WO2020246335A1 - 樹脂組成物及びその製造方法 - Google Patents

樹脂組成物及びその製造方法 Download PDF

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WO2020246335A1
WO2020246335A1 PCT/JP2020/020897 JP2020020897W WO2020246335A1 WO 2020246335 A1 WO2020246335 A1 WO 2020246335A1 JP 2020020897 W JP2020020897 W JP 2020020897W WO 2020246335 A1 WO2020246335 A1 WO 2020246335A1
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Prior art keywords
resin
temperature
resin composition
terephthalate resin
mass
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English (en)
French (fr)
Japanese (ja)
Inventor
流成 松崎
耕一 坂田
一也 五島
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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Priority to JP2021524792A priority Critical patent/JP7507153B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K3/32—Phosphorus-containing 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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

Definitions

  • the present invention relates to a resin composition and a method for producing the same.
  • Polybutylene terephthalate resin is excellent in various properties such as mechanical properties, electrical properties, heat resistance, chemical resistance and solvent resistance, and therefore, as engineering plastics, automobile parts, electric / electronic parts, etc. It is widely used for various purposes.
  • the PBT resin has a property of having a relatively high crystallization rate. Therefore, for the purpose of slowing the solidification rate of the resin in the mold during molding to improve the transferability of the mold surface and thereby improving the appearance of the molded product, the PBT resin is made of polyethylene terephthalate resin (PET resin) or the like. It may be used as an alloy with the low crystalline polyester resin of.
  • PET resin polyethylene terephthalate resin
  • Patent Document 1 proposes a polybutylene terephthalate resin composition containing a specific PET resin as an alloy resin.
  • the polyester resin composition containing the PBT resin and the PET resin tends to undergo an ester exchange reaction between the PBT resin and the PET resin when melted. If the transesterification reaction proceeds too much, the melting point and crystallization temperature of the resin composition may change significantly. In such a case, there may be a problem that the physical properties of the molded product are deteriorated, the moldability such as the releasability from the mold is deteriorated, and the thermal stability is lowered.
  • An object of the present invention is to provide a resin composition suitable for producing a molded product having excellent appearance and excellent thermal stability, and a method for producing the same.
  • the present inventor has found that when the crystallization temperature of the resin composition satisfies a specific condition, both good appearance and thermal stability of the molded product can be achieved, and the present invention has been completed. That is, the present invention relates to the following.
  • Formula I Crystallization temperature Tc1 (° C.) ⁇ 195 ° C.
  • Formula II [Crystallization temperature Tc1 (° C.)]-[Crystalization temperature Tc3 (° C.)] ⁇ 15 ° C.
  • Tc1 is subjected to three cycles of raising the temperature from 40 ° C. to 280 ° C. at a heating rate of 10 ° C./min and lowering the temperature from 280 ° C. to 40 ° C. at a temperature lowering rate of 10 ° C./min based on JIS K7121.
  • it represents the peak temperature (° C.) of the maximum endothermic peak of the DSC curve in the differential scanning calorimetry (DSC) at the temperature decrease in the first cycle
  • Tc3 is the differential scanning calorimetry at the temperature decrease in the third cycle.
  • DSC represents the peak temperature (° C.) of the maximum endothermic peak of the DSC curve.
  • the phosphorus compound contains an organic phosphorus compound, and the content of the organic phosphorus compound is 0.1 to 0.2 parts by mass with respect to a total of 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin.
  • the transesterification accelerator is further contained, and the content of the transesterification accelerator is 0.01 to 2 parts by mass with respect to 100 parts by mass in total of the polybutylene terephthalate resin and the polyethylene terephthalate resin [1].
  • the resin composition according to any one of [4]. [6] The resin composition according to any one of [1] to [5], which does not contain a halogen-based flame retardant or has a halogen-based flame retardant content of 5% by mass or less in the total resin composition.
  • [7] The method for producing a resin composition according to any one of [1] to [6], wherein a polybutylene terephthalate resin and a polyethylene terephthalate resin are heat-treated under the condition of satisfying the following formula III to obtain a resin mixture.
  • a method for producing a resin composition which comprises mixing the resin mixture and a phosphorus compound to obtain a resin composition.
  • Formula III 12000 (° C. s) ⁇ temperature (° C.) x time (s) ⁇ 180000 (° C.
  • the polybutylene terephthalate resin and the polyethylene terephthalate resin are melted and retained in a heating container for heat treatment, and then a phosphorus compound is added and mixed by heating in the heating container to obtain a resin composition.
  • the resin composition is obtained by melt-extruding a polybutylene terephthalate resin and a polyethylene terephthalate resin to obtain a heat-treated resin mixture, and then heating and mixing the resin mixture and a phosphorus compound. Manufacturing method.
  • the resin composition according to the present embodiment contains a polybutylene terephthalate resin, a polyethylene terephthalate resin, and a phosphorus compound.
  • the polybutylene terephthalate resin contains a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) and an alkylene glycol having at least 4 carbon atoms (1).
  • PBT resin contains a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) and an alkylene glycol having at least 4 carbon atoms (1).
  • 4-Butandiol or a polybutylene terephthalate resin obtained by polycondensing with a glycol component containing an ester-forming derivative thereof (acetylated product, etc.).
  • the polybutylene terephthalate resin is not limited to the homopolybutylene terephthalate resin (that is, the butylene terephthalate unit is 100 mol%), and may be a copolymer containing 60 mol% or more of the butylene terephthalate unit. Can also be used as a copolymer containing 75 mol% or more and 95 mol% or less. When the polybutylene terephthalate unit is less than 60 mol%, the crystallization rate is slow and the releasability is lowered.
  • the amount of terminal carboxyl groups in the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin is not particularly limited as long as it does not impair the object of the present invention, but is preferably 0.60 dL / g or more and 1.2 dL / g or less, and more preferably 0.65 dL / g. It is g or more and 0.9 dL / g or less.
  • the obtained polybutylene terephthalate resin composition is particularly excellent in moldability. It is also possible to adjust the intrinsic viscosity by blending polybutylene terephthalate resins having different intrinsic viscosities.
  • a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g can be prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. Can be done.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol under the condition of a temperature of 35 ° C.
  • aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component in the preparation of a polybutylene terephthalate resin
  • isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'- C 8-14 aromatic dicarboxylic acid such as dicarboxydiphenyl ether
  • C 4-16 alcandicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid
  • C 5-10 cycloalcandicarboxylic acid such as cyclohexanedicarboxylic acid Acid
  • Ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.) can be used.
  • These dicarboxylic acid components can be used alone or in combination of two or more.
  • C 8-12 aromatic dicarboxylic acids such as isophthalic acid and C 6-12 alkane dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferable.
  • glycol component other than 1,4-butanediol is used as the comonomer component in the preparation of the polybutylene terephthalate resin
  • polyoxyalkylene glycols such as diethylene glycols, triethylene glycols and dipropylene glycols
  • alicyclic diols such as cyclohexanedimethanol and hydride bisphenol A
  • bisphenols Aromatic diols such as A, 4,4'-dihydroxybiphenyl
  • C 2-4 alkylene oxide adduct of bisphenol A such as ethylene oxide 2 mol adduct of bisphenol A and propylene oxide 3 mol adduct of bisphenol A
  • C 2-6 alkylene glycols such as ethylene glycol and trimethylene glycol
  • polyoxyalkylene glycols such as diethylene glycol
  • alicyclic diols such as cyclohexanedimethanol are more preferable.
  • Examples of the comonomer component that can be used in addition to the dicarboxylic acid component and the glycol component include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4'-hydroxybiphenyl and the like.
  • the crystallization temperature Tc1 PBT of the polybutylene terephthalate resin is preferably 100 ° C. to 200 ° C., more preferably 140 ° C. to 198 ° C., and 160 ° C. to 160 ° C. from the viewpoint of further enhancing the appearance of the resin composition. It is more preferably 195 ° C., and particularly preferably 180 to 195 ° C.
  • the crystallization temperature Tc1 PBT is measured by DSC (differential scanning calorimetry) based on JIS K7121. After raising the temperature from 40 ° C. to 260 ° C.
  • the crystallization temperature of polybutylene terephthalate resin may increase due to melt-kneading.
  • a homopolybutylene terephthalate resin having an IV of 0.70 dL / g has a crystallization temperature of 176 ° C. immediately after polymerization and is melt-kneaded, the temperature may rise to 198 ° C. depending on the extrusion conditions. Therefore, the temperature is a value after melt-kneading.
  • the polybutylene terephthalate resin after melt-kneading under the conditions of 260 ° C., 15 kg / hr, and 130 rpm. Refers to the crystallization temperature.
  • the content of the polybutylene terephthalate resin is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 15 to 60% by mass, based on the total mass of the resin composition. ..
  • the polyethylene terephthalate resin includes terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) as a dicarboxylic acid component, and ethylene glycol or an ester-forming derivative thereof (acetyl) as a diol component.
  • PET resin terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) as a dicarboxylic acid component, and ethylene glycol or an ester-forming derivative thereof (acetyl) as a diol component.
  • a polyethylene terephthalate resin obtained by polycondensing a compound or the like according to a known method can be used.
  • the polyethylene terephthalate resin is a repeating unit derived from an aromatic dicarboxylic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) other than terephthalic acid or an ester-forming derivative thereof as a modifying component.
  • an aromatic dicarboxylic acid or an ester-forming derivative thereof C 1-6 alkyl ester, acid halide, etc.
  • it may have more than 0 mol% and 15 mol% or less with respect to all the repeating units derived from the dicarboxylic acid component.
  • a repeating unit derived from an diol other than ethylene glycol or an ester-forming derivative thereof or an ester-forming derivative thereof (acetylated product, etc.) as a modifying component is converted into, for example, all repeating units derived from the diol component. On the other hand, it may have more than 0 mol% and 1 mol% or less.
  • aromatic dicarboxylic acid or an ester-forming derivative thereof other than terephthalic acid isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, aromatic C 8-14, such as 4,4'-carboxymethyl ether
  • dicarboxylic acids and ester-forming derivatives of these dicarboxylic acid components C 1-6 alkyl ester derivatives, acid halides, etc.
  • These dicarboxylic acid components can be used alone or in combination of two or more.
  • glycols other than ethylene glycol or ester-forming derivatives thereof include propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, and 1,3-octane.
  • C 2-10 alkylene glycols such as diols; polyoxyalkylene glycols such as diethylene glycols, triethylene glycols and dipropylene glycols; alicyclic diols such as cyclohexanedimethanol and hydride bisphenol A; bisphenol A, 4,4'- Aromatic diols such as dihydroxybiphenyl; C 2-4 alkylene oxide adducts of bisphenol A such as ethylene oxide 2 mol adducts of bisphenol A, propylene oxide 3 mol adducts of bisphenol A; or ester formation of these glycols. Examples thereof include sex derivatives (acetylated products, etc.). These glycol components may be used alone or in combination of two or more.
  • the crystallization temperature Tc1 PET of the polyethylene terephthalate resin is preferably 210 ° C. or lower, more preferably 205 ° C. or lower, and further preferably 200 ° C. or lower, in terms of further enhancing the appearance of the resin composition. preferable.
  • the crystallization temperature Tc1 PET is measured by DSC (differential scanning calorimetry) based on JIS K7121. After raising the temperature from 40 ° C. to 280 ° C. at a heating rate of 10 ° C./min, the temperature lowering rate is ⁇ 10 ° C./ The peak of the crystallization temperature in the first cycle is taken when the operation of lowering the temperature to 40 ° C. in minutes is repeated three times.
  • the content of the polyethylene terephthalate resin is preferably 50 to 80 parts by mass, more preferably 55 to 75 parts by mass, and 60 to 70 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin. Is more preferable.
  • the resin composition preferably contains polybutylene terephthalate resin and polyethylene terephthalate resin as main components.
  • the "main component” means that the polybutylene terephthalate resin and the polyethylene terephthalate resin are contained in the resin composition in a total amount of 50% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. ..
  • the resin composition includes polycarbonate resin (PC resin), polytrimethylene terephthalate resin (PTT resin), and polycyclohexylene methylene terephthalate resin (PCT resin), as long as the effects of the invention are not impaired.
  • PC resin polycarbonate resin
  • PTT resin polytrimethylene terephthalate resin
  • PCT resin polycyclohexylene methylene terephthalate resin
  • AS resin Acrylonitrile-styrene copolymer
  • ABS resin acrylonitrile-styrene-butadiene copolymer
  • PS resin polystyrene resin
  • One of these amorphous resins may be used alone, or two or more thereof may be used in combination.
  • the non-crystalline resin is a polyester-based resin
  • the ester exchange with the PBT resin or PET resin may affect the moldability and mechanical properties, and therefore the polyester-based non-crystalline resin is contained.
  • it is preferably 10% by mass or less, and more preferably 5% by mass or less of the entire resin composition.
  • Phosphorus compound Phosphorus compounds include organic phosphorus compounds (eg, organic phosphate, organic phosphate, organic phosphonate, and / or organic phosphonite, etc.) and inorganic phosphorus compounds (alkali metal phosphate, and / or alkaline earth metal phosphate, etc.). Etc.), etc., and at least one selected from these can be used.
  • the phosphorus compound may be either liquid or solid. By containing the phosphorus compound, the thermal stability can be enhanced, and both good appearance and excellent thermal stability can be achieved.
  • organic phosphate examples include mono to trialkyl esters of phosphoric acid (for example, mono to diC 6-24 alkyl esters such as monostearyl acid phosphate and distearyl acid phosphate), and mono to triaryl esters of phosphoric acid (mono or triaryl ester).
  • mono to trialkyl esters of phosphoric acid for example, mono to diC 6-24 alkyl esters such as monostearyl acid phosphate and distearyl acid phosphate
  • mono to triaryl esters of phosphoric acid mono or triaryl ester.
  • Mono such as diphenyl phosphate or di C 6-10 aryl ester etc.
  • organic phosphite examples include bis (2,4-di-t-4 methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and bis (2). , 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and the like.
  • organic phosphonate examples include mono- or dialkylphosphonates such as distearylphosphonate (C 6-24 alkyl phosphonates and the like); aryl phosphonates (C 6-24 alkyl phosphonates and the like) which may have a substituent on an aryl group such as diphenyl phosphonate and di (nonylphenyl) phosphonate. C 6-10 arylphosphonate, etc.); Mono or dialalkylphosphonate ((C 6-10 aryl-C 1-6 alkyl) phosphonate, etc.) such as dibenzylphosphonate, etc. can be mentioned.
  • mono- or dialkylphosphonates such as distearylphosphonate (C 6-24 alkyl phosphonates and the like); aryl phosphonates (C 6-24 alkyl phosphonates and the like) which may have a substituent on an aryl group such as diphenyl phosphonate and di (nonylphenyl)
  • organic phosphonite examples include tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite.
  • the alkali metal phosphate may be a phosphate or a corresponding hydrogen phosphate salt (eg, potassium phosphate, sodium phosphate [(monosodium phosphate (sodium dihydrogen phosphate), disodium phosphate (hydrogen phosphate)).
  • Alkali metal salts such as sodium, sodium monohydrogen phosphate, disodium hydrogen phosphate))] can be exemplified.
  • Alkaline earth metal phosphates include calcium phosphate [primary calcium phosphate (calcium dihydrogen phosphate, bis (dihydrogen phosphate) calcium monohydrate, etc.), dibasic calcium phosphate (calcium hydrogen phosphate, calcium hydrogen phosphate, etc.).
  • alkaline earth metal salts such as magnesium phosphate (magnesium hydrogen phosphate, magnesium dihydrogen phosphate, etc.) can be exemplified.
  • the alkali metal salt or alkaline earth metal salt may be either anhydrous or hydrous.
  • phosphorus compounds it is preferable to use an organic phosphorus-based stabilizer from the viewpoint of better appearance.
  • the content of the phosphorus compound is 0.1 to 1.0 parts by mass, more preferably 0.1 to 0.9 parts by mass, based on 100 parts by mass of the total content of the PBT resin and the PET resin. By keeping the content of the phosphorus compound within the above range, the thermal stability can be further improved.
  • the phosphorus compound contains an inorganic phosphorus compound
  • the content of the inorganic phosphorus compound is preferably 0.2 to 0.8 parts by mass with respect to 100 parts by mass in total of the polybutylene terephthalate resin and the polyethylene terephthalate resin. More preferably, it is 0.3 to 0.6 parts by mass.
  • the content of the organic phosphorus compound is preferably 0.1 to 0.2 parts by mass with respect to 100 parts by mass in total of the polybutylene terephthalate resin and the polyethylene terephthalate resin.
  • the resin composition can contain a transesterification accelerator.
  • a transesterification accelerator By containing the transesterification accelerator, it is possible to maintain excellent appearance when the resin composition contains an inorganic phosphorus compound (alkali metal phosphate, alkaline earth metal phosphate, etc.) as a phosphorus compound. it can.
  • ester exchange accelerator examples include antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium pyroantimonate; germanium compounds such as germanium dioxide and germanium tetraoxide; tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.
  • Titanium alcolates such as, titanium compounds such as titanium phenolates such as tetraphenyl titanate; dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexyl distin oxide, didodecyltin oxide, triethyltin hydro Oxide, Triphenyltin Hydroxide, Triisobutyltin Acetate, Dibutyltin Diacetate, Diphenyltin Dilaurate, Monobutyltin Trichloride, Tributyltin Chloride, Dibutyltin Sulfide, Butylhydroxytinoxide, Methylstannoic Acid, Ethylstannoic Acid, Butylstannonic Acid Tin compounds such as magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alcoxyside, magnesium hydrogen phosphate and the like; calcium acetate, calcium hydro
  • the content of the transesterification accelerator is preferably 0.01 to 2 parts by mass, more preferably 0.02 to 1 part by mass, based on 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin. It is preferably 0.04 to 0.5 parts by mass, and more preferably 0.04 to 0.5 parts by mass.
  • the resin composition when it contains an inorganic phosphorus compound as a phosphorus compound, it preferably further contains a transesterification accelerator, and more preferably contains an antimony compound as a transesterification accelerator.
  • the resin composition can be configured to contain a polybutylene terephthalate resin, a polyethylene terephthalate resin, an inorganic phosphorus compound, and an antimony compound. The content and the like of each component in this case are as described above.
  • the resin composition when the resin composition contains an organic phosphorus compound as the phosphorus compound, it can be configured so as not to contain a transesterification accelerator or to be 0.01% by mass or less in the resin composition. In addition, this description does not exclude that the resin composition further contains a transesterification accelerator when it contains an organic phosphorus compound as a phosphorus compound.
  • the resin composition does not contain a halogen-based flame retardant, or the content of the halogen-based flame retardant can be 5% by mass or less, or 1% by mass or less in the total resin composition.
  • the antimony compound used as the transesterification accelerator described above may be generally added to a resin composition containing a polybutylene terephthalate resin as a flame retardant aid used together with a halogen-based flame retardant.
  • the antimony compound is mainly used as a transesterification accelerator instead of a flame retardant aid, the resin composition does not have to contain a halogen-based flame retardant.
  • the inclusion of a halogen-based flame retardant is not excluded, and the resin composition may contain a known flame retardant such as a halogen-based flame retardant according to desired characteristics.
  • a halogen-based flame retardant is contained, the antimony compound can act as a transesterification accelerator as well as a flame retardant aid.
  • halogen-based flame retardants include organic halides.
  • organic halides include halogen-containing acrylic resins, halogen-containing styrene-based resins, halogen-containing polycarbonate-based resins, halogen-containing epoxy compounds, halogen-containing phenoxy resins, halogen-containing phosphoric acid esters, halogen-containing triazine compounds, and halogen-containing isocyanuric acid compounds.
  • Halogenated polyaryl ether compound halogenated aromatic imide compound and the like.
  • the resin composition can contain, if necessary, a high fluidizing agent for improving the fluidity of the resin composition.
  • a high fluidizing agent for improving the fluidity of the resin composition.
  • the high fluidizing agent include polyvalent hydroxyl group-containing compounds.
  • the polyvalent hydroxyl group-containing compound partial esters of polyhydric alcohols and fatty acids can be used.
  • glycerin mono12 hydroxystearate, glycerin monostearate, triglycerin monostearate, and fatty acid esters of pentaerythritol and dipentaerythritol. Etc., and one or more selected from these can be used.
  • the content of the high fluidizing agent is preferably 0.1 to 4.0 parts by mass, preferably 0.5 to 3.0 parts by mass, based on 100 parts by mass of the total of the polyethylene terephthalate resin and the polyethylene terephthalate resin. It is more preferable to have.
  • the resin composition can contain an inorganic filler, if necessary.
  • an inorganic filler By containing an inorganic filler, high mechanical strength can be imparted.
  • the inorganic filler include fibrous fillers such as glass fiber, silica fiber, silica / alumina fiber, and alumina fiber; carbon black, silica, quartz powder, glass beads, calcium silicate, aluminum silicate, kaolin, talc, calcium carbonate, etc.
  • Powder-granular fillers examples thereof include plate-like fillers such as silica, glass flakes, and various metal foils.
  • the amount of the inorganic filler added is not particularly limited, and is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, based on 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin.
  • the resin composition contains a mold release agent, an antioxidant, a weather stabilizer, a molecular weight modifier, an ultraviolet absorber, an antistatic agent, a dye, a pigment, a lubricant, and a crystallization accelerator as long as the effects of the present invention are not impaired.
  • Crystal nucleating agent, near-infrared absorber, organic filler and the like can be contained, but the additive is not limited to these.
  • the content of the additive is not particularly limited, and may be 10% by mass or less, or 5% by mass or less in the resin composition.
  • the resin composition satisfies the following formulas I and II.
  • Formula I Crystallization temperature Tc1 (° C.) ⁇ 195 ° C.
  • Formula II Crystallization temperature Tc1 (° C.)-Crystalization temperature Tc3 (° C.) ⁇ 15 ° C. Based on JIS K7121, Tc1 in formulas I and II is subjected to a cycle test in which the temperature is raised from 40 ° C. to 280 ° C. at a heating rate of 10 ° C./min and the temperature is lowered from 280 ° C. to 40 ° C. at a temperature lowering rate of 10 ° C./min.
  • Tc1 is rounded off to the first decimal place.
  • Tc1-Tc3 are assumed to be rounded to the first decimal place.
  • the crystallization temperature Tc1 is 195 ° C. or lower, preferably 190 ° C. or lower, and more preferably 185 ° C. or lower.
  • the difference between the crystallization temperature Tc1 and the crystallization temperature Tc3 [crystallization temperature Tc1 (° C.)]-[Crystalization temperature Tc3 (° C.)] is 15 ° C. or lower, preferably 10 ° C. or lower. , More preferably 5 ° C. or lower.
  • Thermal stability can be improved by setting the difference between the crystallization temperature Tc1 and the crystallization temperature Tc3 to 15 ° C. or less.
  • the crystallization temperatures Tc1 and Tc3 of the resin composition are adjusted by adjusting the crystallization temperature and / or content of the PET resin, as well as the type and / or content of the phosphorus compound, and / or the PBT resin and the PET resin. It can be carried out by adding an additive (transesterification accelerator) that promotes the transesterification reaction with and the like.
  • an additive transesterification accelerator
  • the crystallization temperature Tc1 tends to be lowered.
  • the crystallization temperature Tc3 tends to be high.
  • antimony trioxide is used as the transesterification accelerator, the difference between the crystallization temperatures Tc1 and Tc3 tends to be large.
  • the crystallization temperatures Tc1 and Tc3 of the obtained resin composition can be adjusted by devising a method for producing the resin composition. The manufacturing method will be described later.
  • the resin composition can produce a molded product having excellent appearance and excellent thermal stability, it can be used for interior parts and / or exterior parts for automobiles, such as door mirror stays, inner or outer door handles, and ventilator fins. It can be suitably used for molded products such as those exposed on the external surface.
  • the method for producing such a molded product is not particularly limited, and can be formed by, for example, conventionally known injection molding, compression molding, or the like.
  • the method for producing the resin composition is not particularly limited, and the resin composition can be produced using equipment and methods known in the art.
  • the required components can be mixed and kneaded using a single-screw or twin-screw extruder or other melt-kneading device to prepare pellets for molding. Multiple extruders or other melt kneaders may be used. Further, all the components may be input from the hopper at the same time, or some components may be input from the side feed port.
  • the polybutylene terephthalate resin and the polyethylene terephthalate resin satisfy the following formula III from the viewpoint of adjusting the crystallization temperatures Tc1 and Tc3 of the obtained resin composition by the production method. It can be configured to be heat-treated under the conditions to obtain a resin mixture, and then the resin mixture and a phosphorus compound are mixed to obtain a resin composition.
  • Formula III 12000 (° C. s) ⁇ temperature (° C.) x time (s) ⁇ 180000 (° C. s)
  • the temperature (° C.) is the temperature inside the heating container or the extrusion temperature
  • the time (s) is the time for the resin to stay in the heating container.
  • the flow rate Q (kg / h) of the resin when the PBT resin and the PET resin are heat-treated can be, for example, 10 to 20 kg / h, and the rotation speed N (rpm) can be, for example, 100 to 150 rpm. be able to.
  • the conditions for mixing the phosphorus compound with the resin mixture containing the PBT resin and the PET resin are not particularly limited, and are, for example, 10 to 30 ° C. higher than the melting point measured by the differential scanning calorimeter of the PBT resin or the PET resin. It can be melt-kneaded at a temperature for 60 to 240 seconds.
  • the flow rate Q (kg / h) of the resin during melt kneading can be, for example, 10 to 20 kg / h, and the rotation speed N (rpm) can be, for example, 100 to 150 rpm.
  • the method of obtaining a resin mixture by heat-treating the PBT resin and the PET resin in advance and the method of mixing the resin mixture and the phosphorus compound are not particularly limited, and can be carried out using a known extruder or melt-kneading device.
  • the step of obtaining a resin mixture by heat treatment is usually carried out while heating and kneading (heating and mixing) to obtain a resin alloy of PBT resin and PET resin.
  • a step of heat-treating a PBT resin and a PET resin to obtain a resin mixture hereinafter, also referred to as a “heat treatment step” and a step of mixing a resin mixture and a phosphorus compound to obtain a resin composition (hereinafter, “melting”).
  • the "kneading process”) may be a series of processes or may be a separate process.
  • the PBT resin and the PET resin are melt-retained in a heating container using a plast mill or the like to heat-treat the resin, and then the heating container is used.
  • the heating container is used. Examples thereof include a method of obtaining a resin composition by adding a phosphorus compound to the inside and melt-kneading.
  • a composition pellet containing the PBT resin and the PET resin is obtained by melt-extruding the PBT resin and the PET resin using an extruder.
  • a resin composition can be obtained by melt-kneading the composition pellets and the phosphorus compound using an extruder or a melt-kneading device.
  • the number of times the PBT resin and the PET resin are melt-extruded in the heat treatment step can be selected from the viewpoint of the intrinsic viscosity of the obtained composition, and can be, for example, 1 to 10 times.
  • the timing of adding the other resin, the inorganic filling and / or the other additive is not particularly limited, and the PBT resin and the PET resin may be added to the resin composition in the step of heat-treating in advance. It may be added to the resin composition in the step of adding the phosphorus compound and melt-kneading.
  • the manufacturing method can also be configured to have the following steps: i) Step of mixing polybutylene terephthalate resin and polyethylene terephthalate resin to obtain a resin mixture, ii) A step of heat-treating the resin mixture under the conditions satisfying the following formula III, Formula III: 12000 (° C. s) ⁇ temperature (° C.) x time (s) ⁇ 180000 (° C. s) iii) Step of mixing the heat-treated resin mixture with the phosphorus compound
  • the method of mixing the resin in step i) is not particularly limited, and for example, it can be performed using a known stirring / mixing device, extruder, melt-kneading device, or the like.
  • the method of heat-treating in step ii) and the method of mixing the resin mixture and the phosphorus compound in step ii) are the method of preliminarily heat-treating the PBT resin and PET resin to obtain the resin mixture, and the method of obtaining the resin mixture and the resin mixture and phosphorus. It can be carried out in the same manner as the method of mixing the compounds.
  • the molded product according to the present embodiment is a molded product molded by using the above-mentioned resin composition. Since this molded product uses the above-mentioned resin composition, it has excellent appearance and thermal stability. Since it is excellent in thermal stability, it is possible to suppress deterioration of moldability and deterioration of physical properties after melt molding. Since the molded product has excellent appearance and thermal stability, the molded product exposed to the external surface such as an interior part for an automobile and / or an exterior part for an automobile, for example, a door mirror stay, an inner / outer door handle, a ventilator fin, etc. Can be suitably used as.
  • the method for producing the molded product is not particularly limited, and can be formed by, for example, conventionally known injection molding, compression molding, or the like.
  • Example 1 Comparative Examples 1 to 3
  • the components shown in Table 1 are blended according to the composition (part by mass) shown in Table 1 and supplied from a hopper to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mm ⁇ , and the residence time at a cylinder temperature of 260 ° C. Was melt-kneaded for 50 seconds to obtain a pellet-shaped PBT resin composition.
  • Example 2 PBT and PET are blended with the composition (part by mass) shown in "Heat treatment 1" in Table 1 and supplied from a hopper to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mm ⁇ , as shown in Table 1.
  • Examples 3 to 5 Comparative Examples 4 to 13
  • a resin composition was obtained by the same method as in Example 2 except that the composition shown in Table 1, the heat treatment conditions, and the melt kneading conditions were used.
  • Example 6 PBT and PET were blended with the composition (part by mass) shown in Table 1 and melt-kneaded for 10 minutes at a cylinder temperature of 280 ° C. and a screw rotation speed of 100 rpm using a lab plast mill manufactured by Toyo Seiki Co., Ltd. After kneading, the phosphorus compound was added so as to have the composition (parts by mass) shown in Table 1 and kneaded for 2 minutes to obtain a resin composition.
  • Example 7 A resin composition was obtained by the same method as in Example 6 except that the heat treatment conditions and melt kneading conditions in Table 1 were used.
  • the peak temperature (° C.) of the maximum endothermic peak of the DSC curve in differential scanning calorimetry (DSC) was determined as Tc3.
  • the results are shown in Table 1.
  • the examples and comparative examples of Table 1 are the compositions of PBT and PET alloy, and the ones in which two peaks of the melting point Tm are observed are described in the upper row and the lower row. In addition, only one peak could be confirmed at the crystallization temperature Tc in any case.
  • the product was injection-molded, and the transferred state of the grain was visually observed for the molded product at the stage where the molding was stable about 10 shots after the start of molding.
  • the observation results were evaluated according to the following criteria. The results are shown in Table 1. Good: Good transfer condition was confirmed on the entire grain surface. Bad: Transfer unevenness of grain was observed.
  • Tc1-Tc3 The values of ⁇ Tc (Tc1-Tc3) were calculated from the crystallization temperatures Tc1 and Tc3 measured above, and the thermal stability was evaluated according to the following criteria. The results are shown in Table 1. Good: Tc1-Tc3 ⁇ 15 ° C Defective: Tc1-Tc3> 15 ° C
  • the molded product using the resin composition obtained in the examples has excellent appearance and thermal stability.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023100897A1 (ja) 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、複合体、および、金属樹脂複合体
WO2023100895A1 (ja) 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、およびペレット
WO2023100896A1 (ja) 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1149937A (ja) * 1997-07-30 1999-02-23 Polyplastics Co ガスアシスト射出成形用樹脂組成物および成形方法
JP2003055540A (ja) * 2001-08-21 2003-02-26 Toyobo Co Ltd ポリエステル樹脂組成物
JP2006219626A (ja) * 2005-02-14 2006-08-24 Mitsubishi Engineering Plastics Corp ポリブチレンテレフタレート樹脂組成物、およびこれを成形してなる成形品
WO2018225778A1 (ja) * 2017-06-07 2018-12-13 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1149937A (ja) * 1997-07-30 1999-02-23 Polyplastics Co ガスアシスト射出成形用樹脂組成物および成形方法
JP2003055540A (ja) * 2001-08-21 2003-02-26 Toyobo Co Ltd ポリエステル樹脂組成物
JP2006219626A (ja) * 2005-02-14 2006-08-24 Mitsubishi Engineering Plastics Corp ポリブチレンテレフタレート樹脂組成物、およびこれを成形してなる成形品
WO2018225778A1 (ja) * 2017-06-07 2018-12-13 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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023100897A1 (ja) 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、複合体、および、金属樹脂複合体
WO2023100895A1 (ja) 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、およびペレット
WO2023100896A1 (ja) 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品

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