JP2009132861A - Thermoplastic resin composition for laser welding, and molded article and composite molded product produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having high fluidity in addition to laser transmittance, laser-welding performance, fuel resistance, mechanical properties and low warpage and to provide a composite formed article produced by the laser welding of formed articles of the resin composition. <P>SOLUTION: The thermoplastic resin composition for laser welding use is produced by compounding (A) 50-95 wt.% polyester resin and (B) 50-5 wt.% amorphous polyester resin and, based on 100 pts.wt. of the sum of the components (A) and (B), (C) 0.01-5 pts.wt. of a polyfunctional compound having three or more functional groups and (D) 1-120 pts.wt. of an inorganic filler. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laser welding thermoplastic resin composition having not only laser permeability, laser weldability and mechanical properties but also high fluidity, a laser wear molded article, and a laser welded composite molded article.

  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 polyester resin obtained has a problem that the viscosity is increased and the fluidity is lowered.

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

  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.

  In the laser welding method, it is essential for the resin material applied to the laser beam transmission side molded body to transmit the laser beam. When the energy of the irradiated laser beam is 100%, it is transmitted through the laser beam transmission side molded body to the back side. The present inventors have found that at least 10% or more energy is required. When a molded product having a laser beam transmittance of less than 10% is applied to the molded product on the laser beam transmission side, there is a high possibility that problems such as melting and smoke generation occur on the laser beam incident surface.

  However, polyester resins, especially polybutylene terephthalate resins, have a very low laser beam transmittance compared to thermoplastic resins such as nylon resins. When applying a laser welding method with polybutylene terephthalate resin as a molded product on the laser beam transmission side. However, the laser beam transmittance is low, so the thickness is severely limited. In order to improve the laser beam transmittance, it is necessary to deal with the thinning, and the degree of freedom in product design is very small.

  Patent Document 3 describes that the welding condition width is widened by controlling the melting point by using a polybutylene terephthalate-based copolymer in the laser welding method. A great improvement cannot be expected. Therefore, an improvement in the degree of freedom in the thickness design of the molded article cannot be expected, and the moldability of the polybutylene terephthalate resin is impaired.

  Patent Document 4 discloses polybutylene terephthalate resin or polybutylene terephthalate resin and polycarbonate resin made of polybutylene terephthalate and polybutylene terephthalate copolymer, acrylonitrile / styrene copolymer, polyphenylene oxide, styrene resin, acrylic resin, polyether An example of improving laser beam transmittance by blending one or more resins of sulfone, polyarylate, and polyethylene terephthalate and performing laser welding is disclosed in Patent Document 5 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.

Patent Document 4, Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8 include non-polyethylene resins such as polybutylene terephthalate or polybutylene terephthalate-polybutylene terephthalate copolymer, polycarbonate resin, and styrene acrylonitrile resin. A laser welding resin composition comprising a crystal resin is disclosed. In this document, the transmittance sufficient to apply the polybutylene terephthalate resin to the transmission side during laser welding is ensured. In the case of application, sticky matter may be generated due to contact with fuel such as gasoline, and application to automobile electrical parts may be limited.
JP 2001-200038 A (Claims) JP-A-7-304970 (Claims) JP 2001-26656 A (paragraphs [0008] to [0024]) Japanese Patent Laying-Open No. 2003-292752 (Claims) WO2003 / 085046 (Claims) JP 2004-315805 A (Claims) JP-A-2005-133087 (Claims) JP 2005-187798 A (Claims)

  An object of the present invention is to provide a polyester resin composition having not only laser permeability, laser weldability, fuel resistance, mechanical properties and low warpage, but also high fluidity, and a composite molded article obtained by laser welding a molded product comprising the same. Is to provide.

  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) 50 to 95% by weight of a polyester resin other than (A) and (B), and (B) non-comprising terephthalic acid and 1,4-cyclohexanedimethanol, or terephthalic acid, 1,4-cyclohexanedimethanol, ethylene glycol 50% to 5% by weight of a crystalline polyester resin is blended, and (C) a polyfunctional compound having three or more functional groups is added to 0.01 part by weight of the total amount of (A) and (B). ~ 5 parts by weight, (D) a thermoplastic resin composition for laser welding comprising 1 to 120 parts by weight of an inorganic filler,
(2) (C) The thermoplastic resin composition according to (1), wherein the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units.
(3) (C) At least one group in which the functional group of the polyfunctional compound having three or more functional groups is selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group The thermoplastic resin composition according to (1) or (2), wherein
(4) One type of polyester resin other than (A) and (B) selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polybutylene terephthalate resin comprising polybutylene terephthalate and polybutylene terephthalate copolymer It is the above, The thermoplastic resin composition in any one of (1)-(3) characterized by the above-mentioned.
(5) The thermoplastic resin composition according to any one of (1) to (4), wherein the inorganic filler (D) is a glass fiber.
(6) The thermoplastic resin composition according to any one of (1) to (5), further comprising (E) an impact resistance improver.
(7) (E) The impact resistance improver is a styrene elastomer, and 1 to 100 parts by weight of the styrene elastomer is blended with respect to 100 parts by weight of the total amount of (A) and (B). Thermoplastic resin composition.
(8) The thermoplastic resin composition for laser welding according to any one of (1) to (7), comprising (F) a phosphorus-based stabilizer.
(9) A laser welding molded product comprising the laser welding thermoplastic resin composition according to any one of (1) to (8).
(10) A composite molded product obtained by laser welding the molded product according to (9).

  According to the present invention, a polyester resin composition having not only laser permeability, laser weldability, fuel resistance, mechanical properties, low warpage, but also high fluidity, and a composite molded body obtained by laser welding a molded product comprising the polyester resin composition Can be provided.

  The polyester resins other than (A) and (B) used in the present invention are (i) dicarboxylic acid or an ester-forming derivative thereof and diol or an ester-forming derivative thereof, (b) hydroxycarboxylic acid or an ester-forming derivative thereof, (C) A polymer or copolymer having at least one selected from lactones as a main structural unit, and is a polyester resin other than (B) below (hereinafter referred to as a polyester resin other than (A) and (B) Is simply referred to as (A) polyester resin).

  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 a structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene iso Phthalate, polypropylene isophthalate, polybutylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene Terephthalate / naphthalate, polypropylene terephthalate / naphthalate, Ribbylene terephthalate / naphthalate, polybutylene terephthalate / 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 / poly Tramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol, polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene Terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, polybutylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / a Dipetate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate and other aromatic polyester resins, polyethylene oxalate, polypropylene oxalate , Polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate Nate / Adipate, Polypropylene Shineto / adipate, aliphatic polyester resins such as polybutylene succinate / adipate and the like.

  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 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.

  (B) amorphous polyester resin used in the present invention is an amorphous polyester resin composed of terephthalic acid and 1,4-cyclohexanedimethanol, or terephthalic acid, 1,4-cyclohexanedimethanol, ethylene glycol, It is preferable to blend (B) a polyester resin in which a repeating unit in which a terephthalic acid residue and a 1,4-cyclohexanedimethanol residue are bonded accounts for 25% or more, and it is said that laser permeability and adhesion due to fuel are small. In order to have both properties, the repeating unit in which the terephthalic acid residue and the 1,4-cyclohexanedimethanol residue are combined is preferably 30 to 90% or more, more preferably 30 to 80%. . When the repeating unit in which a terephthalic acid residue and a 1,4-cyclohexanedimethanol residue are bonded is less than 25%, it is necessary for welding when the resin composition of the present invention is used as a transmission material during laser welding. The laser beam may not be transmitted to a certain extent, and even if the laser beam can be transmitted, it is not preferable because it is only a thin portion and narrows the size of the molded product and the degree of design freedom.

  The component (B) amorphous polyester resin used in the laser-welded polyester resin composition of the present invention can be produced by the same method as the polybutylene terephthalate in the (A) polybutylene terephthalate resin. The components that can be copolymerized are the same as described above.

  The thermoplastic resin composition for laser welding of the present invention preferably contains (A) 50 to 95% by weight of a polyester resin and (B) 50 to 5% by weight of an amorphous polyester resin. More preferably, (A) the polyester resin is 50 to 92% by weight and (B) the amorphous polyester resin is 50 to 8% by weight. Particularly preferably, (A) the polyester resin is 50 to 90% by weight and (B) the amorphous polyester resin is 50 to 10% by weight.

  (B) When the amount of the amorphous polyester resin is less than 5% by weight, there is no problem in the high fluidity and mechanical properties, which are the problems of the present invention, but the low warpage and the laser transmittance are not satisfactory. It is sufficient and not preferable. On the other hand, when the blending amount of (B) the amorphous polyester resin exceeds 50% by weight, the low warpage 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 polyester resin, but is not limited to these resins. Resins other than those described above can be mixed within a range that does not impair the properties of the plastic resin composition. 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 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 has 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.

  (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.

  Among them, those having a trivalent or tetravalent hydroxyl group are preferable. More preferably, it has a tetravalent hydroxyl group. When those having these are used, the fluidity is particularly good, and the component (C) is less likely to appear on the surface of the molded product during the wet heat treatment.

  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 , Butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, cyclohexane-1, 2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene-2,5,7 -Tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid, naphthalene-1,4,5, - polycarboxylic acid or acrylic acid, such as tetracarboxylic acid, include polymers such as methacrylic acid, it may be used acid anhydrides thereof. Of these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides having a branched structure are preferable from the viewpoint of fluidity.

  (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 And ester derivatives of compounds having a carboxylic acid group.

(C) As a preferable example of the compound having three or more functional groups, when the functional group is an amide group, an amide derivative of the compound having three or more carboxylic acid groups is exemplified.
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 particularly preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit, and it is said that the component (C) is less likely to appear on the surface of the molded product during fluidity and wet heat treatment. It is particularly preferable to use a compound containing a propylene oxide unit.

  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) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) oxyp Pyrenetrimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane, (poly ) Oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (Poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol, (poly) io Simethylenedipentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose, (poly) oxyethylene glucose, (poly ) Oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, (poly) oxytetramethylene glucose and the like.

  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 Examples thereof include 1,2,4-triaminobenzene.

When the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of a compound having three or more hydroxyl groups containing the alkylene oxide unit, or a compound having three or more carboxylic acid groups containing the alkylene oxide unit is used. Examples include ester derivatives.
When the functional group is an amide group, an amide derivative of a compound having three or more carboxylic acid groups containing the above-described alkylene oxide unit can 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 poly) propylene oxide units.

  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. It is more preferable that it is 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 3 or more functional groups used in the present invention is preferably 1% or less. More preferably, the moisture content is 0.5% or less, and further preferably 0.1% or less. There is no particular lower limit 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.

  In the present invention, the compounding amount of the compound (C) having three or more functional groups is in the range of 0.01 to 5 parts by weight of the component (C) with respect to 100 parts by weight of the total of the components (A) + (B). In view of fluidity and mechanical properties, it is preferably blended in the range of 0.01 to 3 parts by weight, more preferably in the range of 0.01 to 1 part by weight, It is particularly preferable to blend 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 polyester resin, and (C) a compound having three or more functional groups, the component (C) has at least one hydroxyl group or carboxylic acid group. From the viewpoint of fluidity, the component (C) preferably has 3 or more hydroxyl groups or carboxylic acid groups, and the component (C) has 3 or more hydroxyl groups. More preferably.

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

  As the kind of (D) inorganic filler that can be used in the resin composition of the present invention, glass fiber can be preferably used. The inorganic filler that can be used is not limited to these, and any filler 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, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers Fibers such as silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, kaolin, silica , Calcium carbonate, glass flakes, glass beads, glass microballoons, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, etc. Is, inter alia glass fibers are preferred. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like.

  In addition, said (D) inorganic filler used for this invention treats the surface with a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent, etc.) and other surface treatment agents. It can also be used. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin.

The inorganic 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.
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 the components (A) + (B) from the viewpoint of fluidity and mechanical properties, It is more preferable to mix | blend in the range of 1-70 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, in the laser welding resin composition of the present invention, the (A) polybutylene terephthalate resin component and (B) the polyester resin component By blending an elastomer, impact resistance and cold resistance can be imparted. Examples of the elastomer include ethylene-based and styrene-based (the amount of the elastomer added is 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the (A) polybutylene terephthalate resin component and the (B) polyester resin component. Is preferred). In particular, by using (D) styrene-based elastomer (hereinafter referred to as “component (D)”) as the elastomer, (A) polybutylene terephthalate-based resin component and (B) polyester resin component have sufficient high laser beam transparency. However, impact resistance and cold resistance can be further imparted. 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 (D) 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 addition amount of the component (D) used in the present invention is 100 parts by weight of the total amount of the (A) polybutylene terephthalate resin component and the (B) polyester resin component, from the balance of laser beam transparency, moldability, and heat resistance. It is the range of 1-50 weight part with respect to this, 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 heat resistance due to the addition of component (D), 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.

  Furthermore, in the present invention, a crystal nucleating agent, a plasticizer, an ultraviolet absorber, an antibacterial agent, a stabilizer, a mold release agent, a colorant including a pigment and a dye, a lubricant, and an antistatic agent, as long as the effects of the present invention are not impaired. One or more 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 polyester resin, (C) 3 A method of uniformly melting and kneading a compound having one or more functional groups and other components as necessary with a single screw or twin screw extruder, a method of removing the solvent after mixing in a solution, and the like are preferably used. From the viewpoint of productivity, a method of uniformly melting and kneading with a single-screw or twin-screw extruder is preferable, and 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 compound having (C) three or more functional groups. 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 two charging ports, and (A) a polyester resin, (B) non-blocking from a main charging port installed on the screw base side. A crystalline polyester resin, (C) a compound having three or more functional groups, and a method of supplying other components as required, and (A) a polyester resin, (B) an amorphous resin and other components from the main inlet Examples thereof include a method of supplying and melt-mixing (C) a compound having three or more functional groups from a sub-inlet installed between the main inlet and the tip of the extruder.

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-mentioned various molded products can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods, and in particular, laser welding is possible. It is suitable for automobile parts and electric / electronic parts for laser welding.

  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, young tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage 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 films for supplies, calendars, stationery, clothing, food, 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, lids Materials, envelopes with windows, fruit baskets, hand cut tapes, 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 fibers Various clothing such as composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tapes, prints, thermal Film for stencil printing, 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. Binder, optical element, conductive embossed tape IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag, chair, table, It is useful as a cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on. Since the resin composition of the present invention has not only high laser transmittance and laser weldability, but also has good mechanical properties and high fluidity and low warpage, various automotive parts that perform laser welding particularly among the above, Especially useful for electrical and electronic parts.

  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: Polycyclohexanedimethylene terephthalate (Easterman Chemical "Easter DN007").

(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, Nippon Emulsifier Co., Ltd. TMP-F32).

(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) Inorganic filler D-1: Chopped strand type glass fiber (fiber diameter 13 μm, 3PE949 manufactured by Nittobo Co., Ltd.).

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

  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., a mold temperature of 80 ° C., and an injection pressure of 65 MPa.

(2) Impact characteristics 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 in accordance with 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 in accordance with ISO178.

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

(5) 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.

(6) Laser beam transmittance L shown in FIG. 3 was 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”.

(7) Laser weldability The laser weldability evaluation test piece is a laser weldability test piece cut out of a molded product having the same shape as the laser beam transmission evaluation test piece 6 of FIG. 3 to 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, the laser welding method is such that a laser welding test piece 7 using a material that transmits a laser beam is placed in the upper part, and a laser welding test piece 8 that uses a material that absorbs the laser beam is placed in the lower part. Laminate and irradiate 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.

(8) Extract amount Gasohol liquid (isooctane 59.15% by weight, toluene 25.35% by weight, methanol 15.00% by weight, water 0.50% by weight) was prepared, and 500 g of sample was added to 500 ml of gasohol liquid at 60 ° C. After soaking for 24 hours, the sample and the gasohol solution were separated by filtration. The gasohol solution was concentrated to dryness, the weight of the extracted one was measured, and the ratio was calculated as% by weight of the entire sample.

(9) Moisture and heat resistance test Using a test piece according to ISO527-1, 2 molded at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, it was treated for 100 hours in an environment of 121 ° C, 100% RH, 2 atm. If the surface of the molded product is visually observed and a liquid adheres to the surface of the molded product, Δ. If the liquid is slightly attached to the surface of the molded product, Δ to ○. If the liquid did not adhere to the surface of the molded product, it was marked as ◯.

[Examples 1 to 26, Comparative Examples 1 to 9]
(A) Polyester resin, (B) Amorphous resin, (C) A compound having three or more functional groups, etc. are blended together at the blending ratios described in Table 1 and Table 2, and (D) an inorganic filler 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 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 1-5. Examples are shown in Tables 1 and 2, and Comparative Examples are shown in Tables 3 and 4.

  From the results of Tables 1 to 4, the following became clear.

  In the comparison between Examples 3, 6-8, 18-20 and Comparative Examples 3 and 10, when (B) the amorphous resin was not added, not only the laser beam sufficient for laser welding was not transmitted. I found out that the warping was great. Further, it was found that when the amount of the amorphous resin added is too large, there is no problem with laser welding, but even when a polyfunctional compound is added, sufficient fluidity may not be ensured.

  In the comparison between Examples 3, 10-12 and Comparative Examples 2, 7, 14-18, (C) When a compound having three or more functional groups is added, the flow of the resin composition according to the amount added It was found that the characteristics were greatly improved.

  Comparison between Examples 3, 13 to 17 and Comparative Examples 2, 6, and 19 reveals that the effect of improving fluidity is large when a polyfunctional compound having three or more functional groups is included.

  From the comparison between Examples 3 to 5 and Comparative Examples 5 and 20, when the addition amount of the inorganic filler is less than 2 parts by weight, the reinforcing effect of the resin composition is small and the amount exceeding 120 parts by weight is used. Was found to be less fluid.

  In comparison between Example 3 and Comparative Examples 8, 10, 11, and 13 to 18, although laser permeability and fluidity were improved, it was found that the amount of extract by the gasohol liquid was very large.

  In the comparison between Examples 3 and 21 and Comparative Example 20, fluidity was improved by using an elastomer other than the styrene elastomer, but the laser transmission was remarkably lowered and laser welding was impossible. I understood.

  Moreover, the following things became clear from the result of Table 5.

  In Examples 22 to 26, (C) the types and amounts of polyfunctional compounds having three or more functional groups are different. By adding C-7, there is no difference in fluidity, mechanical strength, and transmittance compared to C-6, but the adhesion of the liquid on the surface of the molded product after the wet heat resistance test is improved. I understood.

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 (10)

  (A) 50 to 95% by weight of a polyester resin other than (B) and (B) amorphous polyester comprising terephthalic acid and 1,4-cyclohexanedimethanol, or terephthalic acid, 1,4-cyclohexanedimethanol, ethylene glycol 50 to 5% by weight of resin is blended, and (C) 0.01 to 5% by weight of a polyfunctional compound having 3 or more functional groups with respect to 100 parts by weight of the total amount of (A) and (B). Part, (D) thermoplastic resin composition for laser welding formed by blending 1 to 120 parts by weight of an inorganic filler.   (C) The thermoplastic resin composition for laser welding according to claim 1, wherein the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units.   (C) The functional group of the polyfunctional compound having three or more functional groups is at least one group selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. The thermoplastic resin composition for laser welding according to claim 1 or 2.   (A) The polyester resin other than (B) is at least one selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polybutylene terephthalate resin comprising polybutylene terephthalate and polybutylene terephthalate copolymer. The thermoplastic resin composition for laser welding according to any one of claims 1 to 3.   (D) The thermoplastic resin composition for laser welding according to any one of claims 1 to 4, wherein the inorganic filler is glass fiber.   (E) The laser welding thermoplastic resin composition according to any one of claims 1 to 5, further comprising an impact resistance improver.   The laser welding according to claim 6, wherein (E) the impact resistance improving agent is a styrene elastomer, and 1 to 100 parts by weight of the styrene elastomer is blended with respect to 100 parts by weight of the total amount of (A) and (B). Thermoplastic resin composition.   The thermoplastic resin composition for laser welding according to any one of claims 1 to 7, further comprising (F) a phosphorus stabilizer.   A molded article for laser welding comprising the thermoplastic resin composition for laser welding according to any one of claims 1 to 8.   A composite molded body obtained by laser welding the molded product according to claim 9.

Images