WO2021045124A1 - 無機強化熱可塑性ポリエステル樹脂組成物、及びそれからなる成形品 - Google Patents

無機強化熱可塑性ポリエステル樹脂組成物、及びそれからなる成形品 Download PDF

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WO2021045124A1
WO2021045124A1 PCT/JP2020/033324 JP2020033324W WO2021045124A1 WO 2021045124 A1 WO2021045124 A1 WO 2021045124A1 JP 2020033324 W JP2020033324 W JP 2020033324W WO 2021045124 A1 WO2021045124 A1 WO 2021045124A1
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resin composition
mass
polyester resin
inorganic
reinforced thermoplastic
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English (en)
French (fr)
Japanese (ja)
Inventor
鮎澤　佳孝
隆浩 清水
悟 堀口
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to US17/639,669 priority Critical patent/US12371547B2/en
Priority to CN202080062442.2A priority patent/CN114341265B/zh
Priority to JP2021517736A priority patent/JP7609063B2/ja
Publication of WO2021045124A1 publication Critical patent/WO2021045124A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08K3/40—Glass
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • the present invention relates to an inorganic reinforced polyester resin composition containing a thermoplastic polyester resin and an inorganic reinforcing material such as glass fiber. Specifically, even in thin-walled and long molded products, while maintaining high rigidity and high strength, there are few appearance defects due to floating of the inorganic reinforcing material of the molded product, surface gloss is good, warpage deformation is small, and burrs The present invention relates to an inorganic reinforced polyester resin composition capable of obtaining extremely few molded products.
  • polyester resin has excellent mechanical properties, heat resistance, chemical resistance, etc., and is widely used in automobile parts, electrical / electronic parts, household goods, etc.
  • the polyester resin composition reinforced with an inorganic reinforcing material such as glass fiber dramatically improves the rigidity, strength and heat resistance, and in particular, the rigidity is improved according to the amount of the inorganic reinforcing material added. Has been done.
  • the inorganic reinforcing material such as glass fiber may be raised on the surface of the molded product, and the appearance, particularly the surface gloss, may be significantly deteriorated and the commercial value may be impaired.
  • the mold temperature at the time of molding it has been proposed to set the mold temperature at the time of molding to an extremely high temperature, for example, 120 ° C. or higher.
  • this method requires a special device to raise the mold temperature, and not only can it not be molded by any molding machine for general purposes, but also the gate inside the mold even when the mold temperature is raised to a high temperature.
  • glass fibers and the like may float at the end portion of the molded product far away from the molded product, and a good molded appearance may not be obtained, or the molded product may have a large warp, which may cause a problem.
  • Patent Documents 1 and 2 it has been proposed to improve the mold so that a high-gloss molded product can be obtained from various inorganic reinforcing materials such as glass fibers.
  • Patent Documents 1 and 2 ceramics having high heat insulating properties such as zirconia ceramics are nested in the cavity portion of the mold, and the molten resin is controlled to be rapidly cooled immediately after being filled in the cavity.
  • the purpose is to keep the resin inside at a high temperature to obtain a molded product with excellent surface properties.
  • these methods are expensive for mold manufacturing and are effective for simple molded product shapes such as flat plates, but in the case of complicated molded products, it is difficult to process ceramics, and highly accurate mold manufacturing is possible. There was a problem that it was difficult to do.
  • composition of the above document by blending various amorphous resins, copolymerized polyesters and the like to control the crystallization behavior of the resin composition, glass fibers and the like can be obtained even if the mold temperature is 100 ° C. or lower.
  • the resin composition to which the above is added a good surface appearance can be obtained and warpage deformation can be suppressed.
  • burrs of the molded product may become a problem, especially when molding a crystalline resin such as a polyester resin.
  • a deburring step or the like is required, which takes time and cost.
  • the wall thickness of the molded product tends to be thin and the size of the molded product tends to be small, so that the problem of burrs becomes relatively large.
  • the occurrence of burrs is partly due to the formation of gaps due to the aging of the mold, but in general, the effect of the resin factor is large.
  • burrs tend to be reduced due to its viscosity characteristics.
  • burrs are used except for olefin resins which behave similarly to amorphous resins.
  • Patent Document 7 A polyester resin composition that solves this problem has already been proposed (Patent Document 7).
  • the present invention maintains a good surface appearance while maintaining high strength and high rigidity (flexural modulus exceeding 17 GPa) in a composition containing an inorganic reinforcing material such as glass fiber without losing the characteristics as a polyester resin.
  • the inorganic reinforced thermoplastic polyester resin composition particularly by adjusting the blending ratio of at least one kind of polyester resin other than polybutylene terephthalate resin and polybutylene terephthalate resin and other components. It has been found that even in the case of molding that requires high cycle performance, both good moldability and a burr suppressing effect can be achieved. However, when the rigidity required for the material becomes high (the flexural modulus exceeds 17 GPa) and the molded product becomes thinner and longer, the material in the above invention can maintain the effect of suppressing burrs. It was difficult. Therefore, it was essential to design a new composition in consideration of the rigidity of the material and the shape of the molded product.
  • the inorganic reinforced thermoplastic polyester resin composition contains an amorphous resin, and by readjusting the blending ratio of each component, thin-walled and long molding that requires particularly high rigidity is required. We have found that it is possible to effectively suppress burrs even in products, and have arrived at the present invention.
  • the present invention has the following configuration.
  • An inorganic reinforced thermoplastic polyester resin composition comprising .5 kPa ⁇ s or less.
  • the present invention even in a resin composition containing a large amount of an inorganic reinforcing material, it is possible to suppress the embossment of the inorganic reinforcing material on the surface of the molded product by adjusting the blending ratio of each component, so that the appearance of the molded product is large. It can be improved, and it is possible to obtain a molded product having a good appearance and low warpage while having high strength and high rigidity. Further, even in a thin-walled or long-walled molded product or the like, the generation of burrs can be greatly suppressed with respect to the pressure during molding, so that the deburring step after molding can be eliminated.
  • the blending amount of each component described below represents the amount (mass%) when the inorganic reinforced thermoplastic polyester resin composition is 100% by mass. Since the blended amount of each component is the content in the inorganic reinforced thermoplastic polyester resin composition, the blended amount and the content are the same.
  • the polybutylene terephthalate resin (A) in the present invention is a resin having the highest content among all the resins in the inorganic reinforced thermoplastic polyester resin composition of the present invention.
  • the polybutylene terephthalate resin (A) is not particularly limited, but a homopolymer composed mainly of terephthalic acid and 1,4-butanediol is used. Further, other components can be copolymerized up to about 5 mol% within a range that does not impair moldability, crystallinity, surface gloss and the like.
  • the copolymerization amount is the amount when the acid component is 100 mol% and the glycol component is 100 mol%. As other components, the components described below can be mentioned.
  • components to be copolymerized include aromatic or aliphatic polybasic acids such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, and trimellitic acid, or esters thereof as acid components other than terephthalic acid.
  • Glycol components other than 1,4-butanediol include diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-. Examples thereof include 1,3-propanediol.
  • a sample having a reduced viscosity (0.1 g sample is dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane (mass ratio 6/4)) is dissolved in 25 ml, and the temperature is 30 ° C. using an Ubbelohde viscosity tube.
  • Dl / g is preferably in the range of 0.4 to 1.2 dl / g, more preferably in the range of 0.5 to 0.8 dl / g.
  • the reduced viscosity is less than 0.4 dl / g, the toughness of the resin is lowered, and burrs are likely to occur due to the fluidity being too high. If the reduced viscosity is more than 1.2 dl / g, the fluidity is greatly reduced. , This also tends to cause burrs.
  • the blending amount of the polybutylene terephthalate resin (A) is 20 to 60% by mass, preferably 22 to 50% by mass, more preferably 24 to 40% by mass, and further preferably 24 to 35% by mass. is there. By blending the polybutylene terephthalate resin within this range, various characteristics can be satisfied.
  • the (B) amorphous resin in the present invention known ones such as polycarbonate resin, polyarylate resin, polystyrene resin, and acrylic nitrile-styrene copolymer can be used. Considering the compatibility with the polybutylene terephthalate resin and the effect of suppressing burrs, the polycarbonate resin and the polyarylate resin are preferable.
  • the blending amount of the amorphous resin is 5 to 20% by mass, preferably 6 to 20% by mass, and more preferably 10 to 20% by mass. If it is less than 5% by mass, the effect of suppressing burrs is small, and if it exceeds 20% by mass, deterioration of the molding cycle due to a decrease in crystallinity and poor appearance due to a decrease in fluidity are likely to occur, which is not preferable.
  • Polycarbonate resins are prepared by the solvent method, that is, the reaction of dihydric phenol with a carbonate precursor such as phosgene, or dihydric phenol and diphenyl in the presence of known acid acceptors and molecular weight modifiers in solvents such as methylene chloride. It can be produced by a transesterification reaction with a carbonate precursor such as carbonate.
  • a carbonate precursor such as carbonate.
  • the divalent phenol there are bisphenols, and in particular, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A. Further, a part or all of bisphenol A may be replaced with another divalent phenol.
  • dihydric phenols other than bisphenol A examples include compounds such as hydroquinone, 4,4-dihydroxydiphenyl and bis (4-hydroxyphenyl) alkane, bis (3,5-dibromo-4-hydroxyphenyl) propane and bis (3). , 5-Dichloro-4-hydroxyphenyl) Halogenized bisphenols such as propane can be mentioned.
  • Polycarbonate may be a homopolymer using one kind of dihydric phenol or a copolymer using two or more kinds, and a component other than polycarbonate (for example, a polyester component) within a range (20% by mass or less) that does not impair the effect of the present invention. It may be a resin obtained by copolymerizing the above.
  • melt volume rate measured at a load 1.2 kg (unit: cm 3 / 10min) there is preferably used from 1 to 100, melt volume rate is more preferably 2 to 80, more preferably Is 3-40.
  • melt volume rate is more preferably 2 to 80, more preferably Is 3-40.
  • polyarylate resin one produced by a known method can be used.
  • Polyarylate resin 360 ° C., melt volume rate measured under a load 2.16 kg (unit: cm 3 / 10min) there is preferably used from 1 to 100, melt volume rate is more preferably 2 to 80, further It is preferably 3 to 40.
  • melt volume rate is more preferably 2 to 80, further It is preferably 3 to 40.
  • burrs can be effectively suppressed without impairing moldability. If a melt volume rate of less than 1 is used, the fluidity may be significantly reduced and the moldability may be deteriorated. If the melt volume rate exceeds 100, the molecular weight is too low, which tends to cause deterioration of physical properties and problems such as gas generation due to decomposition.
  • the (C) inorganic reinforcing material in the present invention includes plate-shaped crystal talc, mica, unbaked clay, unspecified or spherical calcium carbonate, fired clay, silica, glass beads, and commonly used fibers. Whiskers such as lastnite and acicular warastonite, glass fiber, scaly glass, carbon fiber, aluminum borate, potassium titanate, short glass fiber with an average particle size of about 4 to 20 ⁇ m and a cut length of about 35 to 150 ⁇ m. Mild fiber, etc., but is not limited to these. Talc and wallastnite are the best in terms of the appearance of the molded product, and glass fiber is the best in terms of strength and rigidity. One type of these inorganic reinforcing materials may be used alone, or two or more types may be used in combination, but it is preferable to use glass fiber mainly in terms of rigidity and the like.
  • the glass fiber a chopped strand shape cut to a fiber length of about 1 to 20 mm can be preferably used.
  • a glass fiber having a circular cross section and a non-circular cross section can be used.
  • an average fiber diameter of about 4 to 20 ⁇ m and a cut length of about 3 to 6 mm can be used.
  • Non-circular cross-section glass fibers include those having a substantially elliptical system, a substantially elliptical system, and a substantially cocoon-shaped cross section in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. Is preferable.
  • the flatness is assumed to be a rectangle having the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of this rectangle is the major axis, and the length of the short side is the minor axis. This is the ratio of major axis / minor axis when
  • the thickness of the glass fiber is not particularly limited, but those having a minor axis of about 1 to 20 ⁇ m and a major axis of about 2 to 100 ⁇ m can be used.
  • these glass fibers those which have been pretreated with a conventionally known coupling agent such as an organic silane compound, an organic titanium compound, an organic borane compound and an epoxy compound can be preferably used.
  • a conventionally known coupling agent such as an organic silane compound, an organic titanium compound, an organic borane compound and an epoxy compound
  • the blending amount of the (C) inorganic reinforcing material in the present invention is 30 to 60% by mass, preferably 35 to 60% by mass, and more preferably 35 to 57% by mass. By blending an inorganic reinforcing material within this range, various properties can be satisfied.
  • talc When talc is used as the inorganic reinforcing material, it is important that the blending amount thereof is in the range of 1% by mass or less in the resin composition even when used in combination as the component (C). Since talc acts as a crystal nucleating agent, if it is used in excess of this amount, the crystallization rate becomes high and appearance defects such as glass floating are likely to occur, which is not preferable.
  • the combined use of glass fiber and scaly glass can be preferably selected from the viewpoint of flow characteristics and low warpage.
  • scaly glass By using scaly glass together, not only warpage can be suppressed but also fluidity can be improved.
  • the mass ratio of the glass fiber and scaly glass is preferably 40:60 to 90:10, preferably 45:55 to 80:20. Is more preferable.
  • the inorganic reinforced thermoplastic policel resin composition of the present invention has a flexural modulus of a molded product obtained by injection molding the inorganic reinforced thermoplastic policel resin composition when (C) an inorganic reinforcing material is contained in an amount of 50 to 60% by mass. Can exceed 17 GPa.
  • the (D) ethylene-glycidyl (meth) acrylate copolymer used in the present invention is a ternary copolymer obtained by copolymerizing ethylene, glycidyl (meth) acrylate, vinyl acetate, acrylic acid ester, etc., and a ternary copolymer. Copolymers of four or more elements can also be used.
  • the glycidyl (meth) acrylate refers to either a glycidyl acrylate or a glycidyl methacrylate.
  • linear copolymers random copolymers or block copolymers
  • graft copolymers core-shell type polymers and the like can also be used.
  • Alkyl groups having 1 to 22 carbon atoms such as butyl, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, and methoxyethyl (meth) acrylate (alkyl groups are linear, (May be branched chain) (meth) acrylic acid alkyl ester, (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dialkylamino Examples thereof include alkyl esters, (meth) acrylic acid benzyl esters, (meth) acrylic acid phenoxyalkyl esters, (meth) acrylic acid isobornyl esters, and (meth) acrylic acid alkoxysilylalkyl esters. (Meta) acrylamide and (meth) acrylic dialkylamide can also be used. These can
  • the blending amount of the (D) ethylene-glycidyl (meth) acrylate copolymer is 0.5 to 10% by mass.
  • adding more component (D) improves the viscosity of the entire resin composition and suppresses the occurrence of burrs in the pressure holding process, but conversely, a considerable pressure is applied to thin-walled molded products and the like.
  • the blending amount is preferably 0.7 to 8% by mass, more preferably 0.8 to 5% by mass.
  • the (D) ethylene-glycidyl (meth) acrylate copolymer a copolymer in which the remaining glycidyl (meth) acrylate component of the epoxy group is 3 to 12% by mass of the total copolymer can be preferably used. More preferably, it is a copolymer having 3 to 6% by mass. Within the above range, the effect of suppressing burrs can be improved, and the toughness of the inorganic reinforced thermoplastic polyester resin composition can also be increased.
  • Examples of the (D) ethylene-glycidyl (meth) acrylate copolymer used in the present invention include Bond First (manufactured by Sumitomo Chemical Corporation), Rotada (manufactured by Arkema Co., Ltd.), Elvalois (manufactured by Mitsui DuPont Polychemical Corporation), and Metabrene (manufactured by Mitsui DuPont Polychemical Corporation). Mitsubishi Chemical Corporation), Polymer (Nippon Yushi), etc. are listed as commercial products.
  • the (E) transesterification inhibitor used in the present invention is a stabilizer that prevents a transesterification reaction of a polyester resin or the like.
  • transesterification reactions occur not a little due to the addition of thermal history, no matter how appropriate the manufacturing conditions are. When the degree of the reaction becomes very large, the expected characteristics cannot be obtained by the alloy.
  • the transesterification reaction between the polybutylene terephthalate resin and the polycarbonate resin often occurs, it is not preferable to simply alloy these because the crystallinity of the polybutylene terephthalate is greatly reduced.
  • the addition of the component (E) prevents a transesterification reaction between (A) polybutylene terephthalate resin and (B) amorphous resin (polycarbonate resin, polyarylate resin, etc.). Therefore, appropriate crystallinity can be maintained.
  • a phosphorus compound having a catalytic deactivation effect of a polyester resin can be preferably used, and for example, "ADEKA STAB AX-71" manufactured by ADEKA Corporation can be used.
  • the blending amount of the (E) transesterification inhibitor is 0.05 to 2% by mass, more preferably 0.1 to 1% by mass. If it is less than 0.05% by mass, the required transesterification reaction prevention performance is often not exhibited, and due to the decrease in crystallinity of the inorganic reinforced thermoplastic polyester resin composition, the mechanical properties are deteriorated, the mold release failure at the time of injection molding, etc. May occur. On the contrary, even if it is added in an amount of more than 2% by mass, not only the improvement of the effect is not so much observed, but also it may cause an increase in gas or the like.
  • the inorganic reinforced thermoplastic polyester resin composition of the present invention can be filled in 0.5 seconds for molding a long molded product of 150 mm ⁇ 20 mm ⁇ 3 mmt (thickness) at a cylinder temperature of 275 ° C. and a mold temperature of 110 ° C.
  • the maximum value of the amount of burrs generated at the end of the flow when a holding pressure of 75 MPa is applied can be set to less than 0.20 mm.
  • burrs the resin is most often generated by protruding from the mold in response to pressure in the pressure holding process. It can be improved by adjusting the holding pressure, but in that case, it may lead to other defects (for example, sink marks, poor appearance).
  • the resin surface can be improved by adjusting the resin surface so that it has a resin viscosity that can withstand the pressure applied during holding pressure.
  • a large amount of pressure is required when filling the resin, so the mold opens at the time of injection and burrs are formed. turn into. This tendency is particularly remarkable in thin-walled molded products.
  • a resin having a melt viscosity behavior that raises it examples include an olefin resin such as polyethylene and an amorphous resin such as an acrylic resin. Therefore, it can be easily imagined that these resins are added to the polyester resin.
  • the inorganic reinforced thermoplastic polyester resin composition of the present invention preferably has a crystallization temperature at lower temperature of more than 180 ° C., which is determined by a differential scanning calorimeter (DSC).
  • the crystallization temperature at the time of lowering the temperature is defined as 10 by using a differential scanning calorimeter (DSC), raising the temperature to 300 ° C. at a heating rate of 20 ° C./min under a nitrogen stream, and holding the temperature at that temperature for 5 minutes. This is the top temperature of the crystallization peak of the thermogram obtained by lowering the temperature to 100 ° C. at a rate of ° C./min.
  • the crystallization temperature at the time of lowering the temperature becomes 180 ° C.
  • the crystallization temperature at the time of lowering the temperature is preferably 195 ° C. or lower, more preferably 190 ° C. or lower.
  • the inorganic reinforcing material such as glass fiber is generally conspicuous on the surface of the molded product, so-called glass floating or the like is likely to occur. This is because the crystallization rate of the polyester resin composition increases, so that the propagation rate of the injection pressure tends to decrease, and a part of the inorganic reinforcing material such as glass fiber is exposed on the surface of the molded product. is there.
  • the blending amount of each component is adjusted so that a good appearance can be obtained even at a temperature exceeding 180 ° C., and it is possible to achieve both good moldability and good appearance. is there.
  • the inorganic reinforced thermoplastic polyester resin composition of the present invention may contain various known additives, if necessary, as long as the characteristics of the present invention are not impaired.
  • Known additives include, for example, colorants such as pigments, mold release agents, heat-resistant stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, denaturants, antistatic agents, flame retardants, dyes and the like. Can be mentioned.
  • These various additives can be contained up to 5% by mass in total when the inorganic reinforced thermoplastic polyester resin composition is 100% by mass. That is, the total of the above (A), (B), (C), (D) and (E) is preferably 95 to 100% by mass in 100% by mass of the inorganic reinforced thermoplastic polyester resin composition.
  • Examples of the release agent include long-chain fatty acids or esters and metal salts thereof, amide compounds, polyethylene wax, silicon, polyethylene oxide and the like.
  • the long-chain fatty acid is particularly preferably having 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. It may be formed or may form a metal salt.
  • Examples of the amide compound include ethylenebisterephthalamide and methylenebisstearylamide. These release agents may be used alone or as a mixture.
  • the melt viscosity of the inorganic reinforced thermoplastic polyester resin composition of the present invention at 265 ° C. and a shear rate of 10 sec -1 is 0.5 kPa ⁇ s or more and 1.5 kPa ⁇ s or less, preferably 0.6 kPa ⁇ s or more. It is 4 kPa ⁇ s or less, more preferably 0.7 kPa ⁇ s or more and 1.3 kPa ⁇ s or less. If it is less than 0.5 kPa ⁇ s, injection molding becomes difficult. On the other hand, if it is larger than 1.5 kPa ⁇ s, burrs are likely to occur in the molded product.
  • the inorganic reinforced thermoplastic polyester resin composition of the present invention can be produced by mixing the above-mentioned components and various stabilizers, pigments and the like as necessary, and melt-kneading them. Any method known to those skilled in the art can be used as the melt-kneading method, and a single-screw extruder, a twin-screw extruder, a pressure kneader, a Banbury mixer and the like can be used. Of these, it is preferable to use a twin-screw extruder. As general melt-kneading conditions, in a twin-screw extruder, the cylinder temperature is 230 to 300 ° C. and the kneading time is 2 to 15 minutes.
  • Amount of burrs generated The amount of burrs generated is a filling time of 0. The maximum value of burrs at the end of the flow generated in the molded product at an injection rate of 5 seconds and when a holding pressure of 75 MPa was applied was measured using a microscope.
  • Warp Using a 100 mm ⁇ 100 mm ⁇ 2 mmt (thickness) film gate mold with ribs on one side, resin at resin temperatures 265 to 270 ° C, mold temperatures 80 ° C, 100 ° C and 120 ° C with an injection molding machine.
  • a molded product having five ribs having a length of 100 mm, a height of 1 mm and a thickness of 1 mm was molded in a direction perpendicular to the flow direction of the above, and the amount of warp deformation was measured (value A in FIG. 1, three moldings). Average value of goods). Evaluation was made according to the following criteria.
  • ⁇ Warp deformation amount> 3 mm ⁇ : 3 mm ⁇ warp deformation amount ⁇ 2 mm ⁇ : 1.5 mm ⁇ warp deformation amount ⁇ 2 mm
  • “Bond First 7M” (D-2): Graft copolymer of ethylene-ethyl acrylate copolymer (main chain) and methyl methacrylate-butyl acrylate copolymer (side chain) (main chain epoxy group residual glycidyl methacrylate component: 0% by mass) , Made by Nippon Oil & Fat Co., Ltd., "Modiper A5300” (E) Transesterification inhibitor (E): "ADEKA STAB AX-71" manufactured by ADEKA.
  • the inorganic reinforced thermoplastic polyester resin compositions of Examples and Comparative Examples were weighed according to the blending ratio (mass%) shown in Table 1 and cylinderd with a 35 ⁇ twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.). It was melt-kneaded at a temperature of 270 ° C. and a screw rotation speed of 100 rpm.
  • Raw materials other than the component (C) were charged from the hopper into the twin-screw extruder, and the component (C) was charged from the vent port by side feed.
  • the obtained pellets of the inorganic reinforced thermoplastic polyester resin composition were dried, and then various evaluation samples were molded by an injection molding machine.
  • the molding conditions were a cylinder temperature of 275 ° C. and a mold temperature of 110 ° C.
  • the evaluation results are shown in Table 1.
  • Comparative Example 1 since the component (B) is not contained, the appearance, warpage, and moldability are all inferior, and in Comparative Example 4, the component (B) exceeds a predetermined range, so that the moldability (mold releasability) is deteriorated. did. Further, in Comparative Example 5, since the component (E) was not contained, the transesterification reaction proceeded remarkably and the crystallinity decreased, so that the moldability (release property) deteriorated. Further, in Comparative Example 6, since the melt viscosity was higher than a predetermined range, the fluidity was insufficient, the inorganic reinforcing material was floated, and the appearance was poor due to grain unevenness.
  • the present invention even in a resin composition containing a large amount of an inorganic reinforcing material, it is possible to suppress the embossment of the inorganic reinforcing material on the surface of the molded product by adjusting the blending ratio of each component, so that the appearance of the molded product is large. It can be improved, and it is possible to obtain a molded product having a good appearance and low warpage while having high strength and high rigidity. Further, even in a thin-walled or long-walled molded product or the like, the generation of burrs can be greatly suppressed with respect to the pressure during molding, so that the deburring step after molding can be eliminated. Therefore, it is important to contribute to the industrial world.

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PCT/JP2020/033324 2019-09-05 2020-09-02 無機強化熱可塑性ポリエステル樹脂組成物、及びそれからなる成形品 Ceased WO2021045124A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023003058A (ja) * 2021-06-23 2023-01-11 住友化学株式会社 板状成形体

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024312A (ja) * 2008-07-17 2010-02-04 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物
CN101787183A (zh) * 2009-10-15 2010-07-28 上海锦湖日丽塑料有限公司 一种低翘曲高表面光泽玻纤增强聚酯复合材料及制备方法
JP2013001772A (ja) * 2011-06-15 2013-01-07 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物および成形品
JP2013159732A (ja) * 2012-02-07 2013-08-19 Toyobo Co Ltd 無機強化熱可塑性ポリエステル樹脂組成物
WO2015008831A1 (ja) * 2013-07-19 2015-01-22 東洋紡株式会社 無機強化熱可塑性ポリエステル樹脂組成物
US20150368458A1 (en) * 2014-06-19 2015-12-24 Sabic Global Technologies B.V. Reinforced thermoplastic compound with chemical resistance
WO2019172216A1 (ja) * 2018-03-07 2019-09-12 東洋紡株式会社 無機強化熱可塑性ポリエステル樹脂組成物

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60231757A (ja) * 1984-05-01 1985-11-18 Toray Ind Inc ポリエステル組成物
JP3390539B2 (ja) 1994-09-01 2003-03-24 帝人株式会社 熱可塑性樹脂組成物
JP3421188B2 (ja) 1996-02-01 2003-06-30 三菱エンジニアリングプラスチックス株式会社 射出圧縮成形用の金型組立体及び射出圧縮成形方法
US5741446A (en) 1995-05-26 1998-04-21 Mitsubishi Engineering-Plastics Corp. Method of producing a molded article using a mold assembly with an insert block
JP3549341B2 (ja) 1995-10-16 2004-08-04 三菱エンジニアリングプラスチックス株式会社 ポリマーアロイ材料から成る成形品の成形方法
EP1445282A4 (en) * 2001-08-03 2004-11-24 Toray Industries RESIN COMPOSITION AND MOLDED ARTICLE, FILM AND FIBER
KR100658965B1 (ko) * 2003-07-12 2006-12-18 주식회사 아세아세라텍 시멘트 혼화재 및 그것을 사용한 시멘트 조성물
US7385013B2 (en) * 2004-05-12 2008-06-10 Toray Industries, Inc. Polymer alloy, thermoplastic resin composition, and molded article
JP4696476B2 (ja) 2004-05-28 2011-06-08 東レ株式会社 熱可塑性樹脂組成物
JP4657670B2 (ja) * 2004-10-13 2011-03-23 ウィンテックポリマー株式会社 ポリブチレンテレフタレート樹脂組成物
JP2007269890A (ja) 2006-03-30 2007-10-18 Toray Ind Inc レーザ溶着樹脂組成物およびそれからなる成形品
KR101372345B1 (ko) * 2006-06-30 2014-03-12 도레이 카부시키가이샤 열가소성 수지 조성물 및 그 성형품
AU2007277656A1 (en) * 2006-07-28 2008-01-31 Teijin Chemicals Ltd. Resin composition, method for producing the same and molded article
JP5058565B2 (ja) 2006-11-13 2012-10-24 ウィンテックポリマー株式会社 ポリブチレンテレフタレート樹脂組成物及び成形品
JP5396690B2 (ja) 2007-03-07 2014-01-22 東洋紡株式会社 無機強化ポリエステル系樹脂組成物及びそれを用いた成形品の表面外観改良方法。
US8062574B2 (en) * 2007-09-12 2011-11-22 Kao Corporation Process for production of injection-molded article of polylactic acid resin

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024312A (ja) * 2008-07-17 2010-02-04 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物
CN101787183A (zh) * 2009-10-15 2010-07-28 上海锦湖日丽塑料有限公司 一种低翘曲高表面光泽玻纤增强聚酯复合材料及制备方法
JP2013001772A (ja) * 2011-06-15 2013-01-07 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物および成形品
JP2013159732A (ja) * 2012-02-07 2013-08-19 Toyobo Co Ltd 無機強化熱可塑性ポリエステル樹脂組成物
WO2015008831A1 (ja) * 2013-07-19 2015-01-22 東洋紡株式会社 無機強化熱可塑性ポリエステル樹脂組成物
US20150368458A1 (en) * 2014-06-19 2015-12-24 Sabic Global Technologies B.V. Reinforced thermoplastic compound with chemical resistance
WO2019172216A1 (ja) * 2018-03-07 2019-09-12 東洋紡株式会社 無機強化熱可塑性ポリエステル樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023003058A (ja) * 2021-06-23 2023-01-11 住友化学株式会社 板状成形体
JP7668169B2 (ja) 2021-06-23 2025-04-24 住友化学株式会社 板状成形体

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