JPWO2006051667A1 - Polyester resin composition - Google Patents

Abstract

An object of the present invention is to provide a thermoplastic polyester resin composition having excellent bending elastic modulus and heat resistance, and excellent impact resistance and stretch resistance. The present invention relates to a thermoplastic polyester resin composition containing a thermoplastic polyester resin (A), an inorganic filler (B), and a polyorganosiloxane-containing graft copolymer (C), the polyorganosiloxane graft copolymer (C) 30 to 94.9 parts by weight of a polyorganosiloxane (C2) in a latex state modified with a graft crossing agent (C1) containing a mercapto group-containing silane compound, and a (meth) acryloyloxy group-containing silane compound The graft crossing agent (C3) containing 0.1 to 10 parts by weight is reacted, and further the vinyl monomer (C4) 5 to 69.9 parts by weight ((C2), (C3), (C4) in total 100 weights) Part) is obtained by polymerizing at least one stage, and is a thermoplastic polyester resin composition.

Description

  The present invention relates to a thermoplastic polyester resin composition comprising a thermoplastic polyester resin, an inorganic filler, and a polyorganosiloxane-containing graft copolymer.

  Thermoplastic polyester resins such as polyethylene terephthalate are excellent in heat resistance, chemical resistance, weather resistance, mechanical properties, electrical properties, etc., and are therefore widely used industrially as injection molding materials, fibers, and films. For applications that require higher mechanical properties and heat resistance, it is common practice to add various inorganic fillers to thermoplastic polyester resins (see, for example, Patent Documents 1 and 2). ).

  On the other hand, it has long been known that blending a rubber-containing graft copolymer is effective for improving the impact resistance of a thermoplastic polyester resin. For example, it is disclosed that when 20 to 90% by weight of a copolymer containing an organosiloxane rubber having a toluene swelling degree of 3.0 to 15 is blended with a thermoplastic polyester resin, impact resistance is improved. (For example, refer to Patent Document 3). However, in the art, it has also been shown that the blending of the rubber-containing copolymer greatly reduces the flexural modulus.

As described above, it is very difficult to achieve both the flexural modulus of thermoplastic polyester resin and impact resistance / stretch resistance. For a long time, it has high flexural modulus and heat resistance in the market, and high impact resistance. The appearance of a thermoplastic polyester resin having heat resistance and stretch resistance has been desired.
Japanese Patent Laid-Open No. 10-259016 JP-A-10-310420 Japanese Patent Laid-Open No. Sho 62-121752

  An object of the present invention is to provide a thermoplastic polyester resin composition having excellent bending elastic modulus and heat resistance, and excellent impact resistance and stretch resistance.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by blending a specific polyorganosiloxane-containing graft copolymer together with a thermoplastic polyester resin and an inorganic filler, The present invention has been completed.

  That is, the present invention is a thermoplastic polyester resin composition containing a thermoplastic polyester resin (A), an inorganic filler (B), and a polyorganosiloxane-containing graft copolymer (C), wherein the polyorganosiloxane graft copolymer 30-94.9 parts by weight of a polyorganosiloxane (C2) in a latex state in which the polymer (C) is modified by a graft crossing agent (C1) containing a mercapto group-containing silane compound, and a (meth) acryloyloxy group-containing silane The graft crossing agent (C3) containing the compound is reacted in an amount of 0.1 to 10 parts by weight, and further, the vinyl monomer (C4) in an amount of 5 to 69.9 parts by weight ((C2), (C3), (C4)) 100 parts by weight) is obtained by polymerizing one or more stages, and relates to a thermoplastic polyester resin composition.

  Preferred embodiments include thermoplastic polyester resin (A) 95 to 45% by weight, inorganic filler (B) 0.2 to 50% by weight, polyorganosiloxane-containing graft copolymer (C) 0.5 to 9% by weight. (The (A), (B), and (C) are combined in a range of 100% by weight) in the range of the thermoplastic polyester resin composition.

  A preferred embodiment is characterized in that mercaptopropylmethyldimethoxysilane is used as the grafting agent (C1) and (meth) acryloyloxypropylmethyldimethoxysilane is used as the grafting agent (C3). The present invention relates to a polyester resin composition.

  According to the thermoplastic polyester resin composition of the present invention, it is possible to obtain a molded product having excellent bending elastic modulus, impact resistance, and stretch resistance.

  The present invention relates to a thermoplastic polyester resin composition containing a thermoplastic polyester resin (A), an inorganic filler (B), and a polyorganosiloxane-containing graft copolymer (C), the polyorganosiloxane graft copolymer In the presence of 30 to 94.9 parts by weight of polyorganosiloxane (C2) in a latex state (C) modified with a graft crossing agent (C1) containing a mercapto group-containing silane compound, (meth) acryloyloxy group-containing The graft crossing agent (C3) containing a silane compound is added and reacted in an amount of 0.1 to 10 parts by weight, and further the vinyl monomer (C4) in an amount of 5 to 69.9 parts by weight ((C2), (C3), ( A thermoplastic polyester resin composition obtained by polymerizing one or more stages of C4) together (100 parts by weight) is obtained.

  The thermoplastic polyester resin (A) used in the present invention is not particularly limited, but includes an acid component mainly composed of a dicarboxylic acid compound and / or an ester-forming derivative of dicarboxylic acid, and a diol compound and / or an ester of a diol compound. Any thermoplastic polyester resin obtained by reaction with a diol component having a forming derivative as a main component is used. Here, “main component” means that the proportion of each of the components in the acid component or diol component is 80% by weight or more, further 90% by weight or more, and the upper limit is 100% by weight. is there.

  Specific examples of the thermoplastic polyester resin (A) include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, Examples include polybutylene naphthalate and polyhexamethylene naphthalate. Moreover, the copolyester manufactured using 2 or more types of the acid component and / or diol component which are used for manufacture of these resin is mentioned.

  The above-mentioned thermoplastic polyester resins may be used as appropriate alone or in combination of two or more types having different compositions or components or different intrinsic viscosities. Among the thermoplastic polyester resins, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, and polyethylene naphthalate are more preferable in terms of strength, elastic modulus, cost, and the like. The thermoplastic polyester resin is preferably used in an amount of 45 to 95% by weight, preferably 70 to 95% by weight, and more preferably 80 to 95% by weight in the total amount of the resin composition. Within the above range, the excellent properties of the thermoplastic polyester resin such as heat resistance, chemical resistance, mechanical properties, and electrical properties can be sufficiently exhibited.

  The inorganic filler (B) used in the present invention can be used without any particular limitation, and examples thereof include silicates such as calcium carbonate, talc, mica, aluminum oxide, magnesium hydroxide, boron nitride, beryllium oxide, and calcium silicate. , Phosphates such as zirconium phosphate, titanates such as potassium titanate, tungstates such as sodium tungstate, uranates such as sodium uranate, vanadates such as potassium vanadate, magnesium molybdate, etc. And molybdates, niobates such as potassium niobate, layered compounds such as graphite, and clay. Of these, layered compounds such as silicate, phosphate, titanate, tungstate, uranate, vanadate, molybdate, niobate, and graphite are preferable, and further treatment for improving dispersibility is preferable. Those subjected to are more preferable.

  Specific examples of a layered compound that has been treated to improve dispersibility include layered silicates such as montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers, polyoxyethylene and polyoxyethylene. -What processed the polyether compound which has a cyclic hydrocarbon group in the side chain and / or main chain of polyoxyalkylene compounds, such as a polyoxypropylene copolymer, can be used.

  The amount of the inorganic filler (B) used in the present invention is preferably 0.2 to 50% by weight, more preferably 1 to 29% by weight, particularly 2 to 19% by weight, based on the total amount of the resin composition. If the amount of the inorganic filler (B) is less than 0.2% by weight, the effect of improving the flexural modulus and heat resistance of the thermoplastic polyester resin composition tends to be small. On the other hand, if it exceeds 50% by weight, the surface appearance of the molded article may be impaired.

  The polyorganosiloxane-containing graft copolymer (C) used in the present invention is a latex-like polyorganosiloxane (C2) modified by a graft crossing agent (C1) containing a mercapto group-containing silane compound. In the presence of 0.1 to 10 parts by weight of a graft-crossing agent (C3) containing a (meth) acryloyloxy group-containing silane compound, and further reacted with vinyl monomer (C4) 5 to 69.9. It is characterized by being obtained by polymerizing one part or more of parts by weight (100 parts by weight in total of (C2), (C3) and (C4)). In the present invention, (meth) acryl means acryl and / or methacryl unless otherwise specified.

The polyorganosiloxane (C2) used in the present invention is preferably obtained by emulsion polymerization, but the organosiloxane used as a raw material has a general formula R _m SiO _{(4-m) / 2} (wherein R is substituted or unsubstituted). A monovalent hydrocarbon group, m having an integer of 0 to 3) having a cyclic structure, a straight chain, or a branched chain. Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. Can do.

  Polyorganosiloxanes made from cyclic organosiloxanes can be obtained by ordinary emulsion polymerization, but seed polymerization can also be performed because of the advantage that the particle size distribution in the latex state can be narrowed and flame retardancy is improved. It is preferable to use it. The seed polymer used for the seed polymerization is not particularly limited, but rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile, butyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, etc. Polymers can be used. A chain transfer agent may be added to the polymerization of the seed polymer.

  For example, an organosiloxane having a cyclic structure, a grafting agent and water are emulsified and dispersed in water by mechanical shearing in the presence of an emulsifier, mixed with the seed polymer, and then brought into an acidic state to effect emulsion polymerization of the polyorganosiloxane. Can be done.

  Specific examples of the organosiloxane having a cyclic structure include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenyl. And cyclotrisiloxane. These organosiloxanes may be used alone or in combination of two or more.

  In the polymerization of the polyorganosiloxane (C2) used in the present invention, a graft crossing agent (C1) is used. The graft crossing agent (C1) can be used alone or in combination of two or more of silane compounds generally known as graft crossing agents. The amount of the graft crossing agent (C1) is 100% by weight. It is preferable to use a mercapto group-containing silane compound for 80% by weight or more. The mercapto group-containing silane compound has a characteristic that the reaction efficiency with the vinyl monomer (C4) described later is lower than the (meth) acryloyloxy group-containing silane compound used in the graft crossing agent (C3). Therefore, 80% by weight or more, preferably 90% by weight or more of the graft crossing agent (C1) is used as a mercapto group-containing silane compound, so that the vinyl monomer (C4) in the polyorganosiloxane (C2) particles is contained. The reaction rate is suppressed, and the vinyl monomer (C4) tends to be efficiently polymerized and coated on the (C2) particle surface. For this reason, when the content of the mercapto group-containing silane compound in the graft crossing agent (C1) is lower than 80% by weight, the dispersibility of the polyorganosiloxane-containing graft copolymer in the final molded product is reduced, Impact resistance may be reduced. As the graft crossing agent (C1), a so-called bifunctional silane compound having preferably two hydrolyzable silicon groups can be used. When a trifunctional or higher functional silane compound is used, the impact resistance of the molded article which is the final form of the resin composition of the present invention may be lowered.

  Specific examples of the mercapto group-containing silane compound include, for example, mercaptopropylmethyldimethoxysilane and mercaptopropylethyldimethoxysilane. Among these, mercaptopropylmethyldimethoxysilane is particularly preferable.

  The amount of the grafting agent (C1) used is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, particularly preferably 0.8 to 100% by weight based on 100% by weight of the polyorganosiloxane (C2). 5% by weight. If the amount of the grafting agent (C1) used exceeds 10% by weight, the impact resistance and stretch resistance of the final molded product may be reduced. Conversely, the amount of the grafting agent (C1) used is 0.1% by weight. If it is less than%, the moldability and bending elastic modulus of the final molded product obtained from the resin composition of the present invention may be lowered.

  In the synthesis of the polyorganosiloxane (C2) used in the present invention, a crosslinking agent can be added if necessary. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, tetraethoxysilane, 1,3bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,3-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene 1- [1- (dimethoxymethylsilyl) ethyl] -3- [2- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -4- [2-dimethoxymethylsilyl) And tetrafunctional cross-linking agents such as ethyl] benzene.

  These crosslinking agents can be used singly or in combination of two or more. Moreover, 0 to 2 weight% is preferable with respect to 100 weight% of polyorganosiloxane (C2), and, as for the usage-amount of a crosslinking agent, 0 to 0.5 weight% is more preferable. If the addition amount of the crosslinking agent is more than 2% by weight, the flexibility of the polyorganosiloxane (C2) is impaired, and the impact resistance of the final molded product tends to be lowered. As an index of the flexibility of the polyorganosiloxane (C2), for example, the degree of swelling measured in a toluene solvent can be used. Specifically, if the degree of swelling is less than 15, the flexibility of the polyorganosiloxane may be insufficient. Therefore, the degree of swelling of the polyorganosiloxane (C2) is preferably 15 or more. The degree of swelling is an index indicating how many times the amount of toluene was swollen with respect to the dry polymer weight.

  The amount of the polyorganosiloxane (C2) of the present invention is 30 to 94.9 parts by weight based on 100 parts by weight of the total of the (C2) component, the grafting agent (C3) and the vinyl monomer (C4). Further, it is preferably used in the range of 50 to 80 parts by weight. When the amount of (C2) is less than 30 parts by weight, the impact resistance of the final molded product tends to be reduced due to a substantial decrease in the rubber component, and conversely when it exceeds 94.9 parts by weight, polyorganosiloxane. When the dispersibility of the contained graft copolymer particles is lowered, the impact resistance and appearance of the final molded product tend to be lowered.

  In the emulsion polymerization of the polyorganosiloxane, an emulsifier that does not lose the emulsifying ability under an acidic state can be used. Specific examples include alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, sodium (di) alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfonate, sodium alkyl sulfate, and the like. These may be used alone or in combination of two or more.

  Among these, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, and sodium (di) alkyl sulfosuccinate are preferable because the emulsion has a relatively high emulsion stability. Furthermore, alkylbenzene sulfonic acid and alkyl sulfonic acid are preferable from the point of acting as a polymerization catalyst for the polyorganosiloxane-forming component.

  The acidic state can be obtained by adding inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as alkylbenzene sulfonic acid, alkyl sulfonic acid, and trifluoroacetic acid to the system. Considering that the speed can be obtained, it is preferable to adjust to pH = 1.0 to 3.0, and more preferably to 1.0 to 2.5.

  The heating temperature for the polymerization is not particularly limited, but is preferably 60 to 120 ° C, more preferably 70 to 100 ° C, in that an appropriate polymerization rate can be obtained. When the polymerization temperature is lower than 0 ° C., the productivity is lowered. Conversely, when the polymerization temperature is higher than 100 ° C., the volatile siloxane tends to increase.

  In an acidic state, the Si—O—Si bond forming the polyorganosiloxane skeleton is in an equilibrium reaction state of cleavage and generation, and this equilibrium moves to the generation side as the temperature becomes lower. It becomes easy to generate the one of the degree. For this reason, it is preferable that the polymerization of the polyorganosiloxane-forming component is reacted at 50 ° C. or higher and the polymerization conversion rate reaches equilibrium, and then the polyorganosiloxane latex obtained is cooled to room temperature or lower and held for 6 hours or longer. . When the holding time after cooling is short, the proportion of the low molecular weight polyorganosiloxane is relatively increased, and the impact resistance and stretch resistance of the final molded product obtained from the resin composition of the present invention are lowered. There is a fear.

  The graft crossing agent (C3) used in the present invention is a component used for intensively reacting the vinyl monomer (C4) on the surface of the polyorganosiloxane particles, whereby the vinyl monomer (C4) is used. And the flame retardant property of the molded product, which is the final form obtained from the resin composition of the present invention, functions efficiently to ensure compatibility between the graft copolymer and the thermoplastic resin. Improves impact resistance.

  The graft crossing agent (C3) used in the present invention can be used alone or in combination of two or more of silane compounds generally known as graft crossing agents. The amount of the graft crossing agent (C3) is 100% by weight. The (meth) acryloyloxy group-containing silane compound is preferably used in an amount of 80% by weight or more, preferably 90% by weight or more. The (meth) acryloyloxy group-containing silane compound has a higher reaction efficiency with the vinyl monomer (C4) than the mercapto group-containing silane compound used in the graft crossing agent (C1). Therefore, the vinyl monomer (C4) is efficiently coated on the surface of the polyorganosiloxane (C2) particles by using 80% by weight or more of the graft crossing agent (C3) as the (meth) acryloyloxy group-containing silane compound. Will be able to. Therefore, when the content of the (meth) acryloyloxy group-containing silane compound in the graft crossing agent (C3) is lower than 80% by weight, the dispersibility of the polyorganosiloxane-containing graft copolymer in the final molded product is The impact resistance may decrease. The graft crossing agent (C3) is preferably a so-called bifunctional silane compound having two hydrolyzable groups. When a trifunctional silane compound is used as the graft crossing agent (C3), the impact resistance and stretch resistance of the molded article, which is the final form obtained from the resin composition of the present invention, may be reduced.

  Specific examples of the (meth) acryloyloxy group-containing silane compound include methacryloyloxypropyldimethoxymethylsilane, methacryloyloxypropyldiethoxymethylsilane, and acryloyloxypropyldimethoxymethylsilane. Among these, methacryloyloxypropyldimethoxymethylsilane is particularly preferable.

  The amount of the graft crossing agent (C3) used is 0.1 to 10 weights with respect to the polyorganosiloxane-containing graft copolymer (C) (100 parts by weight in total of (C2), (C3) and (C4)). Parts, preferably 0.5 to 7 parts by weight. If the amount of the grafting agent (C3) used exceeds 10 parts by weight, the flame retardancy and impact resistance of the final molded product obtained from the resin composition of the present invention will be reduced, and conversely the use of the grafting agent (C3). If the amount is less than 0.1 parts by weight, the flame retardancy / impact resistance improving effect of the present invention may not be sufficiently obtained.

  The method of adding the graft crossing agent (C3) to the latex polyorganosiloxane (C2) is not particularly limited. For example, the silane compound is added after emulsifying in advance with pure water containing a small amount of an emulsifier. Is preferred. If the silane compound is added directly to the polyorganosiloxane latex in the acidic state, the graft crossing agent may become a foreign substance before reacting with the polyorganosiloxane particles, which may reduce the impact resistance and stretch resistance of the final molded product. .

  The graft crossing agent (C3) is preferably in the surface layer of the polyorganosiloxane particles. However, if the reaction is continued at a high temperature or for a long time, the polyorganosiloxane particles have a tendency to become uniform, so that the impact resistance can be improved. May not be sufficiently obtained. Therefore, the reaction between the graft crossing agent (C3) and the polyorganosiloxane (C2) is preferably carried out at a polymerization temperature of 20 to 60 ° C., more preferably 20 to 40 ° C., and a polymerization time of 0.5 to 12 It is preferable to carry out in time, and also in 1-4 hours. When the polymerization temperature is less than 20 ° C or when the polymerization time is less than 0.5 hours, the graft crossing agent (C3) may be unreacted, and when the polymerization temperature is higher than 60 ° C or the polymerization time is more than 12 hours. If the length is long, homogenization of the polyorganosiloxane particles tends to proceed, and both the impact resistance and stretch resistance of the final molded product may be lowered.

  If the latex after reacting the graft crossing agent (C3) under acidic conditions is allowed to stand for a long time, the graft crossing agent introduced onto the particle surface by the equilibrium reaction decreases. After completion of the reaction of the organosiloxane (C2), it is preferable to immediately neutralize by adding an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide or sodium carbonate.

  The vinyl monomer (C4) used in the present invention ensures compatibility between the graft copolymer (C) and the thermoplastic polyester resin (A), and the graft copolymer (C) is converted into the thermoplastic polyester resin (A ) Is a component used to uniformly disperse it in). Specifically, for example, aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, Examples include (meth) acrylic acid ester monomers such as butyl methacrylate, vinyl monomers containing an epoxy group in the molecule such as glycidyl (meth) acrylate, and these may be used alone. More than one species may be used in combination.

  For polymerization of the vinyl monomer (C4) of the present invention, generally known radical polymerization can be used. Specific examples of the radical polymerization initiator include, for example, organic peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and inorganic such as potassium persulfate and ammonium persulfate. Examples thereof include peroxides, 2,2′-azobisisobutyronitrile, azo compounds such as 2,2′-azobis-2,4-dimethylvaleronitrile, and the like. Redox such as ferrous sulfate-sodium formaldehydesulfoxylate-ethylenediaminetetraacetic acid 2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate When carried out in the system, the polymerization can be completed even at a low polymerization temperature.

  As a method for separating the polymer from the polyorganosiloxane-containing graft copolymer (C) latex obtained by emulsion polymerization, for example, the latex is coagulated by adding a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate to the latex. Next, the coagulated slurry is separated, washed with water, dehydrated and dried. A spray drying method can also be used.

  The polyorganosiloxane-containing graft copolymer (C) thus obtained is blended with the thermoplastic polyester resin (A) and the inorganic filler (B). The blending amount of the polyorganosiloxane-containing graft copolymer (C) is 0.5 to 9% by weight with respect to the resin composition (100% by weight of (A), (B) and (C)). 3 to 8% by weight, more preferably 5 to 8% by weight. When the blending amount of the polyorganosiloxane-containing graft copolymer (C) in the resin composition is less than 0.5% by weight, the effect of improving the impact resistance and stretch resistance of the final molded product obtained is small. When the blending amount of the graft copolymer (C) exceeds 9% by weight, the flexural modulus of the final molded product may be reduced to the same level as the original thermoplastic polyester resin.

  The method for producing the thermoplastic polyester resin composition of the present invention is not particularly limited. For example, the thermoplastic polyester resin can be melt-kneaded using various general kneaders. Examples of the kneader include a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, and the like, and a kneader with high shear efficiency is particularly preferable. The thermoplastic polyester resin, the inorganic filler and the polyorganosiloxane-containing graft copolymer may be put into the kneading machine and melt-kneaded, or may be pre-molten thermoplastic polyester resin and polyorganosiloxane. An inorganic filler may be added to the graft polymer and melt kneaded.

  In the polyester resin composition of the present invention, other arbitrary thermoplastic resins or thermosetting resins, for example, unsaturated polyester resins, polyester carbonate resins, are used as long as they do not impair the properties such as mechanical properties. , Polyolefin resin, polyamide resin, rubbery polymer reinforced styrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, acrylic resin, and polyarylate resin can be used alone or in combination of two or more. .

  Furthermore, additives such as pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents can be added depending on the purpose.

  The thermoplastic polyester resin composition obtained in the present invention may be molded by injection molding or hot press molding, and can also be used for blow molding. The resulting molded article has an excellent appearance and is excellent in mechanical properties, heat distortion resistance, and the like, and therefore can be suitably used for, for example, automobile parts, household electrical product parts, household daily goods, packaging materials, and other general industrial materials.

  The present invention will be specifically described based on examples, but the present invention is not limited thereto. Measurements and tests in the following examples and comparative examples were performed as follows.

[Polymerization conversion rate]
The latex was dried in a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid component, and calculated by 100 × (solid component amount / charged monomer amount) (%).

[Toluene swelling]
The prepared polyorganosiloxane latex was added to about 3 to 5 times the amount of isopropyl alcohol with stirring, and the emulsion was broken and coagulated to obtain a siloxane polymer. This was washed with water and then dried under reduced pressure at 80 ° C. for 10 hours. Thereafter, about 1 g of the polymer was precisely weighed, immersed in about 30 g of toluene, and allowed to stand at 25 ° C. for 100 hours to swell the toluene in the polymer. Subsequently, the remaining toluene was separated and removed by decantation and precisely weighed, and then dried under reduced pressure at 80 ° C. for 16 hours. The absorbed toluene was removed by evaporation, and then weighed again. Swellability was calculated by the following formula.
Swellability = ((swelled polymer weight) − (dry polymer weight weighed again)) / (dry polymer weight weighed again).

[Volume average particle diameter]
The volume average particle size of the seed polymer, polyorganosiloxane particles, and graft copolymer was measured in a latex state. The volume average particle diameter (μm) was measured by a light scattering method using a MICROTRAC UPA manufactured by LEED & NORTHRUUP INSTRUMENTS as a measuring device.

[Bending elastic modulus]
In accordance with ASTM D-790, evaluation was performed by a bending test at 23 ° C. using a 1/4 inch bar.

[Heat-resistant]
In accordance with ASTM D-648, evaluation was performed by HDT with a load of 4.6 kg / cm ² using a 1/4 inch bar.

[Shock resistance]
According to JIS K7110, an Izod strength test at −10 ° C. was evaluated using No. 2 type A and No. 2 type B test specimens with a 1/8 inch bar.

[Stretch resistance]
In accordance with JIS K7162, a tensile test was conducted at 23 ° C. and a speed of 10 mm / min using a 1/8 inch thick 1A dumbbell test piece, and the elongation at break was evaluated.

(Production Examples 1 to 13)
Mixing 300 parts by weight of pure water and 12 parts by weight (solid content) of sodium dodecylbenzenesulfonate (SDBS) into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, additional monomer port, and thermometer After that, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, 10 parts by weight of butyl acrylate (BA), 3 parts by weight of t-dodecyl mercaptan (tDM), and 0.01 parts by weight of paramentane hydroperoxide were added. After 30 minutes, add 0.002 parts by weight of ferrous sulfate (FeSO ₄ .7H ₂ O), 0.005 parts by weight of ethylenediaminetetraacetic acid 2Na salt, and 0.2 parts by weight of sodium formaldehydesulfoxylate. The polymerization was further continued for 1 hour. Thereafter, a mixed solution of 90 parts by weight of butyl acrylate (BA), 27 parts by weight of t-dodecyl mercaptan (tDM) and 0.1 part by weight of paramentane hydroperoxide was continuously added over 3 hours. Post-polymerization was performed for 2 hours to obtain a seed polymer latex (SE-1). The polymerization rate of the obtained seed polymer latex was 92% by weight, and the volume average particle size was 0.03 μm.

  Subsequently, the seed polymer (SE-1) in parts by weight (solid content) shown in Tables 1 and 2 was added to a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. ) And 161.6 parts by weight of pure water were charged. Next, it heated up to 80 degreeC under nitrogen stream, stirring, and the weight part (solid content) shown in Table 1 and Table 2 was added for dodecylbenzenesulfonic acid (DBSA).

  Thereafter, 78.4 parts by weight of pure water, sodium dodecylbenzenesulfonate (SDBS), octamethylcyclotetrasiloxane (D4), and grafting agent (C1) were added in parts by weight as shown in Tables 1 and 2, and 7000 rpm with a homomixer. The mixture was stirred for 5 minutes to prepare an emulsion, and continuously dropped over 3 hours.

  Thereafter, stirring was continued at 80 ° C. for 4 hours, followed by cooling to 25 ° C. and leaving for 30 hours to obtain a latex of polyorganosiloxane (C2).

  Subsequently, the polyorganosiloxane (C2) latex was heated to 40 ° C. under a nitrogen stream while stirring. Thereafter, 5.2 parts by weight of pure water, sodium dodecylbenzenesulfonate (SDBS) and graft crossing agent (C3) were added in parts by weight as shown in Tables 1 and 2, and the mixture was stirred with a stirrer for 30 minutes to prepare an emulsion. Added all at once.

  Thereafter, stirring was continued at 40 ° C. for 2 hours, and then the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization. Tables 1 and 2 show the toluene swelling degree of the obtained polyorganosiloxane latex.

  Subsequently, the polyorganosiloxane latex was heated to 40 ° C. under a nitrogen stream while stirring. After reaching 40 ° C., 0.2 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of disodium ethylenediaminetetraacetate and 0.0025 parts by weight of ferrous sulfate were added, and then (C4) in Tables 1 and 2 A mixture of 20 parts by weight of the component and 0.06 part by weight of cumene hydroperoxide was added dropwise over 1 hour, and stirring was continued for 1 hour after completion of addition to obtain a polyorganosiloxane graft copolymer latex. Tables 1 and 2 show the volume average particle diameters of the obtained polyorganosiloxane-containing graft copolymer latex.

  Subsequently, the polyorganosiloxane-containing graft copolymer latex is diluted with pure water to a solid content concentration of 15%, and then 4 parts by weight (solid content) of a 25% calcium chloride aqueous solution is added to obtain a coagulated slurry. It was. The coagulated slurry is heated to 95 ° C., cooled to 50 ° C., dehydrated, washed with 10 times the solid content of methanol for 1 hour, filtered and dried to obtain a polyorganosiloxane-containing graft copolymer powder ( SG-1 to 13) were obtained.

(Production Example 14)
Ion exchange water and swellable mica (trade name: Somasif ME100, manufactured by Corp Chemical Co., Ltd.) were mixed. Next, a polyether compound (trade name: Bisol 18EN, manufactured by Toho Chemical Co., Ltd.) was added, and the mixture was treated by continuing mixing for 15 to 30 minutes. Then, the inorganic filler (B) which was pulverized and processed with the polyether compound was obtained.

(Examples 1-8, Comparative Examples 1-6)
85 parts by weight of a thermoplastic polyester resin (manufactured by Kanebo Co., Ltd., trade name: Belpet EFG85A), inorganic filler of Production Example 14 and polyorganosiloxane-containing graft copolymer of Production Examples 1 to 13 (SG-1 to 13) ) Were mixed in the weight parts shown in Tables 3 and 4 and further melt kneaded at 260 ° C. using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44) to obtain pellets. Thereafter, the obtained pellets were molded by a FAS100B injection molding machine manufactured by FANUC Co., Ltd. set at a cylinder temperature of 285 ° C. to obtain a thermoplastic polyester resin composition. Tables 3 and 4 show the results of evaluating the flexural modulus, heat resistance, impact resistance and stretch resistance of this thermoplastic polyester resin.

In the presence of the latex polyorganosiloxane (C2) modified with the graft crossing agent (C1) containing the mercapto group-containing silane compound, the graft crossing agent (C3) containing the (meth) acryloyloxy group-containing silane compound is added. The impact resistance and stretch resistance of thermoplastic polyester resins containing inorganic fillers are improved by using an organosiloxane-containing graft polymer obtained by polymerizing one or more vinyl monomers (C4). Can be made.

Claims (3)

  A thermoplastic polyester resin composition comprising a thermoplastic polyester resin (A), an inorganic filler (B), and a polyorganosiloxane-containing graft copolymer (C), wherein the polyorganosiloxane graft copolymer (C) is A graft crossing agent comprising 30-94.9 parts by weight of a polyorganosiloxane (C2) in a latex state modified with a graft crossing agent (C1) containing a mercapto group-containing silane compound and a (meth) acryloyloxy group-containing silane compound 0.1 to 10 parts by weight of (C3) is reacted, and 5 to 69.9 parts by weight of the vinyl monomer (C4) (100 parts by weight in total of (C2), (C3) and (C4)) is 1 A thermoplastic polyester resin composition obtained by polymerizing in stages or more.   Thermoplastic polyester resin (A) 95-45 wt%, inorganic filler (B) 0.2-50 wt%, polyorganosiloxane-containing graft copolymer (C) 0.5-9 wt% ((A), 2. The thermoplastic polyester resin composition according to claim 1, comprising (B) and (C) in a range of 100 wt% in total. The thermoplastic polyester resin composition according to claim 1 or 2, wherein mercaptopropylmethyldimethoxysilane is used for the graft crossing agent (C1) and (meth) acryloyloxypropylmethyldimethoxysilane is used for the graft crossing agent (C3). object.