WO2006051667A1 - Composition de résine de polyester - Google Patents

Composition de résine de polyester Download PDF

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Publication number
WO2006051667A1
WO2006051667A1 PCT/JP2005/018884 JP2005018884W WO2006051667A1 WO 2006051667 A1 WO2006051667 A1 WO 2006051667A1 JP 2005018884 W JP2005018884 W JP 2005018884W WO 2006051667 A1 WO2006051667 A1 WO 2006051667A1
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Prior art keywords
weight
polyorganosiloxane
polyester resin
parts
thermoplastic polyester
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PCT/JP2005/018884
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English (en)
Japanese (ja)
Inventor
Tomomichi Hashimoto
Akira Takaki
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Kaneka Corporation
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Priority to JP2006544810A priority Critical patent/JPWO2006051667A1/ja
Publication of WO2006051667A1 publication Critical patent/WO2006051667A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

  • the present invention relates to a thermoplastic polyester resin composition
  • 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 widely used industrially as injection molding materials, fibers, and films. in use.
  • various inorganic fillers for example, Patent Documents 1 and 2). reference).
  • thermoplastic polyester resin As described above, it has been extremely difficult to balance the bending elastic modulus and impact resistance / stretch resistance of thermoplastic polyester resin, and the market has high bending elastic modulus and heat resistance. The appearance of a thermoplastic polyester resin having a high impact resistance and stretch resistance has been desired.
  • Patent Document 1 JP-A-10-259016
  • Patent Document 2 JP-A-10-310420
  • Patent Document 3 Japanese Patent Application Laid-Open No. 62-121752
  • the object of the present invention is to provide excellent flexural modulus and heat resistance, as well as excellent impact resistance and stretch resistance. It is in providing the thermoplastic polyester resin composition which has the property.
  • the present inventors have solved the above problem by combining a specific polyorganosiloxane-containing graft copolymer with a thermoplastic polyester resin and an inorganic filler.
  • the present inventors have found that the present invention can be accomplished and have completed the present invention.
  • 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), Polyorganosiloxane graft copolymer (C) force Late cross-linked polyorganosiloxane (C2) modified with a graft-crossing agent (C1) containing a mercapto group-containing silane compound (C2) 30 to 94.9 parts by weight, and (meth) atalyloyl Graft-crossing agent containing oxy group-containing silane compound (C3) 0.1-10 parts by weight are reacted, and vinyl monomer (C4) 5-69. 9 parts by weight ((C2), (C3 ), (C4) and 100 parts by weight in total).
  • thermoplastic polyester resin A 95-45% by weight, inorganic filler (B) O. 2-50% by weight, polyorganosiloxane-containing graft copolymer (C) O. It is contained in the range of 5 to 9% by weight ((A;), (B), (C) in total 100% by weight), and relates to the thermoplastic polyester resin composition described above.
  • the embodiment relates to the thermoplastic polyester resin composition according to any one of the above, wherein mercaptopropylmethyldimethoxysilane is used as the graft crossing agent (C1).
  • thermoplastic polyester resin composition of the present invention it is possible to obtain a molded article exhibiting excellent bending elastic modulus, impact resistance, and stretch resistance.
  • 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), Polyorganosiloxane graft copolymer (C) Force Contains mercapto group-containing silane compound In the presence of 30-94.9 parts by weight of a polyorganosiloxane (C2) in a latex state modified with a graft crossing agent (C1), a graft crossing agent containing a silane compound containing a (meth) ataryloxy group ( C3) 0.1 ⁇ : Add LO parts by weight and react, then vinyl monomer (C4) 5 ⁇ 69.9 parts by weight ((C2), (C3), (C4) in total 100 parts by weight) ) Is obtained by polymerizing at least one stage to obtain a thermoplastic polyester resin composition.
  • a polyorganosiloxane (C2) in a latex state modified with
  • thermoplastic polyester resin (A) used in the present invention is not particularly limited! / ⁇ is an acid component mainly composed of a dicarboxylic acid compound and an ester-forming derivative of Z or dicarboxylic acid, and diol Any thermoplastic polyester resin obtained by a reaction with a diol component mainly comprising a compound and an ester-forming derivative of Z or a dioli compound is used.
  • main component means that the proportion of each of the components in the acid component or diol component is 80% by weight or more, and further 90% by weight or more, and the upper limit is 100% by weight. is there.
  • thermoplastic polyester resin (A) examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate.
  • examples thereof include tantalum, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, and polyhexamethylene naphthalate.
  • a copolymer polyester produced by using two or more kinds of acid components and Z or diol components used in the production of these coconuts can be mentioned.
  • thermoplastic polyester resin can be used as appropriate, alone or in combination of two or more types having different compositions or components or different intrinsic viscosities.
  • thermoplastic polyester resins polyethylene terephthalate, polybutylene terephthalate, polycyclohexane 1,1,4 dimethyl terephthalate, and polyethylene naphthalate are more preferable from the viewpoint of strength, elastic modulus, cost, and the like.
  • the thermoplastic polyester resin is 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 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 particular limitation, for example, Calcium carbonate, talc, mica, magnesium oxide, magnesium hydroxide, boron nitride, beryllium oxide, silicates such as calcium phosphate, phosphates such as zirconium phosphate, titanates such as potassium titanate , Tungstates such as sodium tungstate, uranates such as sodium uranate, vanadate such as potassium vanadate, molybdate such as magnesium molybdate, niobate such as potassium niobate, graphite, etc.
  • Examples include layered compounds and clays.
  • layered compounds such as silicates, phosphates, titanates, tandastates, uranates, vanadates, molybdates, niobates, and graphite are preferred and dispersed. What gave the process for property improvement is more preferable.
  • Specific examples of the treatment for improving dispersibility of the layered composite include montmorillonite, bentonite, hectorite, and layered silicates such as swelling mica having sodium ions between layers,
  • a polyoxyalkylene compound such as polyoxyethylene or polyoxyethylene polyoxypropylene copolymer is treated with a polyether compound having a cyclic hydrocarbon group in the side chain and Z or main chain. 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. % Is most preferred.
  • Inorganic filler (B) Mass strength Less than 0.2% by weight The effect of improving the flexural modulus and heat resistance of thermoplastic polyester resin composition tends to be small. Conversely, if it exceeds 50% by weight, the surface appearance of the molded product may be impaired.
  • the polyorganosiloxane-containing graft copolymer (C) used in the present invention is a latex-like polyorganosiloxane (C2) modified with a graft-crossing agent (C1) containing a mercapto group-containing silane compound.
  • a graft-crossing agent (C3) containing a (meth) atallyloyloxy group-containing silane compound is added and reacted.
  • C4) 5 to 69.9 parts by weight (100 parts by weight in total of (C2), (C3) and (C4)) are obtained by polymerizing one or more stages.
  • (meth) acryl means acrylic and Z or methacryl unless otherwise specified.
  • the polyorganosiloxane (C2) used in the present invention is preferably obtained by emulsion polymerization.
  • the organosiloxane used as a raw material has a general formula R SiO (wherein R is a substituted or m (4-m ) / 2
  • R is a substituted or m (4-m ) / 2
  • An unsubstituted monovalent hydrocarbon group, m is an integer of 0 to 3, and has a cyclic structure, a straight chain, or a branched 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. I can give you.
  • a polyorganosiloxane using an organosiloxane having a cyclic structure as a raw material can also be obtained by ordinary emulsion polymerization, but it has the advantages of being able to narrow the particle size distribution in the latex state and improving flame retardancy. It is better to use seed polymerization.
  • the seed polymer used for the seed polymerization is not particularly limited, but butyl acrylate rubber, butadiene rubber, rubber components such as butadiene-styrene and butadiene-acrylonitrile, butyl acrylate-styrene copolymer, styrene acrylonitrile copolymer, etc.
  • the following polymers can be used.
  • a chain transfer agent may be added to the polymerization of the seed polymer.
  • an organosiloxane having a cyclic structure, a graft-crossing 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, thereby bringing the polyorganosiloxane into an acidic state.
  • Emulsion polymerization can be performed.
  • organosiloxane having a cyclic structure examples include hexamethylcyclotrisiloxane (D3), otamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexane.
  • Hexasiloxane (D6), trimethyltriphenylcyclotrisiloxane and the like can be mentioned.
  • a graft crossing agent (C1) is used in the polymerization of the polyorganosiloxane (C2) used in the present invention.
  • 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 lower reaction efficiency with the vinyl monomer (C4) described later than the (meth) ataryloxy group-containing silane compound used in the graft crossing agent (C3).
  • the graft crossing agent (C1) into a mercapto group-containing silane compound,
  • the reaction rate of the vinyl monomer (C4) inside the ganosiloxane (C2) particle is suppressed, and the vinyl monomer (C4) can be efficiently polymerized and coated on the surface of the particle (C2).
  • 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 The impact resistance may decrease.
  • graft crossing agent (C1) a so-called bifunctional silane compound having two hydrolyzable silicon groups can be preferably used.
  • 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.
  • mercapto group-containing silane compound examples include, for example, mercaptopropyl.
  • mercaptopropylmethyldimethoxysilane is particularly preferred.
  • the amount of the graft-crossing agent (C1) used is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, and particularly preferably 0.8% to 100% by weight of the polyorganosiloxane (C2). 8 5% by weight. If the amount of graft crossing agent (C1) used exceeds 10% by weight, the impact resistance of the final molded product may decrease, and the stretch resistance may decrease. Conversely, the amount of graft crossing agent (C1) used may be 0.1% by weight. If it is less than%, the moldability and the bending elastic modulus of the final molded product obtained from the resin composition of the present invention may be lowered.
  • a crosslinking agent may be added if necessary.
  • 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) And tetrafunctional cross-linking agents such as) ethyl] -3- [2 (dimethoxymethylsilyl)
  • cross-linking agents may be used alone or in combination of two or more. You can also.
  • the amount of the crosslinking agent used is preferably 0 to 2% by weight, more preferably 0 to 0.5% by weight, based on 100% by weight of the polyorganosiloxane (C2).
  • 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.
  • an index of flexibility of the polyorganosiloxane (C2) for example, the degree of swelling measured in a toluene solvent can be used.
  • 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 30-94 based on 100 parts by weight of the total of the component (C2), the graft crossing agent (C 3), and the bull monomer (C4). It is preferably used in an amount of 9 parts by weight, more preferably 50 to 80 parts by weight.
  • the amount of (C2) is less than 30 parts by weight, the impact resistance in the final molded product tends to decrease due to a substantial decrease in the rubber component, and conversely when it exceeds 94.9 parts by weight, polyorgano
  • the dispersibility of the siloxane-containing graft copolymer particles decreases, the impact resistance and appearance of the final molded product tend to decrease.
  • an emulsifier that does not lose the emulsification ability under an acidic state can be used.
  • Specific examples include alkylbenzene sulfonic acid, sodium alkyl benzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, (di) sodium alkyl sulfosuccinate, sodium polyoxyethylene non-ether ether sulfonate, sodium alkyl sulfate, etc. can give. These may be used alone or in combination of two or more.
  • alkylbenzene sulfonic acid sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, and (di) sodium alkyl sulfonate are preferable because the emulsion stability of the emulsion is relatively high. 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 includes inorganic acids such as sulfuric acid and hydrochloric acid, alkylbenzene sulfonic acids, and alcohols. Considering the fact that organic acids such as killed sulfonic acid and trifluoroacetic acid can be added, and that the pH is less likely to corrode production equipment and that an appropriate polymerization rate can be obtained, the pH is adjusted to 1.0 to 3.0. It is preferable to adjust, and it is more preferable to adjust to 1.0 to 2.5.
  • inorganic acids such as sulfuric acid and hydrochloric acid, alkylbenzene sulfonic acids, and alcohols.
  • 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.
  • productivity decreases, and conversely, when the polymerization temperature is higher than 100 ° C, volatile siloxane tends to increase.
  • the graft crossing agent (C3) used in the present invention is a component used for intensively reacting the bulle monomer (C4) on the surface of the polyorganosiloxane particles.
  • the resin-based monomer (C4) has a function of ensuring the compatibility between the graft copolymer and the thermoplastic resin, the resin composition of the present invention can be obtained efficiently. The flame retardancy and impact resistance of a molded body are improved.
  • the graft crossing agent (C3) used in the present invention can be used alone or in combination of two or more of the sylanic compounds generally known as graft crossing agents.
  • C3) It is preferable to use a (meth) attayloxy group-containing silane compound for 80% by weight or more, preferably 90% by weight or more with respect to 100% by weight.
  • the (meth) ataryloxy 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).
  • the graft crossing agent (C3) by making 80% by weight or more of the graft crossing agent (C3) into a (meth) ataryloxy group-containing silane compound,
  • the vinyl monomer (C4) can be efficiently coated on the surface of the polyorganosiloxane (C2) particles.
  • the content of the (meth) ataryloxy group-containing silane compound in the graft-crossing agent (C3) is lower than 80% by weight, the polyorganosiloxane-containing graft copolymer in the final molded product
  • the dispersibility of the resin may decrease, and the impact resistance may decrease.
  • the graft crossing agent (C3) it is preferable to use a so-called bifunctional silane compound having two hydrolyzable groups.
  • the impact resistance of the molded article which is the final form in which the resin composition strength of the present invention can be obtained, may decrease the stretch resistance. is there.
  • Specific examples of the (meth) attayloxy group-containing silane compound include, for example, methacryloyloxypropyldimethoxymethylsilane, methacryloyloxypropyl jet oxy.
  • the amount of the graft crossing agent (C3) used is 0.1 to the polyorganosiloxane-containing graft copolymer (C) (100 parts by weight in total of (C2), (C3), and (C4)).
  • ⁇ : LO parts by weight are preferred, more preferably 0.5 to 7 parts by weight. If the amount of the graft crossing 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. If the amount used is less than 0.1 part by weight, the flame retardant / impact resistance improving effect of the present invention may not be sufficiently obtained.
  • the method of adding the graft crossing agent (C3) to the polyorganosiloxane (C2) in the latex state is not particularly limited, but, for example, the silane compound is emulsified in pure water containing a small amount of an emulsifier in advance. It is preferable to add from the above.
  • the Silane compound is added directly to the polyorganosiloxane latex in the acidic state, the graft crossing agent will become a foreign substance before reacting with the polyorganosiloxane particles, and the impact resistance of the final molded product will be reduced. There is a possibility to make it.
  • the graft crossing agent (C3) is preferably in the surface layer portion of the polyorganosiloxane particles V, but tends to be uniformized to the inside of the polyorganosiloxane particles at a high temperature or when the reaction is continued for a long time. For this reason, the impact resistance improvement effect may not be sufficiently obtained. For this reason, the reaction between the grafting agent (C3) and the polyorganosiloxane (C2) has a polymerization temperature of 20%.
  • the polymerization time is preferably 0.5 to 12 hours, more preferably 1 to 4 hours, preferably performed at ° C to 60 ° C, more preferably 20 to 40 ° C.
  • the graft crossing agent (C3) When the polymerization temperature is less than 20 ° C or when the polymerization time is less than 0.5 hour, the graft crossing agent (C3) may be unreacted, and when the polymerization temperature is higher than 60 ° C or the polymerization time is 12 If it is longer than the time, since homogeneity in the polyorganosiloxane particles tends to progress, both the impact resistance and the stretch resistance of the final molded product may be lowered.
  • the graft crossing agent (C3) 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 due to the equilibrium reaction decreases. It is preferable to neutralize immediately after completion of the reaction between C3) and polyorganosiloxane (C2) by adding an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide and sodium carbonate.
  • an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide and sodium carbonate.
  • the vinyl monomer (C4) used in the present invention ensures the compatibility of the graft copolymer (C) with the thermoplastic polyester resin (A) and heats the graft copolymer (C). It is a component used for uniformly dispersing in the plastic polyester resin (A). Specifically, for example, aromatic butyl monomers such as styrene and ⁇ -methylstyrene, cyanated butyl monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, and metacryl.
  • aromatic butyl monomers such as styrene and ⁇ -methylstyrene
  • cyanated butyl monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, and metacryl.
  • Examples include (meth) acrylic acid ester monomers such as ethenyl and butyl methacrylate, and butyl monomers containing an epoxy group in the molecule such as (meth) glycidyl acrylate. These can be used alone. May be used in combination of two or more.
  • radical polymerization initiators include organic peroxides such as cumene hydride peroxide, t-butyl hydride peroxide, benzoyl peroxide, tert-butylperoxyisopropyl carbonate, potassium persulfate, and persulfate.
  • organic peroxides such as cumene hydride peroxide, t-butyl hydride peroxide, benzoyl peroxide, tert-butylperoxyisopropyl carbonate, potassium persulfate, and persulfate.
  • examples thereof include inorganic peroxides such as ammonia, and azo compounds such as 2,2′-azobisisobutyryl-tolyl and 2,2′-azobis-2,4 dimethylvaleryl-tolyl.
  • This polymerization is carried out in a redox system such as ferrous sulfate, formaldehyde sulfoxylate, ethylenediaminetetraacetic acid '2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate, sodium pyrophosphate, and sodium phosphate.
  • a redox system such as ferrous sulfate, formaldehyde sulfoxylate, ethylenediaminetetraacetic acid '2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate, sodium pyrophosphate, and sodium phosphate.
  • low polymerization temperature Polymerization can be completed even once.
  • a latex is a metal salt such as calcium salt, calcium salt, magnesium sulfate and magnesium sulfate.
  • the method of coagulating the latex by adding, then separating the coagulated slurry, washing with water, dehydrating and drying can be mentioned.
  • a spray drying method can also be used.
  • the polyorganosiloxane-containing graft copolymer (C) thus obtained is blended in 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) in total). 3-8% by weight, even 5-8% by weight is more preferred to U.
  • the blending amount of the polyorganosiloxane-containing draft copolymer (C) in the greave composition is less than 0.5% by weight, the impact resistance of the final molded product obtained is less effective in improving stretch resistance.
  • the blending amount of the graft copolymer (C) exceeds 9% by weight, the flexural modulus of the final molded product may decrease to the same level as the original thermoplastic polyester resin.
  • thermoplastic polyester resin can be melt-kneaded using various general kneaders.
  • 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, inorganic filler, and polyorganosiloxane-containing graft copolymer may be charged into the kneader and melt-kneaded, or may be pre-molten thermoplastic polyester resin and polyester.
  • An inorganic filler may be added to the organosiloxane-containing graft polymer and melt kneaded.
  • polyester resin composition of the present invention if necessary, other arbitrary thermoplastic resin or thermosetting resin, for example, unsaturated, within a range not impairing properties such as mechanical properties.
  • Polyester resin, Polyester carbonate resin, Polyolefin resin, Polyamide resin, Rubber polymer reinforced styrene resin, Polyphenylene sulfide resin, Polyphenylene ether resin, Polyacetal resin, Polysulfone resin, Acrylic resin, and Polyarylate resins or the like may be used alone or in combination of two or more.
  • additives such as pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents are added. be able to.
  • thermoplastic polyester resin composition obtained in the present invention can be used for blow molding which may be molded by injection molding or hot press molding.
  • the resulting molded article has an excellent appearance and is excellent in mechanical properties and heat distortion resistance, 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 latex was dried with a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and calculated as 100 X (solid component amount Z charged monomer amount) (%).
  • 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 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. Next, 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 weighed again. Swellability was calculated by the following formula.
  • the volume average particle size of the seed polymer, polyorganosiloxane particles, and graft copolymer was measured in the latex state.
  • MICROTRAC UPA manufactured by LEED & NORTHHRUP INSTRUMENTS The volume average particle diameter ( ⁇ m) was measured by a light scattering method.
  • a 1Z8 inch thick 1A type dumbbell test piece was used to conduct a tensile test at 23 ° C and a speed of lOmmZ, and evaluated by the elongation at break.
  • a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, additional monomer port, and thermometer is mixed with 300 parts by weight of pure water and 12 parts by weight (solid content) of sodium dodecylbenzenesulfonate (SDBS). 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-decyl mercaptan (tDM), and 0.01 parts by weight of noramentane hydride peroxide were added. 30 minutes later, ferrous sulfate (FeS O 7 ⁇ 0) 0.002 parts by weight, ethylenediaminetetraacetic acid 2Na salt 0.00
  • DBS DBS
  • graft crossing agent (C3) were added in parts by weight as shown in Tables 1 and 2 and stirred for 30 minutes with a stirrer to prepare emulsion, which was added all at once.
  • 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 diethylenediamine tetraacetate, and 0.0125 parts by weight of ferrous sulfate were added. A mixture of 20 parts by weight of component (C4) and 0.06 parts by weight of cumene hydride peroxide was added dropwise over 1 hour, and after completion of the addition, stirring was continued for 1 hour 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.
  • Ion exchange water and swelling mica (trade name: Somasif ME100, manufactured by Corp Chemical Co., Ltd.) were mixed. Then, a polyethery compound (trade name: Bisol 18EN, manufactured by Toho Chemical Co., Ltd.) was added, and the mixture was processed by continuing mixing for 15 to 30 minutes. Thereafter, it was powdered to obtain an inorganic filler (B) treated with a polyether compound.
  • a polyethery compound trade name: Bisol 18EN, manufactured by Toho Chemical Co., Ltd.
  • Thermoplastic polyester resin (manufactured by Kanebo Co., Ltd., trade name: Belpet EFG85A) 85 parts by weight, 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 Table 3 and Table 4, and further melt kneaded at 260 ° C. using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44) to obtain pellets.
  • a twin screw extruder manufactured by Nippon Steel Co., Ltd., TEX44
  • thermoplastic polyester resin composition Thereafter, the obtained pellets were molded by a FASIOOB injection molding machine manufactured by FANUC Co., Ltd., which was 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.
  • Thermoplastic resin Tellurium resin (A) (Part) 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85
  • Type 2 B-type eye '/ t strength (KJ / m2) 7.3 7.7 7.6 8.4 8.9 7.2 7 7.4
  • Stretch resistance Tensile test Elongation at break (%) ⁇ 6.4 6.1 10.4 6.3 6.3 10.1 13.3
  • thermoplastic polyester resin containing inorganic filler is obtained by the addition of an agent (C3) and reaction, and further by polymerization of one or more vinyl monomers (C4) with an organosiloxane-containing graft polymer. And stretchability can be improved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition de résine de polyester thermoplastique, excellente en termes de module de résistance à la flexion, de résistance à la chaleur, de résistance aux chocs et de résistance à l'étirement, précisément une composition de résine de polyester thermoplastique comprenant une résine de polyester thermoplastique (A), une charge inorganique (B) et un copolymère greffé contenant un polyorganosiloxane (C), caractérisée en ce que le copolymère greffé (C) est un copolymère obtenu en faisant réagir 30 à 94,9 parties en poids d'un polyorganosiloxane (C2) qui est sous la forme d'un latex et qui est modifié avec un agent de greffage (C1) contenant un composé silane portant un groupe mercapto avec 0,1à 10 parties en poids d'un agent de greffage (C3) contenant un composé silane portant un groupe (méth)acryloyloxy et en polymérisant ensuite 5 à 69,9 parties en poids d'un monomère vinylique (C4) en présence du produit de réaction en une ou plusieurs étapes à condition que la quantité totale de (C2), (C3) et (C4) soit de 100 parties en poids.
PCT/JP2005/018884 2004-11-09 2005-10-13 Composition de résine de polyester WO2006051667A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862964A (zh) * 2015-06-09 2015-08-26 科凯精细化工（上海）有限公司 一种用于涤纶织物的核壳结构乳液增深剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476293A1 (fr) * 1990-08-27 1992-03-25 Mitsubishi Rayon Co., Ltd. Composition de résine polyester
JP2005255961A (ja) * 2004-03-15 2005-09-22 Kaneka Corp ポリエステル樹脂組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476293A1 (fr) * 1990-08-27 1992-03-25 Mitsubishi Rayon Co., Ltd. Composition de résine polyester
JP2005255961A (ja) * 2004-03-15 2005-09-22 Kaneka Corp ポリエステル樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862964A (zh) * 2015-06-09 2015-08-26 科凯精细化工（上海）有限公司 一种用于涤纶织物的核壳结构乳液增深剂及其制备方法

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