WO2012121066A1 - Procédé de production pour article moulé par injection - Google Patents

Procédé de production pour article moulé par injection Download PDF

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Publication number
WO2012121066A1
WO2012121066A1 PCT/JP2012/054983 JP2012054983W WO2012121066A1 WO 2012121066 A1 WO2012121066 A1 WO 2012121066A1 JP 2012054983 W JP2012054983 W JP 2012054983W WO 2012121066 A1 WO2012121066 A1 WO 2012121066A1
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WO
WIPO (PCT)
Prior art keywords
mold
molded product
injection
heat
insulating layer
Prior art date
Application number
PCT/JP2012/054983
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English (en)
Japanese (ja)
Inventor
貴之 宮下
Original Assignee
ポリプラスチックス株式会社
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.)
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Priority to CN2012800119363A priority Critical patent/CN103402727A/zh
Publication of WO2012121066A1 publication Critical patent/WO2012121066A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3828—Moulds made of at least two different materials having different thermal conductivities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2909/00—Use of inorganic materials not provided for in groups B29K2803/00 - B29K2807/00, as mould material
    • B29K2909/14—Stones

Definitions

  • the present invention relates to a method for manufacturing an injection molded product.
  • PAS resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. . For this reason, PAS resin is widely used for electrical / electronic equipment component materials, automotive equipment component materials, chemical equipment component materials, and the like, and is particularly used for applications with a high use environment temperature.
  • the PAS resin has a slow crystallization rate and a high glass transition temperature, so that the crystallinity of the surface of the molded product is difficult to increase, and a locally non-uniform crystal structure tends to be obtained. For this reason, the surface of the molded product containing the PAS resin is likely to be uneven in appearance and structure.
  • PAS resin composition some resin compositions containing a PAS resin (hereinafter sometimes referred to as “PAS resin composition”) have a heat distortion temperature of less than 140 ° C.
  • PAS resin composition When an injection molded product is manufactured using a resin composition having a thermal deformation temperature of less than 140 ° C. under a condition where the mold temperature is 140 ° C. or higher, the injection molded product is deformed or separated when the injection molded product is taken out from the mold. Problems such as mold defects may occur.
  • the mold temperature is set to a temperature equal to or lower than the heat deformation temperature to produce a molded product.
  • the injection molded product obtained under such conditions has a low crystallinity. Therefore, heat treatment is performed on the injection molded product having a low crystallinity to increase the crystallinity of the injection molded product.
  • a technique for increasing the crystallization degree by subjecting such an injection-molded product to heat treatment is a general technique, and is described in, for example, Patent Document 1.
  • the present invention has been made in order to solve the above-mentioned problems, and the object thereof is to produce the above-mentioned injection molded article when a molded article is produced from a PAS resin composition having a heat distortion temperature of less than 140 ° C. as a raw material. It is an object of the present invention to provide a technique capable of sufficiently increasing the degree of crystallinity of a molded product without lowering the mold temperature condition so as not to cause problems such as deformation, and without performing the above heat treatment.
  • a polyarylene sulfide-based resin composition having a heat deformation temperature of less than 140 ° C. is injection molded at a mold temperature equal to or lower than the heat deformation temperature using a mold having a heat insulating layer formed on the inner surface of the mold.
  • the present inventors have found that the above problems can be solved, and have completed the present invention. More specifically, the present invention provides the following.
  • the polyarylene sulfide-based resin composition is substantially composed of a polyarylene sulfide-based resin, or is substantially composed of a polyarylene sulfide-based resin and an elastomer resin (1) or (2 ) A method for producing an injection-molded article.
  • the molded product when a molded product is produced using a resin composition containing a PAS resin having a heat distortion temperature of less than 140 ° C. as a raw material, the molded product can be obtained without subjecting the molded product to heat treatment after molding.
  • the crystallinity can be sufficiently increased.
  • the production method of the present invention uses a mold having a heat insulating layer formed on the inner surface of the mold, and injection-molds a polyarylene sulfide-based resin composition having a heat deformation temperature of less than 140 ° C. under the heat deformation temperature or lower. To do.
  • the polyarylene sulfide-based resin composition has a heat distortion temperature of less than 140 ° C.
  • the heat distortion temperature a value measured under a load of 1.8 MPa in accordance with ISO 75-1 and 2 is adopted.
  • the polyarylene sulfide-based resin composition includes a polyarylene sulfide-based resin.
  • the polyarylene sulfide resin is mainly composed of — (Ar—S) — (Ar is an arylene group) as a repeating unit.
  • a PAS resin having a generally known molecular structure can be used.
  • the arylene group is not particularly limited.
  • arylene sulfide groups composed of the above arylene groups in addition to a homopolymer using the same repeating unit, a polymer containing a repetition of different arylene sulfide groups is preferable depending on the application.
  • the homopolymer preferably has a p-phenylene sulfide group as a repeating unit as an arylene group. This is because a homopolymer having a p-phenylene sulfide group as a repeating unit has extremely high heat resistance and exhibits high strength, high rigidity and high dimensional stability in a wide temperature range. By using such a homopolymer, an injection molded product having very excellent physical properties can be obtained.
  • a combination of two or more types of arylene sulfide groups which are different from the arylene sulfide groups containing the above-mentioned arylene groups can be used.
  • a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferable from the viewpoint of obtaining an injection molded product having high physical properties such as heat resistance, moldability and mechanical properties.
  • a polymer containing 70 mol% or more of p-phenylene sulfide groups is more preferred, and a polymer containing 80 mol% or more is more preferred.
  • the PAS resin having the p-phenylene sulfide group and m-phenylene sulfide group as a repeating unit as described above is a material that is particularly required to improve the crystallinity of a molded product.
  • a high crystallinity of the molded product can be realized.
  • the manufacturing method of the injection molded product of the present invention has no problem of workability and productivity.
  • the PAS resin having a phenylene sulfide group is a PPS (polyphenylene sulfide) resin.
  • the polyarylene sulfide-based resin composition used in the present invention has a heat distortion temperature of less than 140 ° C.
  • the heat distortion temperature tends to be low. Specifically, when the content of the PAS resin is 95% by mass or more, the heat distortion temperature tends to be 100 ° C. or less.
  • the present invention after the PAS resin composition as a raw material is determined, even if the heat distortion temperature of the PAS resin composition becomes a low value as described above, The crystallinity can be sufficiently increased. As a result, an injection molded product having a high degree of crystallinity can be obtained without performing a heat treatment step required to increase the degree of crystallinity.
  • the PAS resin composition used in the present invention may contain other resins such as an elastomer resin as long as the effects of the present invention are not impaired.
  • resins such as an elastomer resin
  • pigments such as nucleating agent, carbon black and inorganic calcined pigment
  • inorganic fillers such as glass fiber, antioxidant, stabilizer, plasticizer, lubricant, mold release agent
  • the composition which added additives, such as a flame retardant, and provided the desired characteristic is also contained in the PAS type-resin composition used by this invention.
  • the heat distortion temperature of the PAS resin composition may change depending on the type and amount of the additive.
  • fibrous fillers such as glass fibers and plate-like fillers such as talc tend to increase the heat distortion temperature of the PAS resin composition.
  • a PAS resin composition composed of such an additive and a PAS resin tends to have a heat distortion temperature of less than 140 ° C., particularly 100 ° C. or less.
  • elastomer resin examples include polyolefin elastomer resin, polyester elastomer resin, fluorine elastomer resin, silicone elastomer resin, butadiene elastomer resin, polyamide elastomer resin, polystyrene elastomer resin, urethane elastomer resin, center
  • elastomer resin examples include various types of particle-based elastomer resins having a crosslinked structure, and one or more types can be used.
  • the crystallinity of the injection molded product can be sufficiently increased during molding. .
  • die used for the manufacturing method of this invention has the heat insulation layer formed in the metal mold
  • a heat insulating layer is formed on the entire inner surface of the mold.
  • the heat insulation layer is not formed.
  • any material may be used as long as it has low heat conductivity and has heat resistance to such an extent that it does not cause a problem even when it comes into contact with a high-temperature PAS resin composition, and the material constituting the heat insulating layer is not particularly limited.
  • Examples of the material that satisfies the heat resistance and thermal conductivity required for the heat insulating layer include resins having high heat resistance such as polyimide resin and low thermal conductivity, and porous ceramics such as porous zirconia. Hereinafter, these materials will be described.
  • polyimide resin examples include pyromellitic acid (PMDA) -based polyimide, biphenyltetracarboxylic acid-based polyimide, polyamideimide using trimellitic acid, bismaleimide-based resin (bismaleimide / triazine-based, etc.), benzophenone tetracarboxylic acid Based polyimide, acetylene-terminated polyimide, thermoplastic polyimide, and the like.
  • Preferable materials other than polyimide resin include, for example, tetrafluoroethylene resin.
  • the heat insulating layer may contain a resin other than polyimide resin and tetrafluoroethylene resin, additives, and the like as long as the effects of the present invention are not impaired.
  • the method for forming the heat insulating layer on the inner surface of the mold is not particularly limited.
  • a solution of a polymer precursor such as a polyimide precursor capable of forming a heat insulating layer is applied to the mold surface, heated to evaporate the solvent, and further heated to polymerize to form a heat insulating layer such as a polyimide film.
  • a polymer precursor such as a polyimide precursor capable of forming a heat insulating layer
  • die using a tape-shaped polymer heat insulation film and forming a heat insulation layer is mentioned. It is also possible to form a polyimide film and further form a chromium (Cr) film or a titanium nitride (TiN) film as a metal-based hard film on the surface thereof.
  • required by the said heat insulation layer comprised from resin changes with uses etc., it is especially preferable that it is 2 W / m * K or less.
  • the thermal conductivity of the heat insulating layer is adjusted to the above range, even when an injection molded product is molded at a mold temperature of 100 ° C. or less, an injection molded product with a high degree of crystallinity can be obtained more easily.
  • the said heat conductivity points out the heat conductivity measured by the method as described in an Example.
  • the thickness of the heat insulating layer made of resin is not particularly limited, and can be appropriately set to a preferable thickness depending on the material used, the shape of the molded product, and the like.
  • the heat insulating layer is composed of a polyimide resin, it is preferable that the heat insulating layer has a thickness of 20 ⁇ m or more because a sufficiently high heat insulating effect can be obtained.
  • the thickness of the heat insulating layer formed on the inner surface of the mold may be uniform or may include portions having different thicknesses.
  • the zirconia contained in the porous zirconia is not particularly limited, and may be any of stabilized zirconia, partially stabilized zirconia, and unstabilized zirconia.
  • Stabilized zirconia is one in which cubic zirconia is stabilized even at room temperature, and is excellent in mechanical properties such as strength and toughness and wear resistance.
  • Partially stabilized zirconia refers to a state in which tetragonal zirconia partially remains even at room temperature, and when subjected to external stress, a martensitic transformation from tetragonal to monoclinic crystal occurs, and is particularly advanced by the action of tensile stress. Suppresses crack growth and has high fracture toughness.
  • Unstabilized zirconia refers to zirconia that is not stabilized by a stabilizer. In addition, you may use combining at least 2 or more types selected from stabilized zirconia, partially stabilized zirconia, and unstabilized zirconia.
  • the stabilizer contained in the stabilized zirconia and the partially stabilized zirconia conventionally known general ones can be employed.
  • yttria, ceria, magnesia and the like can be mentioned.
  • the amount of the stabilizer used is not particularly limited, and the amount used can be appropriately set according to the application, the material used, and the like.
  • porous ceramics other than porous zirconia can be used, but porous zirconia has higher durability than other porous ceramics. For this reason, if a mold having a heat insulating layer composed of porous zirconia is used, problems such as deformation of the heat insulating layer are unlikely to occur, so there are a large number of injection molded products that can be continuously injection molded. Productivity is greatly increased.
  • the raw material for forming the heat insulating layer may further contain conventionally known additives in addition to the above-mentioned zirconia and stabilizer as long as the effects of the present invention are not impaired.
  • the method for forming the heat insulating layer using the above raw materials is not particularly limited, but it is preferable to employ a thermal spraying method.
  • the thermal spraying method By adopting the thermal spraying method, the thermal conductivity of porous zirconia is easily adjusted to a desired range. Moreover, problems such as a significant decrease in the mechanical strength of the heat insulating layer due to excessive formation of bubbles inside the porous zirconia do not occur.
  • the structure of a heat insulation layer becomes a thing suitable for the use of this invention.
  • Formation of the heat insulation layer by thermal spraying can be performed as follows, for example. First, the raw material is melted to form a liquid. This liquid is accelerated and collides with the inner surface of the cavity. Finally, the material that collides with and adheres to the inner surface of the cavity is solidified. By doing so, a very thin heat insulating layer is formed on the inner surface of the mold. The thickness of the heat insulating layer can be adjusted by causing the melted raw material to collide with the very thin heat insulating layer and solidify it. As a method for solidifying the raw material, a conventionally known cooling means may be used, or the raw material may be solidified simply by leaving it to stand.
  • the thermal spraying method is not particularly limited, and a preferable method can be appropriately selected from conventionally known methods such as arc spraying, plasma spraying, and flame spraying.
  • the thermal conductivity of the heat insulating layer made of porous ceramic can be adjusted as appropriate according to the use of the molded product, the type of PAS resin, and the like. In the present invention, it is preferably 2 W / m ⁇ K or less, more preferably 0.3 W / m ⁇ K or more and 2 W / m ⁇ K or less. A thermal conductivity of 2 W / m ⁇ K or less is preferable because an injection-molded product having a high degree of crystallinity tends to be obtained even when an injection-molded product is molded at a mold temperature of 100 ° C. or less.
  • the thermal conductivity is 0.3 W / m ⁇ K or more, the productivity of the injection-molded product is hardly lowered due to the decrease in the strength of the heat insulating layer due to the excessive number of bubbles in the heat insulating layer.
  • the thermal conductivity of the heat insulation layer is 0.7 W / m ⁇ K or more, the decrease in strength of the heat insulation layer due to excessive bubbles in the heat insulation layer tends to be suppressed to a very small range. preferable.
  • the value obtained with the measuring method as described in an Example is employ
  • the thickness of the heat insulating layer is not particularly limited but is preferably 200 ⁇ m or more, more preferably 500 ⁇ m or more and 1000 ⁇ m or less. If it is 500 micrometers or more, it is preferable because the intensity
  • the production method of the present invention uses the above-described PAS resin composition and mold, and performs injection molding under conditions where the mold temperature is equal to or lower than the heat distortion temperature. According to the present invention, since the heat insulating layer is formed on the mold, the crystallinity of the injection molded article can be sufficiently increased even if the injection molded article is manufactured under a mold temperature condition of less than 140 ° C. .
  • the effect of the present invention described above is caused by the fact that the heat of the PAS resin composition that has flowed into the mold is not easily released outside the mold as described above.
  • the heat insulation layer suppresses the release of heat to the outside of the mold, so that the resin composition is crystallized in the mold. A necessary high temperature can be maintained.
  • the PAS resin contained in the PAS resin composition is crystallized by the heat of the PAS resin composition flowing into the mold, if a heat insulating layer is formed on the inner surface of the mold, Even if the mold temperature is adjusted to be equal to or lower than the heat distortion temperature of the PAS resin composition, the crystallinity of the PAS resin can be sufficiently increased. Therefore, the temperature of the mold when releasing the injection-molded product from the mold is also equal to or lower than the above-described heat deformation temperature, and it is possible to suppress deformation and defective release when the injection-molded product is removed from the mold. “The degree of crystallinity can be increased sufficiently” means that the crystallinity of the molded product is set at a mold temperature of 140 ° C.
  • the degree of crystallinity is equal to or higher than the degree of crystallinity of a molded product produced using a mold in which a heat insulating layer is not formed.
  • the injection molded product obtained by the production method of the present invention has a crystallinity (relative crystallinity) of 95 or more as measured by the X-ray diffraction method.
  • the “mold having no heat insulation layer” may be a mold in which a laminate is not formed at all, and an injection molded product is manufactured using the mold, The crystallinity of the injection molded product may be derived and set to 100.
  • the manufacturing method of the present invention it is possible to suppress deformation of the injection molded product and defective mold release when the injection molded product is taken out from the mold. Therefore, even if it is an injection-molded product having a shape that tends to cause deformation and mold release defects, the deformation and mold release defects can be made difficult to occur by employing the manufacturing method of the present invention.
  • the “shape that is likely to cause deformation or mold release failure” is a long shape, for example, a square bar shape, a round bar shape, a cylindrical shape, a rectangular tube shape, a hollow rectangular parallelepiped shape, or a hollow columnar shape. Even if it exists, it is easy to produce a deformation
  • the crystallinity of the PAS resin in the injection-molded product can be sufficiently increased even if the mold temperature is adjusted to 100 ° C. or lower.
  • the following effects can be obtained by adjusting the mold temperature condition to 100 ° C. or lower.
  • the mold temperature is 100 ° C. or less, even if a molten PAS resin composition flows into the mold joint surface or the like, the mold temperature is low, so that it immediately solidifies. For this reason, the generation amount of burrs can be significantly suppressed.
  • the temperature of the mold can be adjusted with water by adjusting the mold temperature to 100 ° C. or less. Therefore, by adjusting the mold temperature to 100 ° C. or less, a molded product having a high crystallinity can be easily obtained.
  • the mold temperature is preferably set to 40 ° C. or higher and 80 ° C. or lower. This is because the amount of burrs can be greatly suppressed while sufficiently increasing the crystallinity of the molded product.
  • PAS resin composition Polyphenylene sulfide resin composition (“Fortron 0220A9”, manufactured by Polyplastics Co., Ltd.), heat deformation temperature of 100 ° C. measured under conditions of a load of 1.8 MPa in accordance with ISO 75-1 and 2 (note that The thermal deformation temperature corresponds to the “deflection temperature under load” in the table)
  • Raw material for heat insulating layer zirconia or polyimide resin
  • Mold 1 for crystallinity measurement
  • Mold 2 for evaluation of releasability
  • a polyimide precursor was applied to the inner surface of the mold and solidified by heating to prepare a mold 1 with a heat insulating layer thickness of 150 ⁇ m.
  • a raw material mainly composed of zirconia was sprayed on the inner surface of the mold by a thermal spraying method.
  • the surface of the heat insulating layer was adjusted so as to increase the density, and a heat insulating layer having a multilayer structure was formed on the inner surface of the mold. Thermal spraying was continued until the thickness of the heat insulating layer reached 500 ⁇ m.
  • the heat insulation layer was formed in the metal mold
  • die used by the comparative example is the same as that of an Example except the heat insulation layer not being formed.
  • the thermal conductivity of the heat insulating layer is measured by the laser flash method, the thermal diffusivity by DSC, the specific heat by DSC, and the specific gravity by water displacement method (based on the JIS Z8807 solid specific gravity measurement method). Rate ⁇ specific heat ⁇ specific gravity].
  • the values of thermal conductivity are shown in Table 1.
  • the thermal conductivity ( ⁇ ) of the heat insulating layer having a multilayer structure is obtained by calculating the thermal conductivity of each of the low density layer and the high density layer, and the thermal conductivity ( ⁇ l) of the low density layer and the thermal conductivity of the high density layer.
  • Example 1 The PAS resin composition was used as a molding material, and an injection molded product was produced using the mold 1 under the following molding conditions. The injection molded product was taken out from the mold by ejection using an eject pin.
  • Example 2 An injection-molded product was produced in the same manner as in Example 1 except that the mold 1 was changed to the mold 2 and the mold temperature condition was changed from 80 ° C. to 90 ° C.
  • the measurement of crystallinity by the X-ray diffraction method was performed using wide-angle X-ray diffraction (reflection method). Specifically, the degree of crystallinity was determined by the Ruland method.
  • the mold 2 was used to evaluate the amount of eject pin (EP) dents and releasability. As an evaluation of the amount of EP indentation, it was confirmed whether or not the injection molded product was indented by ejecting the injection molded product with an eject pin, and the amount of indentation (EP indentation amount) was measured for the indented one. In addition, as for releasability, it was confirmed whether or not it was released from the mold without being deformed at the time of ejection with an eject pin.
  • EP indentation amount the amount of indentation

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une technologie permettant d'augmenter suffisamment le taux de cristallinité d'un article moulé même sans traitement thermique lors de la production d'un article moulé au moyen d'une composition de résine de sulfure de polyarylène présentant une température de déformation thermique inférieure à 140°C utilisée comme matière première. Une composition de résine de sulfure de polyarylène présentant une température de déformation thermique inférieure à 140°C est moulée par injection à une température de moule de métal pouvant atteindre ladite température de déformation thermique au moyen d'un moule de métal comprenant une couche d'isolation thermique formée sur sa surface interne. Il est souhaitable que les conditions de température du moule de métal soient inférieures ou égales à 100°C. Il est également souhaitable d'utiliser un moule de métal produit au moyen d'un procédé selon lequel la couche d'isolation thermique composée de zircone poreuse est formée sur la surface interne du moule de métal par pulvérisation thermique.
PCT/JP2012/054983 2011-03-08 2012-02-28 Procédé de production pour article moulé par injection WO2012121066A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2012800119363A CN103402727A (zh) 2011-03-08 2012-02-28 注塑成型品的制造方法

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Application Number Priority Date Filing Date Title
JP2011-050877 2011-03-08
JP2011050877A JP2012187727A (ja) 2011-03-08 2011-03-08 射出成形品の製造方法

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WO2012121066A1 true WO2012121066A1 (fr) 2012-09-13

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CN (1) CN103402727A (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3020304A1 (fr) * 2014-04-28 2015-10-30 Valeo Systemes Thermiques Procede d'isolation thermique d'un moule metallique pour moulage de matiere plastique

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Publication number Priority date Publication date Assignee Title
JP6085450B2 (ja) * 2012-10-31 2017-02-22 ポリプラスチックス株式会社 入れ子の製造方法
CN111319199A (zh) * 2020-03-06 2020-06-23 盐城摩因宝新材料有限公司 一种冷循环易脱模注塑模具及其制作工艺
CN117067451B (zh) * 2023-10-16 2024-04-09 歌尔股份有限公司 模具、热塑性复合材料及其加工方法、电子设备

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JPH0391563A (ja) * 1989-09-05 1991-04-17 Nippon G Ii Plast Kk ポリフェニレンサルファイド系樹脂組成物
JPH04209654A (ja) * 1990-12-07 1992-07-31 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィド樹脂組成物
JP2006062369A (ja) * 1997-05-28 2006-03-09 Mitsubishi Engineering Plastics Corp 熱可塑性樹脂成形用の金型組立体及び成形品の製造方法
JP2009274352A (ja) * 2008-05-15 2009-11-26 Mitsubishi Engineering Plastics Corp 金型組立体、射出成形方法、及び、成形品

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Publication number Priority date Publication date Assignee Title
JPH0391563A (ja) * 1989-09-05 1991-04-17 Nippon G Ii Plast Kk ポリフェニレンサルファイド系樹脂組成物
JPH04209654A (ja) * 1990-12-07 1992-07-31 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィド樹脂組成物
JP2006062369A (ja) * 1997-05-28 2006-03-09 Mitsubishi Engineering Plastics Corp 熱可塑性樹脂成形用の金型組立体及び成形品の製造方法
JP2009274352A (ja) * 2008-05-15 2009-11-26 Mitsubishi Engineering Plastics Corp 金型組立体、射出成形方法、及び、成形品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3020304A1 (fr) * 2014-04-28 2015-10-30 Valeo Systemes Thermiques Procede d'isolation thermique d'un moule metallique pour moulage de matiere plastique

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TW201302426A (zh) 2013-01-16
CN103402727A (zh) 2013-11-20

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