylene oxide units, 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, ( 1,2,4,5-tetraminocyclohexane containing poly) methylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) ethylene oxide units, 1,2,4 containing (poly) trimethylene oxide units , 5-tetraminocyclohexane, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) tetramethylene oxide units, (poly) methylene oxide 1,3,5-triaminobenzene containing units, (poly) ethylene 1,3,5-triaminobenzene containing oxide units, 1,3,5-triaminobenzene containing (poly) trimethylene oxide units, 1,3,5-triaminobenzene containing (poly) propylene oxide units 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, 1,2,4-triaminobenzene containing (poly) methylene oxide units, 1,2,4 containing (poly) ethylene oxide units -Triaminobenzene, 1,2,4-triaminobenzene containing (poly) trimethylene oxide units, 1,2,4-triaminobenzene containing (poly) propylene oxide units, (poly) tetramethylene oxide units 1,2,4-triaminobenzene and the like including trimethylolpropane tris [poly (pro Etc. glycol) amine] ether are also suitable.

  When the functional group is an ester group, an aliphatic acid ester or an aromatic acid ester of a compound having three or more hydroxyl groups containing the alkylene oxide unit, or an ester of a compound having three or more carboxyl groups containing the alkylene oxide unit Derivatives and the like.

  In the case where the functional group is an amide group, an amide derivative of a compound having three or more carboxyl groups containing the above alkylene oxide unit may be used.

  As a particularly preferred example of a compound having three or more functional groups (C) containing one or more alkylene oxide units from the viewpoint of fluidity, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, (poly) oxy Propylene glycerin, (poly) oxyethylene diglycerin, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly) oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) Examples include oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, and (poly) oxypropylene dipentaerythritol. When the functional group is a carboxylic acid, (poly) ethyl Propane-1,2,3-tricarboxylic acid containing propane oxide unit, propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide unit, trimellitic acid containing (poly) ethylene oxide unit, (poly) propylene oxide Trimellitic acid containing units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, (poly) propylene And cyclohexane-1,3,5-tricarboxylic acid containing an oxide unit. When the functional group is an amino group, 1,2,3-triaminopropane containing a (poly) ethylene oxide unit, (poly) propylene oxide unit 1,2,3-triaminopropane containing (poly 1,3,5-triaminocyclohexane containing ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, ( 1,3,5-triaminobenzene containing a poly) propylene oxide unit, trimethylolpropane tris [poly (propylene glycol) amine] ether.

  The compound (C) having three or more functional groups used in the present invention reacts with the component (A) and may be introduced into the main chain and side chain of the component (A), and reacts with the component (A). Instead, the structure at the time of blending may be maintained. (C) The reaction rate of the functional group of the compound having three or more functional groups is preferably 40% or more, more preferably 50% or more, and particularly preferably 60% or more.

  The viscosity of the compound (C) having three 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 at the time of molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  The molecular weight or weight average molecular weight (Mw) of the compound having three or more functional groups (C) 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, (C) Mw of a compound having three or more functional groups is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. .

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

  (C) 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, (C) the compounding amount of the compound having three or more functional groups is a total of 100 of (A) and (B) in terms of fluidity, mechanical properties, hydrolysis resistance and bleed-out resistance. Component (C) is preferably in the range of 0.01 to 5 parts by weight with respect to parts by weight, more preferably in the range of 0.01 to 3 parts by weight from the viewpoint of fluidity and mechanical properties, More preferably, it is blended in the range of 0.01 to 1 part by weight, and particularly preferably in the range of 0.1 to 1 part by weight. (C) When the compounding amount of the compound having three or more functional groups is less than 0.01 parts by weight, the mechanical properties are good, but the effect of improving fluidity is poor. On the other hand, when it is added in an amount exceeding 5 parts by weight, the fluidity is greatly improved as compared with the case where it is not added, but the mechanical properties of the resin composition may be deteriorated, which is not preferable.

  In the present invention, (A) a polyester resin, (B) an amorphous resin, and (C) a compound having three or more functional groups are blended in terms of fluidity, mechanical properties, laser permeability, or laser weldability. It is preferable that the component (C) has at least one hydroxyl group or carboxyl group from the viewpoint of fluidity, and the component (C) has three or more hydroxyl groups, carboxyl groups, Or it is more preferable that it has an amino group, and it is still more preferable that (C) component has three or more hydroxyl groups.

  In the thermoplastic resin composition of this invention, it is preferable to mix | blend (D) a filler from the point of a mechanical characteristic or a moldability. The blending amount of the filler (D) is preferably 0.01 to 120 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B) in terms of fluidity and mechanical properties. More preferably, it is blended in the range of 1 to 100 parts by weight, and more preferably in the range of 5 to 90 parts by weight. When the added amount of the filler is less than 1 part by weight, the effect of improving the mechanical properties by adding the filler is small. On the other hand, when the added amount exceeds 120 parts by weight, the mechanical properties are improved. However, even if a polyfunctional compound is added, the fluidity of the resin composition is lowered, which is not preferable.

  As a kind of (D) filler which can be used for the resin composition of this invention, glass fiber can be used preferably. The fillers that can be used are not limited to these, and any fillers such as fibrous, plate-like, powdery, and granular can be mixed and used. Specifically, 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, organic natural fibers such as kenaf fibers, bamboo fibers, and cellulose fibers. , Gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, 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. Fibrous, whisker-like filler, mica, talc, kaolin, silica, calcium carbonate, glass flake, glass beads, glass microballoon, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, calcium polyphosphate , Graphite, barium sulfate, powdered, such as zirconium silicate, 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 selected from long fiber type or short fiber type chopped strand, cut fiber, milled fiber, etc. Can be any of a round shape, a rectangular shape, an eyebrows shape, and the like.

  The (D) 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.

  The filler (D) 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.

  Moreover, in this invention, it is preferable to mix | blend layered silicate with respect to fluidity | liquidity, mechanical characteristics, hydrolysis resistance, etc., and it is still more preferable that it is an organic modified layered silicate.

  In the present invention, in order to impart mechanical strength and other characteristics of the resin composition, it is preferable to blend (E) an impact resistance improver. (E) The blending amount of the impact resistance improver is preferably in the range of 1 to 100 parts by weight with respect to the total of 100 parts by weight of (A) and (B) in terms of fluidity and mechanical properties. It is more preferable to mix | blend in the range of -70 weight part, and it is further more preferable to mix | blend in the range of 1-50 weight part.

  As the (E) impact resistance improver that can be used in the present invention, known ones can be used for the thermoplastic resin, but in the thermoplastic resin composition of the present invention, (A) By adding an elastomer to the polyester resin component and the (B) amorphous resin component, impact resistance and cold resistance can be imparted. Examples of such elastomers include ethylene and styrene. The addition amount of the elastomer is preferably 1 to 50 parts by weight with respect to 100 parts by weight as a total of (A) the polyester resin component and (B) the amorphous resin component. In particular, (E) styrene-based elastomer (hereinafter referred to as “component (E)”) is used as the elastomer, so that (A) polyester resin component and (B) amorphous resin component have high laser beam transparency. However, it is possible to further impart impact resistance and cold resistance. The heat resistance here is a resin molded body formed by insert molding of metal or the like, which is greatly different from polybutylene terephthalate resin, etc., for example, in a low temperature and high temperature repeated environment. To tell.

  As said (E) component, it is preferable to use the styrene-type elastomer which has a light transmittance higher than the light transmittance in the same wavelength range of a polybutylene terephthalate in a 400-1100 nm wavelength range. As such a styrene-based elastomer, a styrene-butadiene block copolymer is preferably exemplified, and an epoxidized product of a styrene-butadiene block copolymer is more preferred. As an epoxidized product of this styrene-butadiene block copolymer, “Epofriend A1010” manufactured by Daicel Chemical Industries, Ltd. can be suitably used.

  The added amount of the component (E) used in the present invention is 100 parts by weight based on the total amount of the (A) polyester resin component and the (B) amorphous resin component, from the balance of laser beam transparency, moldability, and cold resistance. It is the range of 1-50 weight part, and the range of 2-20 weight part is more preferable. If the addition amount is less than 1 part by weight, there is almost no effect of impact resistance and cold resistance due to the addition of the component (E), and if it exceeds 50 parts by weight, the moldability, particularly the fluidity, is not preferred.

  In addition, aliphatic and aromatic glycidyl esters or glycidyl ethers can be added to the resin composition of the present invention.

  The thermoplastic resin composition of the present invention is characterized by comprising (F) a stabilizer. (F) By blending a stabilizer, the melt viscosity of the thermoplastic resin composition can be greatly reduced, such as mechanical properties, laser permeability, laser weldability, recyclability, hydrolysis resistance, or dry heat resistance. Can also be improved.

  In the present invention, as the stabilizer (F), any of those usually used as stabilizers for thermoplastic resins can be used. Specific examples include antioxidants, light stabilizers, heat stabilizers, metal deactivators, etc., and include fluidity, mechanical properties, heat resistance, laser permeability, laser weldability, recyclability, A metal deactivator is preferred in that it is excellent in hydrolyzability or dry heat resistance. In the present invention, the metal deactivator is a catalyst deactivator that deactivates a catalyst that can be added when producing (A) a polyester resin, (B) an amorphous resin, or (C) a fluidity improver. By working, a transesterification reaction or the like that can occur between (A) the polyester resin and (B) the amorphous resin can be suppressed, so that a thermoplastic resin composition having particularly excellent fluidity can be obtained.

  It is essential that the stabilizer (F) used in the present invention is blended in an amount of 0.01 to 1 part by weight with respect to a total of 100 parts by weight of (A) and (B). 0.03 to 1 part by weight is preferable, 0.04 to 0.5 part by weight is more preferable, and 0.04 to 0.5 part by weight is more preferable in view of excellent heat resistance, laser weldability, recyclability, hydrolysis resistance, and dry heat resistance. More preferably, it is from 05 to 0.3 parts by weight.

  Examples of the antioxidant used in the present invention include hindered phenol compounds, phosphite compounds, thioether compounds, vitamin compounds, etc., which are excellent in fluidity, mechanical properties, laser permeability, or laser weldability. In this respect, hindered phenol compounds and / or phosphite compounds are more preferable, and phosphite compounds are more preferable.

  Examples of hindered phenol compounds used in the present invention include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3 '-Methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1, 6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t -Butyl-4-hydroxyphenyl) -propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3 t-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9- Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) Undecane, N, N′-bis-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis-3- (3 ′ -Methyl-5'-tert-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenol) Pionyl] hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′- Hexamethylene bis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide etc. can be mentioned. Preferably, triethylene glycol bis- [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) ) Propionate] methane, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], pentaerythrityl-tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide). Specific product names of hindered phenol compounds include “ADEKA STAB” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330 manufactured by ADEKA. "Irganox" 245, 259, 565, 1010, 1035, 1076, 1098, 1222, 1330, 1425, 1520, 3114, 5057, manufactured by Ciba Specialty Chemicals, Sumitomo Chemical "Smilizer" BHT-R, MDP-S , BBM-S, WX-R, NW, BP-76, BP-101, GA-80, GM, GS, “Sianox” CY-1790 manufactured by Cyanamid, and the like.

  In the present invention, the phosphite compound is preferably one in which at least one P—O bond is bonded to an aromatic group, and specific examples thereof include tris (2,4-di-t-butylphenyl) phosphine. Phyto, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-Methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5 t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkyl phosphite), etc. Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4) -Methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphonite and the like can be preferably used. Specific product names of phosphite compounds include “ADEKA STAB” manufactured by ADEKA PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A, 329A, 1178, 1500, C, 135A, 3010, TPP, Ciba Specialty Chemicals “Irgaphos” 168, Sumitomo Chemical “Smilizer” P-16, Clariant “Sand Stub” P-EPQ, GE “Weston” 618 619G, 624, and the like.

  The (F) phosphite compound used in the present invention includes tridecyl phosphite, triisodecyl phosphite, bis (2-ethylhexyl phosphite, trimethyl phosphate, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diester Dodecyl phosphite, diphenyloctyl phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (4-nonylphenyl) phosphite, tris (3 -Nonylphenyl) phosphite, tribenzyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-tert-butyl) Phenyl) [1,1-biphenyl] -4 4'-diylbisphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2-nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, ditridecyl Any phosphite compound such as pentaerythritol diphosphite and bis (3-methyl-2,6-di-tert-butylphenyl) pentaerythritol diphosphite can be used. As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, tetrakis ( 2,4-di-t-butylphenyl) 4,4'-bi Enylene phosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phos Phyto, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite 4,4′-isopropylidenebis (phenyl-dialkyl phosphite) and the like, and tris (2,4-di-t-butyl). Tilphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite can be preferably used. Specific product names of phosphite compounds include “ADEKA STAB” manufactured by ADEKA PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A, 329A, 1178, 1500, C, 135A, 3010, TPP, Ciba Specialty Chemicals “Irgaphos” 168, Sumitomo Chemical “Smilizer” P-16, Clariant “Sand Stub” P-EPQ, GE “Weston” 618 619G, 624, and the like.

  The (F) phosphite compound used in the present invention is preferably contained in an amount of 0.01 to 1 part by weight with respect to a total of 100 parts by weight of (A) and (B). More preferably, it is 0.05-0.4 weight part, More preferably, it is 0.1-0.3 weight part. When the addition amount is less than 0.01 parts by weight, there is no effect on the retention stability improvement, and when the addition amount exceeds 1 part by weight, the mechanical properties may be lowered, which is not preferable. .

  Examples of the light stabilizer used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, nickel compounds, and the like. It is preferable to use a hindered amine compound in combination with at least one of a benzophenone compound, a benzotriazole compound, and an aromatic benzoate compound in terms of excellent properties, light resistance, and weather resistance.

  Examples of the metal deactivator used in the present invention include triazole compounds, polyvalent amine compounds, hydrazine derivative compounds, phosphate compounds, etc., which are excellent in fluidity, mechanical properties, laser transparency or laser weldability. In this respect, phosphate compounds are preferred. Specific trade names of metal deactivators include “Irganox” MD1024 from Ciba Specialty Chemicals, “Inhibitor” OABH from Eastman Kodak, “Adekastab” CDA-1, CDA-6 from ADEKA, AX -71, Uniroyal “Nauguard” XL-1, and the like.

  Examples of the (F) phosphate compound used in the present invention include 2-ethylhexyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, monostearyl acid Examples include phosphate, distearyl acid phosphate, methyl phosphate, isopropyl phosphate, butyl phosphate, hexyl phosphate, 2-ethylhexyl phosphate, lauryl phosphate, octyl phosphate, isodecyl phosphate, dioctadecyl phosphate, dibenzyl phosphate and the like.

  Furthermore, in the present invention, crystal nucleating agents, plasticizers, ultraviolet absorbers, antibacterial agents, other stabilizers, mold release agents, colorants including pigments and dyes, lubricants, and antistatics, as long as the effects of the present invention are not impaired. One or more agents or flame retardants can be added.

  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) polyester resin, (B) amorphous resin, (C) fluidity | liquidity Improving agent and (F) stabilizer, and other components as needed, in a single-screw or twin-screw extruder or a triaxial or more multi-screw extruder. The method of removing is 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 with a twin-screw extruder, uniformly melting and kneading in that a resin composition excellent in fluidity and mechanical properties can be obtained. The method is more preferred. In particular, when the screw length is L and the screw diameter is D, a melt kneading method using a twin screw extruder with L / D> 30 is particularly preferable. The screw length here refers to the length from the position where the screw base material is supplied to the tip of the screw. The greater the L / D, the greater the fluidity improving effect of the (C) fluidity improving agent. The upper limit of L / D of a 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 (kneading zone) of the kneading disk to the total screw length 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 charging 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 ) Polyester resin, (B) Amorphous resin, (C) Fluidity improver, (F) Stabilizer, and other components as needed are batch feed kneading method, from the main feed port (A ) Polyester resin, (B) Amorphous resin, (F) Stabilizer and other components are supplied, and (C) Fluidity improver is supplied from the secondary input port installed between the main input port and the extruder tip. An individual charging kneading method, which is a method of melt mixing, may be mentioned. The individual charging method is preferable in terms of excellent fluidity, mechanical properties, and production stability, and (C) continuously supplying a fluidity improver. Is more preferable. In addition, (A) a thermoplastic resin, (B) an amorphous resin, (F) a stabilizer and other components are melt-kneaded into pellets, and then (C) a fluidity improver and other components are melt-kneaded. A method of melt kneading in multiple stages such as a kneading method is also preferable. Furthermore, in the present invention, when (D) the filler is blended, the side feed method, which is a method of blending (D) filler from the sub-feed port installed between the main feed port and the extruder tip, is used. It is preferable.

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

  In the present invention, the above 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, and in particular, laser welding is possible. It is suitable for automotive parts and laser / electrical parts.

  The resin composition of the present invention can be used for the following specific applications. Specific examples 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, rotation sensors, Accelerometer, Distributor cap, Coil base, Actuator case for ABS, Top and bottom of radiator tank, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer, Distribution Turcap, vapor canister housing , Air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control levers, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Automotive products such as wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Accessories, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, electrical connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings, and Internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers, handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings And electric / electronic parts represented by internal parts, facsimile housings and internal parts, parabolic antennas, and the like.

  Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROM , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts.

  Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases , Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brushes Electric and electronic parts such as holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels Thermal insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weed bags Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection Non-woven fabric, seedling pots, vegetation piles, seed string tape, germination sheets, house lining sheets, farmhouse fasteners, slow-release fertilizers, root-proof sheets, garden nets , Insect repellent nets, infant tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage prevention nets, incentive strings, windproof nets and other agricultural materials, paper diapers, sanitary products packaging materials, cotton swabs, towels, toilet seat wipes, etc. Medical products such as hygiene products, medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressings, wound tape bandages, sticker base fabrics, surgical sutures, fracture reinforcements, medical films, etc. Packaging film for supplies, calendars, stationery, clothing, food, etc., trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets and other containers, tableware, hot fill containers, electronic Range cooking containers, cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, Cover materials, envelopes with windows, fruit baskets, hand tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural Textile composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tapes, prints, Heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, nonwoven fabric, hot melt binder, magnetic material, zinc sulfide, electrode material powder, etc. Body binder, optical element, conductive emboss stay , IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag, chair, table Useful as cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on. In a preferred embodiment, the thermoplastic resin composition of the present invention has not only good mechanical properties and high fluidity, but also high laser permeability and laser weldability, as well as low warpage. It is particularly useful for various automotive parts and electrical / electronic parts that perform laser welding.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention and can also carry out various deformation | transformation.

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

(A) Polyester resin A-1: Polybutylene terephthalate ("Toraycon" 1100S manufactured by Toray Industries, Inc.).

(B) Amorphous resin B-1: Polycarbonate (“Taflon” A1900 manufactured by Idemitsu Kosan Co., Ltd.)
B-2: Acrylonitrile-styrene resin (acrylonitrile / styrene = 25/75 manufactured by Toray Industries, Inc.).

(C) Compound C-1 having three or more functional groups: Glycerin (molecular weight 92, 0 alkylene oxide units per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
C-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, manufactured by ARDRICH)
C-3: Pentaerythritol (molecular weight 136, 0 alkylene oxide units per functional group, manufactured by Tokyo Chemical Industry Co., Ltd.)
C-4: Polyoxyethylene diglycerin (molecular weight 410, number of alkylene oxide units per functional group 1.5, Sakamoto Pharmaceutical Co., Ltd. SC-E450)
C-5: Oxyethylenetrimethylolpropane (molecular weight 266, number of alkylene oxide units per functional group, TMP-30U manufactured by Nippon Emulsifier Co., Ltd.)
C-6: Polyoxyethylene pentaerythritol (Molecular weight 400, number of alkylene oxide units per functional group 1.5, Nippon Emulsifier Co., Ltd. PNT-60U)
C-7: Polyoxypropylene trimethylolpropane (molecular weight 308, 1 alkylene oxide (propylene oxide) unit per functional group, Nippon Emulsifier TMP-F32)
C-8: Polyoxypropylene pentaerythritol (molecular weight 630, number of alkylene oxide (propylene oxide) units 2.1 per functional group, “Polyol” 4360 manufactured by Perstorp).

(C ′) Compound C′-1: 1,6-hexanediol having less than 3 functional groups (manufactured by ARDRICH)
C′-2: 4,4′-dihydroxybiphenyl (Honshu Chemical Co., Ltd.).

(D) Filler D-1: Talc (Nippon Talc "Microace" P-6)
D-2: Chopped strand type glass fiber (fiber diameter 13 μm, manufactured by Nittobo Co., Ltd. 3PE949).

(E) Impact modifier E-1: Olefin elastomer (“Evaflex” EEA A709, manufactured by Mitsui Chemicals, Inc.)
E-2: Styrene-butadiene resin (“Epofriend” AT501 manufactured by Daicel Chemical Industries, Ltd.).

(F) Stabilizer F-1: Phosphate compound (“ADEKA STAB” AX71 manufactured by ADEKA).

  Moreover, the evaluation method used for the Example and the comparative example is collectively 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 were a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Examples 1 to 12 and Comparative Examples 1 to 7 were performed at an injection pressure of 35 MPa, and other than that, an injection pressure of 65 MPa.

(2) Impact properties Using a test piece molded at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, Charpy impact strength with a notch was measured according to ISO179.

(3) Bending characteristics Using a test piece molded at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, bending strength and bending elastic modulus were measured according to ISO178.

(4) Tensile properties Using test pieces molded at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, the tensile strength was measured in accordance with ISO527-1,2.

(5) Heat resistance Using a test piece molded at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, the deflection temperature under load was measured in accordance with ASTM D648.

(6) Low Warpage Property A test piece having the shape shown in FIG. 1 was molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and the amount of warpage on the side opposite to the gate was measured as shown in FIG.

(7) Stability of retention during molding Using an injection molding machine (Toshiba IS80EPN), cylinder temperature 260 ° C., mold temperature 80 ° C., weighing 80 mm, injection pressure 90 MPa, injection time / cooling time = 8/8 seconds. Under the molding conditions, the spiral flow length (10 mm width, 2 mm thickness) was used to measure the spiral flow length. Molding from 1 shot to 30 shots, when the spiral flow length of the 30th shot is less than -10% lower than that of the 1st shot, "○", when the reduction is over -10% It was written as “×”. A material having a large decrease width indicates that the residence heat stability during molding is poor and the viscosity of the material is increased during continuous molding.

(8) Laser beam transmittance L shown in FIG. 3 was a 80 mm square, and a laser beam transmittance evaluation test piece having a thickness D of 3 mm was molded. The molding conditions are a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. FIG. 3A is a plan view of the laser beam transmittance evaluation test piece, and FIG. 3B is a side view of the test piece. The sprue 3 and runner 4 portions of the molded piece as shown in FIG. 3 were cut by the gate 5, and the remaining portion 6 was used as a laser beam transmission evaluation test piece. The tester used was an ultraviolet near infrared spectrophotometer (UV-3100) manufactured by Shimadzu Corporation, and an integrating sphere was used as the detector. The transmittance represents the ratio between the transmitted light amount and the incident light amount as a percentage. In the tables showing Examples and Comparative Examples, the light transmittance in the near infrared 800 to 1100 nm wavelength region is described as “transmittance”.

(9) Laser weldability The laser weldability evaluation test piece is a laser weldability test piece obtained by cutting a molded product having the same shape as the laser beam transmission evaluation test piece 6 of FIG. 3 into a width W of 24 mm and a length L of 70 mm. It was set to 7.
FIG. 4A is a plan view of the test piece after the processing, and FIG. 4B is a side view thereof.
As the laser welding machine, MODULAS C manufactured by Leister was used. This welding machine is an apparatus using a semiconductor laser, and the wavelength of the laser beam is near infrared of 940 nm. The maximum output is 35 W, the focal length L is 38 mm, and the focal diameter D is 0.6 mm.
FIG. 5 is a schematic view showing a laser welding method.

  As shown in FIG. 5, a laser welding test piece 7 using a material that transmits a laser beam is placed on the upper part, and a laser welding test piece 8 that uses a material that absorbs the laser beam is placed on the lower part. Combine and irradiate with laser beam from the top. Laser irradiation was performed along the laser welding trajectory 9, and laser welding conditions were performed under conditions where the best welding strength was obtained in the range of 15 to 35 W output and 1 to 50 mm / sec. The focal length was 38 mm and the focal diameter was fixed at 0.6 mm.

  Whether or not laser welding is possible is described as “welding or not”. When possible, “○” was indicated.

  FIG. 6A is a plan view of the laser welding strength measurement test piece 12 laser-welded by the above method, and FIG. 6B is a side view of the test piece. The laser welding strength measurement test piece is a laser welding test piece shown in FIG. 4 in which the laser beam transmission side sample 7 and the laser beam absorption side sample 8 are overlapped with an overlapping length L of 30 mm and a welding distance Y of 20 mm. These are welded together at the welded portion 13. A general tensile tester (AG-500B) was used to measure the welding strength, and both ends of the test piece were fixed, and a tensile test was performed so that a tensile shear stress was generated at the welded portion. The tensile speed during strength measurement is 1 mm / min, and the span is 40 mm. The welding strength was the stress when the welded site was broken. In addition, the laser welding resin composition of the present invention is used for the laser beam transmitting sample, and 30% by weight of glass fiber and 0% of carbon black are added to the laser beam absorption side sample 8 with respect to 70% by weight of the polybutylene terephthalate resin. The material added by 4 parts by weight was used.

[Examples 1-12, Comparative Examples 1-7]
(A) Polyester resin, (B) Amorphous resin, (C) Fluidity improver, (D) Filler and (F) Stabilizer are blended together at the mixing ratio described in Table 1 and Table 2, and L Using a twin screw extruder with / D = 45, melt kneading was performed under the conditions of a cylinder temperature of 250 ° C. and a rotation speed of 200 rpm to obtain a pellet-shaped resin composition. The obtained resin composition was injection molded using a Sumitomo Heavy Industries, Ltd. injection molding machine SG75H-MIV at a cylinder temperature of 250 ° C. and a mold temperature of 80. The above evaluation was performed using each molded article for evaluation.

  The evaluation results are shown in Tables 1 and 2.

  From the results of Examples 1 to 12 and Comparative Examples 1 to 7, 0.01 to 10 weight percent of (C) fluidity improver was added to 100 weight parts of (A) polyester resin and (B) amorphous resin in total. It can be seen that the thermoplastic resin composition comprising 0.01 to 1 part by weight of the part and (F) stabilizer is excellent in fluidity and mechanical properties. Furthermore, from Examples 7 to 10, by blending 0.03 to 1 part by weight of (F) stabilizer, it is particularly excellent in fluidity, and by blending (D) a filler, heat resistance It turns out that it is excellent.

[Examples 13 to 36, Comparative Examples 8 to 22]
(A) Polyester resin, (B) Amorphous resin, (C) Fluidity improver, (F) Stabilizer, etc. are blended together at the blending ratio described in Tables 3 to 6, and (D) filler is added. It supplied from the side feeder and melt-kneaded on the conditions of cylinder temperature 250 degreeC and rotation speed 200rpm using the twin-screw extruder of L / D = 45, and obtained the pellet-shaped resin composition. The obtained resin composition was injection molded using a Sumitomo Heavy Industries, Ltd. injection molding machine SG75H-MIV at a cylinder temperature of 250 ° C. and a mold temperature of 80. The above evaluation was performed using each molded article for evaluation.

  The evaluation results are shown in Tables 4-7. Tables 3 to 5 show examples, and Tables 6 to 7 show comparative examples.

  From the results of Tables 3 to 7, the following became clear.

  In comparison between Examples 13 to 18 and Comparative Examples 8 and 19, when (D) a filler (example is glass fiber) is not included, there is an effect of improving fluidity, but warpage and mechanical strength. It was found that there is a tendency to decrease. On the other hand, when a large amount of filler is contained, not only the fluidity during molding is significantly reduced, but also laser transmittance may be lowered, which is not preferable.

  In the comparison between Examples 16, 19 to 21, 31 and Comparative Examples 9 and 10, when (B) the amorphous resin was not added, not only the laser beam sufficient for laser welding was not transmitted, It turns out that the warpage is large. Further, it was found that when the amount of the amorphous resin added is too large, there is no problem in laser welding, but even when a polyfunctional compound is added, fluidity may not be sufficiently secured.

  In the comparison between Examples 16, 22 to 25 and Comparative Examples 11 and 12 to 17, when a compound having three or more functional groups was added as the (C) fluidity improver, the resin composition depending on the amount added It has been found that the fluidity of the product is greatly improved.

  In comparison between Examples 16 and 26 to 31 and Comparative Examples 9 to 12 and 15 to 18, when (C) a compound having three or more functional groups is included as a fluidity improver, the fluidity improvement effect is large. I understand.

  From a comparison between Example 16 and Comparative Examples 8 and 19, when the amount of filler added is less than 2 parts by weight, the reinforcing effect of the resin composition is small, and when used in an amount exceeding 120 parts by weight, It turned out that fluidity | liquidity becomes low.

It is a perspective view of the test piece used for evaluation of low curvature in an example. It is a bottom view of the test piece used for evaluation of low curvature in an example. (A) is a top view of the test piece for evaluating the laser beam transmittance used in the Example, (b) is a side view of the test piece. (A) is a top view of the laser welding test piece used in the Example, (b) is a side view of the test piece. It is a schematic perspective view which shows the outline of the laser welding method in the laser welding test used in the Example. (A) is a top view of the test piece for laser welding strength measurement after the laser welding used in the Example, (b) is a side view of the test piece.

Explanation of symbols

1: Gate 2: Opening part 3: Sprue 4: Runner 5: Gate 6: Laser beam transmission evaluation test piece 7: Laser welding test piece (transmission side)
8: Laser welding specimen (absorption side)
9: Laser beam orbit 10: Laser beam irradiation device 11: Laser beam 12: Test piece for measuring laser welding strength 13: Laser welding part

Claims (13)

  (A) 0.01 to 10 parts by weight of a fluidity improver and (F) 0.01 to 1 part by weight of a stabilizer for a total of 100 parts by weight of the polyester resin and (B) an amorphous resin. A thermoplastic resin composition obtained by blending.   The thermoplastic resin composition according to claim 1, wherein (C) the fluidity improver is a compound having three or more functional groups, and includes one or more alkylene oxide units.   (C) The fluidity improver is a compound having three or more functional groups, and the functional groups are selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, or an amide group. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition is at least one group.   (A) The polyester resin is one or more selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polybutylene terephthalate resin composed of polybutylene terephthalate and polybutylene terephthalate copolymer, The thermoplastic resin composition according to any one of claims 1 to 3.   (B) The amorphous resin is at least one selected from polycarbonate resin, styrene resin, acrylic resin, polyarylate resin, and polyphenylene ether resin. Thermoplastic resin composition.   Furthermore, the thermoplastic resin composition in any one of Claims 1-5 formed by mix | blending (D) a filler.   The filler (D) is talc or glass fiber and is blended in an amount of 0.01 to 120 parts by weight with respect to a total of 100 parts by weight of (A) and (B). Thermoplastic resin composition.   Furthermore, (E) The thermoplastic resin composition in any one of Claims 1-7 formed by mix | blending an impact resistance improving agent.   (E) The impact resistance improver is a styrene elastomer which is a copolymer of styrene and butadiene, and the styrene elastomer is blended in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of (A) and (B). The thermoplastic resin composition according to claim 8.   The thermoplastic resin composition according to any one of claims 1 to 9, wherein the stabilizer (F) is a phosphite compound or / and a phosphate compound.   The thermoplastic resin composition for laser welding according to any one of claims 1 to 10.   A molded article for laser welding comprising the thermoplastic resin composition for laser welding according to claim 11.   A composite molded body obtained by laser welding the molded product according to claim 12.

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