JPWO2006054477A1 - Graft polymer and resin composition containing the polymer - Google Patents

Abstract

An object of the present invention is to provide a thermoplastic polyester resin composition having an excellent flexural modulus, heat resistance and excellent impact resistance. A polymer obtained by polymerizing the monomer (d) in the presence of a polyorganosiloxane (a) having a volume average particle size of 0.001 to 0.05 μm and further polymerizing the vinyl monomer (e), A polyorganosiloxane-containing graft polymer obtained by adding the water-soluble electrolyte (f) during the polymerization of (d) and / or (e). The monomer (d) is composed of a polyfunctional monomer (b) having two or more polymerizable unsaturated bonds in the molecule and other copolymerizable vinyl monomers (c). And And a composition containing the graft polymer (A), a thermoplastic polyester resin (B), and optionally an inorganic filler (C).

Description

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

  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, various inorganic fillers are generally blended (see, for example, Patent Documents 1 and 2).

  It has long been known that the incorporation of rubber-containing graft copolymers is effective for improving the impact resistance of thermoplastic polyester resins. Further, 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, (See Patent Document 3). However, it is also shown here that the blending of the rubber-containing copolymer greatly reduces the flexural modulus of the thermoplastic polyester resin.

In this way, it is very difficult to achieve both the flexural modulus and impact resistance of thermoplastic polyester resin. For a long time, the thermoplastic polyester resin has high elasticity and heat resistance in the market and has high impact resistance. The appearance of was desired.
Japanese Patent Laid-Open No. 10-259016 JP-A-10-310420 Japanese Patent Laid-Open No. Sho 62-121752

  The present invention includes a graft polymer having a specific volume average particle diameter obtained by adding a water-soluble electrolyte during the polymerization of a polyorganosiloxane-containing graft polymer, and an excellent bending elasticity obtained by blending the graft polymer. It is providing the thermoplastic polyester resin composition which has a rate, heat resistance, and the outstanding impact resistance.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.

  That is, the present invention is polyfunctional having two or more polymerizable unsaturated bonds in the molecule in the presence of 30 to 95 parts by weight of polyorganosiloxane (a) having a volume average particle size of 0.001 to 0.05 μm. From monomer (b) 100 to 50% by weight, and other copolymerizable vinyl monomers (c) 0 to 50% by weight (provided that (b) and (c) are combined 100% by weight) 0 to 10 parts by weight of the monomer (d) to be polymerized, and further 5 to 70 parts by weight of the vinyl monomer (e) (provided that 100 parts by weight of (a), (d) and (e) are combined) The volume average particle diameter obtained by adding the water-soluble electrolyte (f) during the polymerization of (d) and / or (e) is 0.01 to 0.6 μm. The present invention relates to a polyorganosiloxane-containing graft polymer.

  A preferred embodiment relates to the aforementioned polyorganosiloxane-containing graft polymer, wherein the vinyl monomer (e) contains a monomer having an epoxy group.

  A preferred embodiment relates to the polyorganosiloxane-containing graft polymer as described above, wherein the graft polymer has a volume average particle diameter of 0.06 to 0.2 μm.

  The present invention is characterized by containing 0.5 to 9% by weight of the polyorganosiloxane-containing graft polymer (A) described above and 99.5 to 91% by weight of a thermoplastic polyester resin (B). , And a thermoplastic polyester resin composition (however, (A) and (B) are combined to be 100% by weight).

  The present invention relates to any one of the above-mentioned polyorganosiloxane-containing graft polymer (A) 0.5 to 9% by weight, thermoplastic polyester resin (B) 99.3 to 49.5% by weight, and inorganic filler ( C) It relates to a thermoplastic polyester resin composition characterized by containing 0.2 to 50% by weight.

  Volume-average particle size of 0.01-0.05 μm obtained by adding a water-soluble electrolyte during graft polymerization of a vinyl monomer onto a polyorganosiloxane having a volume-average particle size of 0.001-0.05 μm. By blending a 0.6 μm polyorganosiloxane-containing graft polymer with a thermoplastic resin, and further blending with an inorganic filler, the resulting thermoplastic resin composition, especially a thermoplastic polyester resin composition, is excellent. Bending elastic modulus and excellent impact resistance can be exhibited.

  In the present invention, a polyfunctional monomer comprising two or more polymerizable unsaturated bonds in the molecule in the presence of 30 to 95 parts by weight of a polyorganosiloxane (a) having a volume average particle size of 0.001 to 0.05 μm. A body (b) 100 to 50% by weight and other copolymerizable vinyl monomer (c) 0 to 50% by weight (provided that (b) and (c) are combined 100% by weight) Polymerize 0 to 10 parts by weight of monomer (d), and further polymerize 5 to 70 parts by weight of vinyl monomer (e) (however, (a), (d) and (e) are combined to be 100 parts by weight). A polymer having a volume average particle diameter of 0.01 to 0.6 μm obtained by adding a water-soluble electrolyte (f) during the polymerization of (d) and / or (e). Contains an organosiloxane-containing graft polymer, and the polymer and a thermoplastic polyester resin The present invention relates to a thermoplastic polyester resin composition.

  First, the polyorganosiloxane-containing graft polymer (A) used in the present invention will be described. The polyorganosiloxane-containing graft polymer of the present invention has 2 polymerizable unsaturated bonds in the molecule in the presence of 30 to 95 parts by weight of polyorganosiloxane (a) having a volume average particle size of 0.001 to 0.05 μm. Polyfunctional monomer (b) containing 100 to 50% by weight, and vinyl monomer (c) 0 to 50% by weight copolymerizable with other (b) ((b) and (c) Are combined to polymerize 0 to 10 parts by weight of a monomer (d) consisting of 100% by weight), and further 5 to 70 parts by weight of a vinyl monomer (e) ((a), (d) and (e) 100 parts by weight) is polymerized, and a water-soluble electrolyte (f) is added during the polymerization to enlarge and polymerize, resulting in a final volume average particle size of 0.01 to 0.6 μm after polymerization. Is.

  Although the polyorganosiloxane (a) used in the present invention can be obtained by ordinary emulsion polymerization, it is preferable to produce it using seed polymerization because of the advantage that the particle size distribution in the latex state can be narrowed. The seed polymer used for the seed polymerization is not limited to rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile rubber, but butyl acrylate-styrene copolymer or styrene-acrylonitrile. There is no problem with a polymer such as a copolymer. A chain transfer agent may be used for the polymerization of the seed polymer.

  In the polymerization of the polyorganosiloxane (a) used in the present invention, a graft crossing agent and, if necessary, a crosslinking agent can be used.

The organosiloxane used has the general formula: R _m SiO _{(4-m) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and m represents an integer of 0 to 3). The organosiloxane has a linear, branched or cyclic structure, and is preferably an organosiloxane having a cyclic structure. 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. it can.

  Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane. In addition to cyclic compounds such as these, linear or branched organosiloxanes can be mentioned. These organosiloxanes can be used alone or in combination of two or more.

  Examples of the grafting agent that can be used in the production of the polyorganosiloxane (a) include p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, methacryloxypropylmethyl Examples include dimethoxysilane.

  The proportion of the grafting agent used can be appropriately set, but is preferably 1 to 5% by weight based on the organosiloxane. If the amount of the grafting agent used is too large, the impact resistance of the final molded product tends to decrease. If the amount of the grafting agent used is too small, a large lump is formed during solidification and heat treatment, and a good resin powder is obtained. Or the formability of the final molded product tends to decrease.

  In the production of the polyorganosiloxane (a) used in the present invention, a crosslinking agent may be added as 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.

  If the amount of the crosslinking agent added in the production of the polyorganosiloxane (a) is too large, the flexibility of the polyorganosiloxane (a) is impaired, so that the impact resistance of the final molded product tends to decrease. As an index of flexibility of the polyorganosiloxane (a), a degree of swelling described below measured in a toluene solvent can be used. Specifically, if the degree of swelling is less than 15, it can be said that the flexibility of the polyorganosiloxane is insufficient.

  The polyorganosiloxane (a) used in the present invention is preferably one having a volume average particle diameter of 0.001 to 0.05 μm, from the viewpoint of greatly improving the impact resistance of the final molded product. It is more preferable to use one having a thickness of ˜0.03 μm. The volume average particle diameter can be measured by a light scattering method using MICROTRAC UPA manufactured by LEED & NORTHRUP INSTRUMENTS.

  In 100 parts by weight of the polyorganosiloxane-containing graft polymer of the present invention, the polyorganosiloxane (a) is preferably contained in an amount of 30 to 95 parts by weight, more preferably 60 to 90 parts by weight. If the polyorganosiloxane (a) is less than 30 parts by weight, the impact resistance of the final molded product tends to be difficult to increase. Conversely, if it exceeds 95 parts by weight, the polyorganosiloxane-containing graft polymer is agglomerated during solidification and is normal. It may be difficult to obtain a powder resin.

  There is no restriction | limiting in particular about the polyfunctional monomer (b) which contains two or more polymerizable unsaturated bonds in the molecule | numerator used for this invention, A well-known thing can be used. Specific examples of the polyfunctional monomer (b) include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. These may be used alone or in combination of two or more.

  The other copolymerizable vinyl monomer (c) is not particularly limited as long as it is a vinyl monomer copolymerizable with the above (b). Specific examples thereof include styrene, α -Aromatic vinyl monomers such as methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Examples thereof include (meth) acrylic acid ester monomers such as butyl methacrylate and 2-ethylhexyl methacrylate, and vinyl monomers containing an epoxy group in the molecule such as glycidyl methacrylate. These may be used alone or in combination of two or more. In addition, unless otherwise indicated in this invention, (meth) acryl means an acryl and / or methacryl.

  In the present invention, a monomer (d) comprising a polyfunctional monomer (b) containing two or more polymerizable unsaturated bonds in the molecule and another copolymerizable vinyl monomer (c). Serves to facilitate pulverization of the polyorganosiloxane-containing graft polymer resin. As the monomer (d), the polyfunctional monomer (b) is preferably 50 to 100% by weight, more preferably 90 to 100% by weight, and the other copolymerizable vinyl monomer (c). ) Is preferably 0 to 50% by weight, more preferably 0 to 10% by weight. However, the total of (b) and (c) is 100% by weight.

  The amount of the monomer (d) used in the production of the polyorganosiloxane-containing graft polymer is preferably 0 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, in 100 parts by weight of the polyorganosiloxane-containing graft polymer. Part is more preferred. The larger the amount of monomer (d) used, the better the state of the powder obtained, but when the amount of monomer (d) used exceeds 10 parts by weight, the final molded body obtained from the resin composition of the present invention There is a risk that the impact resistance of the will be reduced.

  The vinyl monomer (e) used in the present invention ensures compatibility between the polyorganosiloxane-containing graft polymer and the thermoplastic resin, in particular, the thermoplastic polyester resin, and the graft polymer is contained in the thermoplastic resin. A component used for uniform dispersion. Specific examples of the vinyl monomer (e) may be the same as the other copolymerizable vinyl monomers (c).

  Specifically, aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Examples include (meth) acrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and vinyl monomers having an epoxy group in the molecule such as glycidyl methacrylate. . These may be used alone or in combination of two or more. In order to ensure compatibility with the thermoplastic polyester resin, it is effective that the vinyl monomer (e) contains a monomer having an epoxy group.

  The vinyl monomer (e) is preferably used in an amount of 5 to 70 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polyorganosiloxane-containing graft polymer. When the vinyl monomer (e) is less than 5 parts by weight, the polyorganosiloxane-containing graft polymer is agglomerated at the time of solidification, and it is difficult to obtain a normal powder resin. There is a tendency that impact resistance is difficult to increase. The total of the polyorganosiloxane (a), the monomer (d), and the vinyl monomer (e) is 100 parts by weight.

  In the present invention, specific examples of the radical polymerization initiator in polymerizing the monomers (d) and (e) include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t- Organic peroxides such as butyl peroxyisopropyl carbonate, inorganic peroxides such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvalero Examples thereof include azo compounds such as nitrile. 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 a system, the polymerization can be completed even if the polymerization is carried out at a low polymerization temperature.

The water-soluble electrolyte (f) used in the present invention is used to agglomerate and enlarge the polyorganosiloxane during the polymerization of the monomer (d) and / or the vinyl monomer (e). Specifically, Na ⁺ , K ⁺ , Mg ⁺ , Ca ²⁺ , Al ³⁺ , H ⁺ and the like, Cl ⁻ , Br ⁻ , SO ₄ ²⁻ , SO ₃ ²⁻ , NO ₂ ⁻ , NO ₃ ⁻ , Examples thereof include compounds that dissociate into PO ₄ ³⁻ , CO ₃ ²⁻ , OH ^{−, and the} like. Specific examples of the compound include NaCl, KCl, Na ₂ SO ₄ , CaCl ₂ , and AlCl ₃ . The amount of the water-soluble electrolyte (f) added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 6 with respect to 100 parts by weight of the above (a), (d) and (e). Part by weight is more preferred. If the addition amount of the water-soluble electrolyte (f) is less than 0.1 parts by weight, it is difficult to agglomerate and enlarge, on the contrary, if it exceeds 10 parts by weight, the stability of the latex may be insufficient and the polymerization scale may increase.

  The addition timing of the water-soluble electrolyte (f) is preferably during the polymerization of the monomer (d) and / or the vinyl monomer (e). The term “in the middle of polymerization” here is not particularly limited as long as the monomer (d) and / or the vinyl monomer (e) is being polymerized in the presence of the polyorganosiloxane (a), If the addition time is too early, the impact resistance of the final molded product tends to be difficult to increase, and if the addition time is too late, cohesive enlargement may not occur easily.

  The final volume average particle diameter of the polyorganosiloxane-containing graft polymer after enlargement / polymerization is 0.01 to 0.6 μm. The impact strength of the final molded product obtained from the resin composition of the present invention is greatly influenced by the particle size of the polyorganosiloxane-containing graft polymer, and the volume average particle size is smaller than 0.01 μm or conversely exceeds 0.6 μm. In such a case, the impact strength of the molded product obtained from the resin composition tends to greatly decrease when blended with a thermoplastic resin. In particular, when the polyorganosiloxane-containing graft polymer of the present invention is blended with a thermoplastic polyester resin, the volume average particle diameter of the graft polymer is more preferably 0.06 to 0.2 μm. When compared with the same particle size, the polyorganosiloxane-containing graft polymer enlarged by adding the water-soluble electrolyte according to the present invention, rather than the usual polyorganosiloxane-containing graft polymer produced without the enlargement operation This can improve the impact strength of the final molded body.

  As a method for separating the polymer from the polyorganosiloxane-containing graft polymer (A) latex obtained as described above, for example, the latex is coagulated by adding a metal salt such as calcium chloride, magnesium chloride, magnesium sulfate to the latex, Next, a method of separating the polymer by post-treatment, washing with water, dehydrating and drying can be used. A spray drying method can also be used.

  The polyorganosiloxane-containing graft polymer (A) thus obtained can be blended with various thermoplastic resins. The blending amount is preferably 0.3 to 10% by weight, more preferably 0.5 to 9% by weight. When blended in the thermoplastic resin (B), the inorganic filler (C) is preferably blended together with 0.2 to 50% by weight, more preferably 1 to 30% by weight, particularly 2 to 15% by weight. (However, A + B or A + B + C together is 100% by weight). When the blending amount of the polyorganosiloxane-containing graft polymer (A) is less than the above range, the resulting impact resistance improvement effect is small, and conversely, when exceeding the above range, the flexural modulus of the final molded body is the original thermoplastic resin. There is a case where it falls as well.

  As the thermoplastic resin, a thermoplastic polyester resin is particularly preferable. The blending amount of the polyorganosiloxane-containing graft polymer (A) is preferably within the above range. For example, when blended with a thermoplastic polyester resin, 0.5 to 9% by weight, further 2 to 8% by weight, In particular, 5 to 8% by weight is preferable. For example, when the graft polymer (A) is 0.5 to 9% by weight and the inorganic filler amount (C) is 0.2 to 50% by weight, the thermoplastic polyester resin (B) is 99.5 to 99.5%. 91% by weight. If these components are within the above ranges, in addition to impact resistance and flexural modulus, the excellent properties of thermoplastic polyester resins such as heat resistance, chemical resistance, mechanical properties, electrical properties, etc. can be sufficiently exerted. preferable.

  The thermoplastic polyester resin (B) used in the present invention includes a dicarboxylic acid compound and / or an acid component mainly composed of an ester-forming derivative of dicarboxylic acid, and a diol compound and / or an ester-forming derivative of a diol compound. It is an arbitrary thermoplastic polyester resin obtained by a reaction with a diol component as a main component. With the said main component, the ratio which occupies in an acid component or a diol component intends that it is 80 weight% or more, Furthermore, 90 weight% or more, and an upper limit is 100 weight%.

  Specific examples of the thermoplastic polyester resin (B) 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 thermoplastic polyester resins may be used alone or in combination of two or more types having different compositions or components and / or different intrinsic viscosities. Among the polyester resins, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, and polyethylene naphthalate are preferable in terms of strength, elastic modulus, cost, and the like.

  In the present invention, the inorganic filler (C) used in the resin composition with a thermoplastic resin, preferably a thermoplastic polyester resin, for example, calcium carbonate, talc, mica, aluminum oxide, magnesium hydroxide, boron nitride, Examples include beryllium oxide, calcium silicate, and clay. Among them, silicate, phosphate such as zirconium phosphate, titanate such as potassium titanate, tungstate such as sodium tungstate, uranate such as sodium uranate, vanadate such as potassium vanadate, It is preferable to apply a treatment for improving dispersibility to a molybdate such as magnesium molybdate, a niobate such as potassium niobate, or a layered compound such as graphite.

  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.

  When the blending amount of the inorganic filler (C) used in the present invention is less than 0.2% by weight, the bending elastic modulus and heat resistance improving effect of the thermoplastic resin and further the thermoplastic polyester resin may be reduced. On the other hand, if it exceeds 50% by weight, the surface appearance of the molded product may be impaired.

  The method for producing the thermoplastic resin composition or the thermoplastic polyester resin composition of the present invention is not particularly limited. For example, the thermoplastic resin is melt kneaded with other components using various general kneaders. can do. 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 resin, the inorganic filler, and the polyorganosiloxane-containing graft polymer may be charged into the kneader and melt-kneaded, or may be pre-molten thermoplastic polyester resin and polyorganosiloxane-containing graft polymer. An inorganic filler may be added to the coalescence and melt kneaded.

  In the thermoplastic resin composition or the thermoplastic polyester resin composition of the present invention, if necessary, any other thermoplastic resin or thermosetting resin, for example, within a range not impairing properties such as mechanical properties, for example, Unsaturated polyester resin, polyester carbonate resin, liquid crystal polyester resin, polyolefin resin, polyamide resin, rubbery polymer reinforced styrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, and polyarylate resin alone or Two or more types can be used in combination.

  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 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. Since the obtained molded article has excellent appearance and excellent mechanical properties and heat distortion resistance, it is 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 with 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 (%).

[Volume average particle diameter]
The volume average particle diameters of the seed polymer, polyorganosiloxane particles, and graft polymer were 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.

[Swelling degree]
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. The degree of swelling was calculated by the following formula.
Swelling degree = ((swelled polymer weight) − (dry polymer weight weighed again)) / (dry polymer weight weighed again).

[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.

[Gardner strength]
In accordance with the ASTM D-5420 GE method, evaluation was performed by a Gardner impact test at 23 ° C. using a イ ン チ inch plate.

(Examples 1-3)
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 400 parts by weight of water (total amount of water including various dilution water) and sodium dodecylbenzenesulfonate (SDBS) ) After 8 parts by weight (solid content) were mixed, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, a mixed solution of 10 parts by weight of butyl acrylate, 3 parts by weight of t-dodecyl mercaptan, and 0.01 parts by weight of paramentane hydroperoxide was 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, 27 parts by weight of t-dodecyl mercaptan, and 0.1 parts by weight of paramentane hydroperoxide was continuously added over 3 hours. Post-polymerization was performed for 2 hours to obtain a seed latex (seed 1). The volume average particle diameter after synthesis was 0.04 μm.

  In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 450 parts by weight of water (total amount of water including various dilution water), seed latex (seed 1) 2 After mixing parts by weight (solid content) and dodecylbenzenesulfonic acid (DBSA) in the amount shown in Table 1 (solid content), the temperature was raised to 80 ° C, and after the liquid temperature reached 80 ° C, nitrogen substitution was performed. It was. Thereafter, a mixture of 150 parts by weight of pure water, 0.5 part by weight of SDBS (solid content), 98 parts by weight of octamethylcyclotetrasiloxane, and 3 parts by weight of methacryloxypropylmethyldimethoxysilane (DSMA) was 7000 rpm with a homomixer. The emulsion obtained by stirring for 5 minutes was continuously added over 3 hours. After completion of the addition, stirring was continued at 80 ° C. for 2 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.4 with sodium hydroxide to complete the polymerization, and a polyorganosiloxane latex (R1) was obtained. Table 1 shows the volume average particle diameter and the degree of swelling of the lux.

  In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 240 parts by weight of water (total amount of water including various dilution waters), polyorganosiloxane (R1) 80 A part by weight (solid content) was charged, and the temperature was raised 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, 0.0025 parts by weight of ferrous sulfate, 18 parts by weight of methyl methacrylate, methacrylic acid A mixture of 2 parts by weight of glycidyl and 0.06 parts by weight of cumene hydroperoxide was added dropwise over 1 hour, and stirring was continued for 1 hour after the addition was completed to obtain a graft polymer latex.

During the dropping of the mixture (30 minutes after the start of dropping), a 10 wt% Na ₂ SO ₄ aqueous solution was added in the amount (solid content) shown in Table 2 to enlarge the mixture during the polymerization. Subsequently, the graft polymer latex was diluted with pure water to a solid content concentration of 15% by weight, and then 4 parts by weight (solid content) of a 25% by weight calcium chloride aqueous solution was added to obtain a coagulated slurry. 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 polymer powder. It was.

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

  Biaxial extrusion of 100 parts by weight of thermoplastic polyester resin (manufactured by Kanebo Co., Ltd., trade name: Belpet EFG85A), 10 parts by weight of inorganic filler and 7.5 parts by weight of the polyorganosiloxane-containing graft polymer shown in Table 2 A thermoplastic polyester resin composition was obtained by melt-kneading using a machine (manufactured by Nippon Steel Co., Ltd., TEX44), and physical properties were evaluated. The results are shown in Table 2.

(Comparative Examples 1-4)
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 450 parts by weight of water (total amount of water including various dilution water), and 150 parts by weight of pure water, Emulsification obtained by stirring a mixture of 0.5 parts by weight (solid content) of SDBS, 100 parts by weight of octamethylcyclotetrasiloxane, and 3 parts by weight of methacryloxypropylmethyldimethoxysilane (DSMA) with a homomixer at 7000 rpm for 5 minutes. The liquid was mixed and purged with nitrogen. Then, the quantity (solid content) shown in Table 1 was mixed for dodecylbenzenesulfonic acid (DBSA), and it heated up at 80 degreeC. After the liquid temperature reached 80 ° C., stirring was continued at 80 ° C. for 7 hours. Then, it cooled to 25 degreeC and left to stand for 20 hours. Thereafter, the pH was adjusted to 6.4 with sodium hydroxide to complete the polymerization, and a polyorganosiloxane latex (R2 to R4) was obtained. Table 1 shows the volume average particle diameter and the degree of swelling of the lux.

  In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 240 parts by weight of water (total amount of water including various dilution waters), polyorgano shown in Table 2 80 parts by weight (solid content) of siloxane was charged, and the temperature was raised to 40 ° C. in 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, 0.0025 parts by weight of ferrous sulfate, 18 parts by weight of methyl methacrylate, methacrylic acid A mixture of 2 parts by weight of glycidyl and 0.06 parts by weight of cumene hydroperoxide was added dropwise over 1 hour, and stirring was continued for 1 hour after the addition was completed to obtain a graft polymer latex.

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

A polyester resin composition was obtained in the same manner as in the examples, and the physical properties were evaluated. The results are shown in Table 2.
(Comparative Example 5)
Polyester by melt-kneading 100 parts by weight of a thermoplastic polyester resin (manufactured by Kanebo Co., Ltd., trade name: Belpet EFG85A) using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44) in the same manner as in the examples A resin composition was obtained and physical properties were evaluated. The results are shown in Table 2.

As described in Table 2, according to the present invention, the impact resistance and bending elastic modulus of the thermoplastic polyester resin can be improved.

Claims (5)

In the presence of 30 to 95 parts by weight of polyorganosiloxane (a) having a volume average particle size of 0.001 to 0.05 μm,
100 to 50% by weight of polyfunctional monomer (b) containing two or more polymerizable unsaturated bonds in the molecule, and 0 to 50% by weight of other copolymerizable vinyl monomer (c) (however, , (B) and (c) are combined to polymerize a monomer (d) of 0 to 10 parts by weight,
Furthermore, a polymer obtained by polymerizing 5 to 70 parts by weight of a vinyl monomer (e) (however, 100 parts by weight of (a), (d) and (e) are combined),
A polyorganosiloxane-containing graft polymer having a volume average particle diameter of 0.01 to 0.6 μm obtained by adding the water-soluble electrolyte (f) during the polymerization of (d) and / or (e).   The polyorganosiloxane-containing graft polymer according to claim 1, wherein the vinyl monomer (e) contains a monomer having an epoxy group.   3. The polyorganosiloxane-containing graft polymer according to claim 1, wherein the graft polymer has a volume average particle diameter of 0.06 to 0.2 μm.   It contains 0.5 to 9% by weight of the polyorganosiloxane-containing graft polymer (A) according to any one of claims 1 to 3, and 99.5 to 91% by weight of a thermoplastic polyester resin (B). A thermoplastic polyester resin composition (however, (A) and (B) are combined in 100% by weight). The polyorganosiloxane-containing graft polymer (A) according to any one of claims 1 to 3, 0.5 to 9% by weight, thermoplastic polyester resin (B), 99.3 to 49.5% by weight, and inorganic filler (C) A thermoplastic polyester resin composition comprising 0.2 to 50% by weight.