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WO2013012004A1 - Corps moulé en résine, et pièce interne de véhicule - Google Patents

Corps moulé en résine, et pièce interne de véhicule Download PDF

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Publication number
WO2013012004A1
WO2013012004A1 PCT/JP2012/068202 JP2012068202W WO2013012004A1 WO 2013012004 A1 WO2013012004 A1 WO 2013012004A1 JP 2012068202 W JP2012068202 W JP 2012068202W WO 2013012004 A1 WO2013012004 A1 WO 2013012004A1
Authority
WO
WIPO (PCT)
Prior art keywords
polybutylene terephthalate
terephthalate resin
resin molded
acetaldehyde
molded body
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/068202
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English (en)
Japanese (ja)
Inventor
久美子 土居
一也 五島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wintech Polymer Ltd
Original Assignee
Wintech Polymer Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wintech Polymer Ltd filed Critical Wintech Polymer Ltd
Priority to JP2013525680A priority Critical patent/JP5932792B2/ja
Publication of WO2013012004A1 publication Critical patent/WO2013012004A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings

Definitions

  • the present invention relates to a resin molded body formed by molding a polybutylene terephthalate resin composition, and an automobile interior part (part used for the interior of an automobile) composed of the resin molded body.
  • Thermoplastic polyester resins are widely used in automobile parts, films, electrical / electronic parts, etc., because they have excellent mechanical properties, heat resistance, and moldability.
  • polybutylene terephthalate resin and polyethylene terephthalate resin which are a kind of polyester resin, have a high reinforcing effect by an inorganic reinforcing material and are excellent in chemical resistance.
  • these resins are widely used as materials for industrial molded products such as connectors, relays, and switches for automobiles and electrical / electronic devices.
  • the above polyethylene terephthalate resin is thermally decomposed during molding to produce acetaldehyde. Specifically, when the polyethylene terephthalate resin exposed to a high temperature environment during molding is thermally decomposed, the ester bond in the polymer chain is cleaved to produce components such as ethylene glycol. The component becomes acetaldehyde.
  • Acetaldehyde is a substance that causes malodors and odors. For this reason, the technique which suppresses generation
  • acetaldehyde is not generated during the molding of polybutylene terephthalate resin.
  • the present inventors have found that acetaldehyde is also produced during molding from polybutylene terephthalate resin.
  • the present inventors have also found that formaldehyde is generated during molding of polybutylene terephthalate resin.
  • the present invention has been made to solve the above-mentioned problems, and its purpose is to provide a technique capable of suppressing the discharge amount of acetaldehyde and the discharge amount of formaldehyde from the molded article of the polybutylene terephthalate resin composition. There is to do.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by producing a resin molded body using a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and a nitrogen-containing compound having a ureido group as a raw material, and complete the present invention. It came to. More specifically, the present invention provides the following.
  • the formaldehyde gas emission measured by the following method is 0.10 ⁇ g or less, and the acetaldehyde gas emission is 0.15 ⁇ g or less.
  • Resin molded body. Formmaldehyde and acetaldehyde gas measurement method
  • the discharge amount of acetaldehyde and the discharge amount of formaldehyde from the molded body of the polybutylene terephthalate resin composition can be suppressed. For this reason, the amount of acetaldehyde and formaldehyde which the resin molding of this invention leaks from a resin molding at the time of use is small.
  • the resin molded body of the present invention is composed of a polybutylene terephthalate resin composition (hereinafter sometimes simply referred to as “resin composition”) containing a polybutylene terephthalate resin and a nitrogen-containing compound having a ureido group.
  • resin composition a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and a nitrogen-containing compound having a ureido group.
  • the polybutylene terephthalate resin contained in the resin composition includes 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. It is a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing (1,4-butanediol) or an ester-forming derivative thereof (acetylated product, etc.).
  • the polybutylene terephthalate resin is not limited to a homopolybutylene terephthalate resin, but may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
  • examples of dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′ C 8-14 aromatic dicarboxylic acids such as dicarboxydiphenyl ether; C 4-16 alkane dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid; C 5-10 cycloalkanes such as cyclohexane dicarboxylic acid Dicarboxylic acids; 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.
  • C 8-12 aromatic dicarboxylic acids such as isophthalic acid
  • C 6-12 alkanedicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.
  • glycol components (comonomer components) other than 1,4-butanediol for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, C 2-10 alkylene glycol such as neopentyl glycol and 1,3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; alicyclic diol such as cyclohexanedimethanol and hydrogenated bisphenol A Aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; ethylene oxide 2-mol adduct of bisphenol A, propylene of bisphenol A Kisaido such as a three molar adduct, alkylene oxide adducts of C 2-4 of bisphenol A; or ester-forming derivatives of these glycols
  • C 2-6 alkylene glycol such as ethylene glycol and trimethylene glycol
  • polyoxyalkylene glycol such as diethylene glycol
  • alicyclic such as cyclohexanedimethanol Diols and the like are more preferable.
  • acetaldehyde When ethylene glycol is used, acetaldehyde is generated without cleavage of a single bond between carbons as in the case of polyethylene terephthalate resin.
  • the polybutylene terephthalate resin does not contain an ethylene glycol component, even if the ethylene glycol component contains only a trace amount, acetaldehyde may be generated during molding of the polybutylene terephthalate resin. It is characterized in that the production of acetaldehyde can be suppressed.
  • the intrinsic viscosity of the polybutylene terephthalate resin used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 0.65 dL / g or more and 1.4 dL / g or less.
  • the intrinsic viscosity can also be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities.
  • a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g is 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 do.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.
  • the amount of terminal carboxyl groups of the polybutylene terephthalate resin used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
  • the amount of terminal carboxyl groups of the polybutylene terephthalate resin used in the present invention is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.
  • the resulting polybutylene terephthalate resin composition is less susceptible to strength reduction due to hydrolysis in a moist heat environment.
  • the content of the polybutylene terephthalate resin in the resin molded body is preferably 30% by mass or more and 99.96% by mass or less. If it is 30 mass% or more, since the improvement of the physical property by containing polybutylene terephthalate resin appears in a resin molding, it is preferable.
  • the content of the polybutylene terephthalate resin is more preferably 50% by mass or more and 99.96% by mass or less.
  • the resin composition contains a compound having a ureido group (hereinafter sometimes referred to as “ureido compound”).
  • ureido compound a compound having a ureido group
  • the amount of formaldehyde and the amount of acetaldehyde contained in the obtained resin molding can be reduced.
  • VOC low molecular weight organic compound that easily volatilizes even at room temperature
  • the compound having a ureido group is not particularly limited as long as it has a ureido group.
  • Examples of the compound having a ureido group include acyclic ureido compounds, cyclic monoureido compounds, and cyclic diureido compounds.
  • Examples of acyclic ureido compounds include ureido acids of C 2-6 dicarboxylic acids such as oxalic acid, ureido group-containing C 1-6 monocarboxylic acids such as ureidoacetic acid, and carbamide group-containing C 2-6 dicarboxylic acids such as ureidosuccinic acid. Or monoureido such as derivatives thereof (amide, ester, etc.); diureido of C 2-6 dicarboxylic acid such as allantoic acid, and the like.
  • Examples of the cyclic monoureido compound include alkylene urea [C 1-10 alkylene urea (preferably C 1-6 alkylene urea) such as methylene urea, ethylene urea, crotonylidene urea (CDU)], alkenylene urea (vinylene urea, cytosine, etc.).
  • alkynylene urea C 2-10 alkenylene urea etc.
  • alkynylene urea C 2-10 alkynylene urea (preferably C 2-6 alkynylene urea) etc.
  • arylene urea eg mesatin etc., ureido of dicarboxylic acid (parabanic acid, dimethylparabanic acid) , Barbituric acid, 5,5-diethylbarbituric acid, dilituric acid, dialuric acid, alloxan, alloxanic acid, isocyanuric acid, uramil, etc.), ⁇ -aldehyde acid ureido [uracil, 5-methyluracil (thymine), dihydro Uracil, urazole, benzoylene urine Element], ⁇ -oxyacid ureido [hydantoin, 5,5-dimethylhydantoin, 1,1-methylenebis (5,5-dimethylhydanto
  • cyclic diureido compounds include uric acid, 3-methyluric acid, pseudouric acid, acetylene urea (glycoluril), diureido of ⁇ -oxy acid [1,1-methylenebis (5,5-dimethylhydantoin), allantoin, etc.], p- Examples include diurea such as urazine, diureido of dicarboxylic acid (alloxanthin, purpuric acid and the like), and derivatives thereof.
  • allantoin As Among these compounds having a ureido group, it is preferable to use allantoin. By using allantoin, the effect of reducing the amount of acetaldehyde and the amount of formaldehyde contained in the resin molding is greatly enhanced.
  • content of the compound which has a ureido group in a resin composition is not specifically limited, 0.04 mass% or more and 0.4 mass% or less are preferable. If the content of the compound having a ureido group is within this range, both the amount of acetaldehyde and the amount of formaldehyde contained in the resin molded product can be sufficiently reduced.
  • the content of the compound having a ureido group is 0.05% by mass or more and 0.3% by mass or less, the effect of sufficiently reducing both the amount of acetaldehyde and the amount of formaldehyde contained in the resin molded body In addition, there is an effect that a decrease in mechanical strength is small even when exposed to a high temperature environment. Moreover, if it is the range of this content, discoloration can be suppressed even if it does not use antioxidant.
  • the content of the ureido compound can be adjusted as appropriate depending on the use of the resin molded body to be obtained.
  • hindered phenol antioxidants and phosphorus stabilizers can be used as other components.
  • One of the features of the present invention is that the use of allantoin has a certain heat aging resistance without using the above antioxidants and stabilizers.
  • the hindered phenol-based antioxidant includes a monocyclic hindered phenol compound, a polycyclic hindered phenol compound linked with a hydrocarbon group or a group containing a sulfur atom, an hindered phenol compound having an ester group or an amide group. Etc.
  • examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, C 2-10 alkylene bis (t-butylphenol) [for example, 2,2′-methylene bis (4-methyl).
  • phenolic antioxidants can be used alone or in combination of two or more.
  • tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferably used.
  • the content of the hindered phenolic antioxidant in the resin composition is preferably 0.01% by mass or more and 3% by mass or less. If it is less than 0.01% by mass, the effect of inhibiting acetaldehyde production is insufficient, and the long-term thermal stability effect may be insufficient. On the other hand, when it exceeds 3 mass%, it may lead to deterioration of mechanical properties.
  • the content of the more preferred hindered phenol antioxidant is 0.1% by mass or more and 1% by mass or less.
  • phosphorus stabilizers include mono to tris (branched C3-6 alkyl-phenyl) such as tris (2,4-di-t-butylphenyl) phosphite and bis (2-t-butylphenyl) phenylphosphite.
  • the content of the phosphorus stabilizer in the resin composition is preferably 0.01% by mass or more and 3% by mass or less. If it is less than 0.01% by mass, the effect of inhibiting acetaldehyde production is insufficient, and the long-term thermal stability effect may be insufficient. If it exceeds 3 mass%, mechanical properties may be deteriorated.
  • a more preferable range of the content of the phosphorus stabilizer is 0.1% by mass or more and 1% by mass or less.
  • antioxidants hindered phenolic antioxidants, phosphorus stabilizers, other resins, reinforcing agents such as glass fibers, and pigments, as long as the resin molded body does not impair the effects of the present invention
  • additives such as antioxidants and stabilizers may be included.
  • the resin molded body of the present invention is formed by molding a resin composition containing the above-described components by a general molding method.
  • the molding method include an injection molding method and an extrusion molding method.
  • the method for producing a resin molded body of the present invention will be described by taking the case of using an extruder as an example.
  • a screw is disposed in a cylinder having a hopper for charging raw materials.
  • the screw has a feed zone (feeding unit), a compression zone (compression unit), and a metering zone (measuring unit) in this order from the upstream side to the downstream side of the screw.
  • a die is provided at the downstream end of the cylinder.
  • the supply unit normally has a function of transferring the raw material from the hopper side to the die direction side at a temperature setting so that the raw material does not melt, and sends the raw material to the compression unit.
  • the compression unit melt-kneads the raw material while applying pressure to the raw material, and sends the melt-kneaded raw material to the measuring unit.
  • the metering unit sends the melt-kneaded raw material to the die by a constant amount under a constant pressure.
  • raw materials are charged into an extrusion molding machine.
  • the raw materials are the above-mentioned components, and all the components may be charged into the molding machine at the same time, or some of the components may be charged at the compression part or other parts.
  • polybutylene terephthalate resin pellets and powdered polybutylene terephthalate resin may be added from a hopper together with components such as a ureido compound.
  • a ureido compound By adding the powdery polybutylene terephthalate resin, the polybutylene terephthalate resin and the ureido compound can be sufficiently kneaded in the compression portion or the like.
  • the raw material is kneaded while applying pressure and heat.
  • the degree of kneading depends on the molding conditions such as the type of screw element used and the screw rotation speed. In the production of the resin molded body of the present invention, the degree of kneading can be appropriately adjusted according to the type of resin, the shape of the resin molded body, and the like.
  • acetaldehyde is generated by applying pressure or heat to the raw material.
  • the amount of acetaldehyde generated is very small compared to the case where polyethylene terephthalate resin is used. This is considered to be because a single bond between carbons needs to be cleaved in order to produce acetaldehyde from polybutylene terephthalate resin.
  • formaldehyde may be generated by applying pressure to the raw material in the compression section.
  • components such as a ureido compound can be sufficiently dispersed in the resin molding. By sufficiently dispersing them, it is possible to efficiently suppress the discharge of acetaldehyde inside the resin molded body.
  • the raw materials kneaded in the compression unit are sent out to the die by a certain amount under a certain pressure.
  • the above “constant pressure” and “constant amount” can be appropriately changed according to the shape of the resin molded body and the like. These can be adjusted by adjusting the groove width and groove depth of the screw element.
  • the resin molded body of the present invention is obtained by being extruded from the die.
  • the shape of the resin molding varies depending on the shape of the discharge hole of the die, and is, for example, a sheet shape, a strand shape, a tube shape, or the like.
  • a resin pellet can be manufactured by cut
  • the resin molded product of the present invention has a very low acetaldehyde content and formaldehyde content.
  • the formaldehyde emission measured by the following method is 0.10 ⁇ g or less, and the acetaldehyde emission is 0.15 ⁇ g or less.
  • the generated acetaldehyde gas discharge amount and formaldehyde gas discharge amount are measured. More specifically, as described in the examples.
  • the resin molded body of the present invention can be suitably used as a part used in a sealed space or a space that can be sealed. This is because, in a sealed space, even if a trace amount of acetaldehyde, formaldehyde, etc. leaks from the resin molded body, there is a possibility that it will be a problem. Specific examples of such parts include automobile interior parts.
  • ⁇ Material> Polybutylene terephthalate resin
  • Polycondensate of terephthalic acid and 1,4-butanediol, inherent viscosity (IV) is 0.69
  • "DURANEX 300FP” manufactured by Wintech Polymer (Nitrogen-containing compound having a ureido group) Allantoin, manufactured by Tokyo Chemical Industry Co., Ltd.
  • the manufacturing method of the resin composition pellet for producing a resin molding> A mixture of the components shown in Table 1 in the proportions shown in Table 1 (unit: mass%) was used as a raw material, and this raw material was charged into a twin screw extruder (manufactured by JSW, TEX-30). Under the following conditions, the raw materials were melt-kneaded to produce a polybutylene terephthalate resin composition.
  • test piece The pellets of the polybutylene terephthalate resin composition were kept in a thermostat at 140 ° C. for 3 hours, and the pellets were dried. A test piece of 100 mm ⁇ 40 mm ⁇ 2 mm was molded by an injection molding machine (manufactured by JSW, J75EP) using the dried pellets. (Injection molding conditions) Cylinder temperature: 250 ° C Mold temperature: 60 °C Injection speed: 16.7 mm / sec
  • acetaldehyde gas discharge amount and formaldehyde gas discharge amount was performed by the method described in the following (i) to (ii).
  • Examples 1 to 5 and Comparative Examples 1 to 3 were exposed to a pressure cooker tester at 121 ° C./2 atm for 0 hour (indicating before being put into the tester), 20 hours, 40 hours, and then ISO527.
  • the tensile strength (MPa), the tensile strength retention rate (%), and the tensile fracture strain (%) were measured to evaluate hydrolysis resistance.
  • the used test piece was manufactured based on ISO3167. The measurement results are shown in Table 2.
  • Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to heat treatment in a hot air oven at 180 ° C. for a predetermined time (described in Table 3), and then maintained in accordance with ISO 527, tensile strength (MPa) and tensile strength. The rate (%), tensile fracture strain (%), and tensile fracture strain retention rate (%) were measured, and the change in hue ( ⁇ E) was further confirmed. The results are shown in Table 3. For the change in hue, a Z-300A type color sensor manufactured by Nippon Denshoku Industries Co., Ltd. was used.
  • Example 3 By comparing Example 3 and Comparative Example 2, and comparing Example 4 and Comparative Example 3, it was confirmed that the nitrogen-containing compound having a ureido group had no particular adverse effect on the antioxidant. .

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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)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention fournit une technique permettant de réguler la quantité d'acétaldéhyde et de formaldéhyde déchargés par un corps moulé d'une composition de résine polybutylène téréphthalate. Un corps moulé en résine est fabriqué avec pour matériau de base la composition de résine polybutylène téréphthalate qui contient une résine polybutylène téréphthalate, et un composé à teneur en azote possédant un groupe uréide. De préférence, une allantoïne est mise en œuvre en tant que composé à teneur en azote possédant un groupe uréide. Enfin, dans le corps moulé en résine de l'invention, la teneur en composé à teneur en azote est supérieure ou égale à 0,04% en masse, et inférieure ou égale à 0,4% en masse.
PCT/JP2012/068202 2011-07-20 2012-07-18 Corps moulé en résine, et pièce interne de véhicule Ceased WO2013012004A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013525680A JP5932792B2 (ja) 2011-07-20 2012-07-18 樹脂成形体及び自動車内装部品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011158576 2011-07-20
JP2011-158576 2011-07-20

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WO2013012004A1 true WO2013012004A1 (fr) 2013-01-24

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004196998A (ja) * 2002-12-19 2004-07-15 Wintech Polymer Ltd 難燃性樹脂組成物
JP2006028318A (ja) * 2004-07-15 2006-02-02 Mitsubishi Chemicals Corp ポリエステル系樹脂およびその製造方法
JP2007538126A (ja) * 2004-05-18 2007-12-27 エンメ エ ジ・ポリメリ・イタリア・ソチエタ・ペル・アツィオーニ 区画化された樹脂ペレット
JP2008174726A (ja) * 2007-01-19 2008-07-31 Far Eastern Textile Ltd アセトアルデヒドスカベンジャー、ポリエステルブレンド及びその製造方法及び成形容器
JP2008254232A (ja) * 2007-04-02 2008-10-23 Toyobo Co Ltd 多層成形体および多層成形体の製造方法
JP2009531519A (ja) * 2006-03-24 2009-09-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ｐｂｔ単位を含有する、減少した有機炭素排出量を有する熱可塑性樹脂

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4478294B2 (ja) * 2000-06-02 2010-06-09 ポリプラスチックス株式会社 難燃性樹脂組成物
JP4700852B2 (ja) * 2000-07-26 2011-06-15 ポリプラスチックス株式会社 難燃性樹脂組成物
AU2003292608A1 (en) * 2002-12-27 2004-07-29 Polyplastics Co., Ltd. Flame-retardant resin composition
US7498368B2 (en) * 2003-05-26 2009-03-03 Polyplastics Co., Ltd. Flame-retardant resin composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004196998A (ja) * 2002-12-19 2004-07-15 Wintech Polymer Ltd 難燃性樹脂組成物
JP2007538126A (ja) * 2004-05-18 2007-12-27 エンメ エ ジ・ポリメリ・イタリア・ソチエタ・ペル・アツィオーニ 区画化された樹脂ペレット
JP2006028318A (ja) * 2004-07-15 2006-02-02 Mitsubishi Chemicals Corp ポリエステル系樹脂およびその製造方法
JP2009531519A (ja) * 2006-03-24 2009-09-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ｐｂｔ単位を含有する、減少した有機炭素排出量を有する熱可塑性樹脂
JP2008174726A (ja) * 2007-01-19 2008-07-31 Far Eastern Textile Ltd アセトアルデヒドスカベンジャー、ポリエステルブレンド及びその製造方法及び成形容器
JP2008254232A (ja) * 2007-04-02 2008-10-23 Toyobo Co Ltd 多層成形体および多層成形体の製造方法

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JPWO2013012004A1 (ja) 2015-02-23

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