WO1997023563A1 - Composition de resine polyacetal - Google Patents

Composition de resine polyacetal Download PDF

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Publication number
WO1997023563A1
WO1997023563A1 PCT/JP1996/003688 JP9603688W WO9723563A1 WO 1997023563 A1 WO1997023563 A1 WO 1997023563A1 JP 9603688 W JP9603688 W JP 9603688W WO 9723563 A1 WO9723563 A1 WO 9723563A1
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WO
WIPO (PCT)
Prior art keywords
polyacetal resin
polymer
core
resin composition
shell
Prior art date
Application number
PCT/JP1996/003688
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English (en)
Japanese (ja)
Inventor
Yasuyuki Fukute
Original Assignee
Polyplastics Co., 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 Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Publication of WO1997023563A1 publication Critical patent/WO1997023563A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention provides a method for attaching and locking a mating material to an article or part in an automobile or the like by utilizing elastic repulsion while maintaining the mechanical properties, friction and wear properties, moldability, and the like inherently possessed by the polyacetal resin.
  • An object of the present invention is to provide a polyacetal resin composition which can be suitably used for a hinge which is a thin portion to which a clip or a part of a part is subjected to bending or bending load more than once.
  • polyacetal resin is used in an extremely wide range of fields as an engineering resin having excellent physical properties such as mechanical properties and electrical properties, or chemical properties such as chemical resistance and heat resistance. I have. In recent years, with the expansion of fields in which polyacetal resins are used, there may be cases where special properties are required for the materials.
  • Polyamide resins and polyacetal resins are used as clip plastic materials for attaching and locking articles or parts to mating materials using elastic repulsion in automobiles and other equipment and appliances. It is widely used. Polyamide resin materials are excellent in flexibility and impact resistance, and also excellent in clipping properties, making them suitable as clip materials.However, moisture absorption easily changes flexibility and impact resistance. However, it is necessary to pay attention to the environmental conditions (temperature, humidity, etc.) at the time of clip mounting, and the poor assembly workability poses a practical problem. On the other hand, those made of polyacetal resin have little change in physical properties such as impact resistance due to moisture absorption, but have the problem that the crib characteristics are inferior to those made of boriamid resin. Was.
  • a composition containing a thermoplastic polyurethane for the purpose of improving impact resistance is used, and although it has some desirable properties in terms of impact resistance, it is molded. Separation phenomenon of the polyacetal resin and thermoplastic polyurethane occurs on the surface of the product, causing a problem that the appearance of the molded product is remarkably impaired.Also, the thermal stability is reduced, and the strong elongation of the molded part is extremely low. Therefore, there are various problems such as a decrease in the degree of freedom in clip design, and improvements have been required.
  • the present invention provides a polyacetal resin composition having more excellent clip characteristics and hinge characteristics without impairing other physical properties, and a polyacetal resin clip part obtained by molding the composition. A hinge part is provided.
  • the present inventors have solved the above-mentioned problems without sacrificing the original properties of the polyacetal resin as much as possible, and have satisfied all the performances required as a resin composition for clips or a resin composition for hinges.
  • the polyacetal resin composition of the present invention has a stable clip characteristic and high fluidity against environmental changes, a preferable clip insertion force, heat resistance during injection molding, and heat resistance, which have been difficult with the prior art. Since impact and good hinge properties can be achieved, it is a very suitable material as both a clip material and a hinge material.
  • the polyacetal resin composition of the present invention which is obtained by adding and blending a core-shell polymer and a polyethylene resin in combination with a polyacetal resin, has a well-balanced mechanical property of the polyacetal. While maintaining the properties, it exhibited excellent effects of maintaining excellent clip characteristics, fluidity, and hinge characteristics, and maintaining toughness and heat stability.
  • Examples of applications of parts obtained by molding such a polyacetal resin composition include various parts in the fields of automobiles, electricity, electronics, building materials, miscellaneous goods, and the like. It is preferably used.
  • the (A) polyacetal resin used in the present invention is a polymer compound having oxymethylene groups (-CH2O-) as main structural units, and is a polyoxymethylene homopolymer, a copolymer having a small amount of other structural units in addition to oxymethylene groups.
  • the polymer may be any one of a copolymer, a block copolymer, and a molecule having not only a linear but also a branched or crosslinked structure.
  • the core-shell polymer (B) used in the present invention is a compound having a rubber-like polymer core and a glass-like polymer shell, and can be prepared by a known method. Commercial products can also be used.
  • a typical example is the mouth —Mach Haas Acryloids KM330 and KM653; Kureha Chemical Co., Ltd. Paraloid CA-102 and KCA-301; Takeda Pharmaceutical Co., Ltd. Staphyloids P0-0270 and PO-0148; Kaneace FM of Chemical Industry Co., Ltd .; and Metaprene C-102, E-901, W-800, S-2001 of Mitsubishi Rayon Co., Ltd.
  • a core-shell polymer having a rubber-like polymer core and a glass-like polymer shell containing methyl methacrylate as a main component is preferred.
  • a core shell polymer in which anion is detected decomposition of polyacetal may be promoted during melt-kneading or injection molding, and a desired clip characteristic may not be obtained.
  • the core-shell polymer in which anion is not substantially detected means a core-shell polymer in which anion is not detected in a usual qualitative test of anion.
  • a sample core-shell polymer
  • 20 ml of ion-exchanged water is added, the mixture is stirred for 3 hours with a magnetic stirrer, and then with No. 5C filter paper.
  • the filtered filtrate was divided into two parts, and 0.5 tnl of a 1% barium chloride aqueous solution was added to one of the two parts.
  • a method of comparing and observing the occurrence of turbidity (qualitative test of sulfate ion) or the same treatment was performed.
  • 0.1 N silver nitrate aqueous solution is added, and the presence of anion can be confirmed by a method of comparing the generation of turbidity (qualitative test of halogen ions).
  • a core shell polymer in which these aons are not present at all is suitably used.
  • a core-shell polymer that is preferable for use in the present invention is obtained by emulsion polymerization using a nonionic surfactant and a polymerization initiator in which a generated radical is neutral.
  • a core-shell polymer can be produced, for example, by using an emulsion polymerization technique described in JP-A-3-14856.
  • Emulsion polymerization can be carried out using, for example, the following surfactant and polymerization initiator.
  • nonionic surfactants include ethers such as polyoxyethylene nouryl ether, polyoxyethylene stearyl ether, and polyoxyethylene lauryl ether, and esters such as polyoxyethylene monostearate.
  • sorbitan ester type such as polyoxyethylene sorbitan monolaurate
  • block polymer type such as polyoxyethylenepolypropylene propylene block copolymer
  • the addition amount is appropriately selected according to the particle stabilizing ability of the surfactant.
  • Azo-based polymerization initiators such as dihydrochloride, peroxide-based polymerization initiators such as cumenehydroxide peroxyde, diisopropylbenzene hydroxoxide, and hydrogen peroxide are used alone or in combination of two or more. Are used in combination.
  • a core-shell polymer that contains substantially no anion or contains a very small amount of anion is contained. can get.
  • a polyacetal resin composition using such a core-shell polymer that does not substantially contain anion has excellent clip characteristics and hinge characteristics.
  • the core-shell polymer (B) used in the present invention has a rubber-like polymer core and a glass-like polymer shell.
  • the polymer in the former stage is usually used in the latter stage.
  • the three- core shell polymer obtained by the continuous multi-stage emulsion polymerization method in which the polymer of the present invention is successively coated has an intermediate phase described below, the polymer of the previous stage is put into the polymer of the previous stage. In some cases, an intermediate phase is formed by a multi-stage emulsification polymerization method in which water enters.
  • the polymerization of the first stage is a monomer constituting the three rubbery polymer is a reaction to form a rubbery polymer, such as alkyl ⁇ chestnut rates or their number of carbon atoms of the conjugated diene or an alkyl group is 2-8 And the like.
  • a rubbery polymer such as alkyl ⁇ chestnut rates or their number of carbon atoms of the conjugated diene or an alkyl group is 2-8 And the like.
  • These monomers are polymerized to form a rubbery polymer having a glass transition temperature of preferably 30 ° C or lower. Examples of such a conjugated diene include butadiene, isoprene, and chloroprene.
  • alkyl acrylate having an alkyl group having 2 to 8 carbon atoms examples include, for example, ethyl acrylate, propynole acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and the like. Can be mentioned. In particular, butyl acrylate is preferably used as the rubber-like polymer. 3 In the first stage of polymerization, copolymerizable monomers such as conjugated gens and alkyl acrylates, for example, aromatic compounds such as styrene, vinyl toluene and ⁇ -methylstyrene are used.
  • vinyl aromatic It is also possible to copolymerize vinyl cyanide such as vinylidene, acrylonitrile and methacrylonitrile, and alkyl methacrylate such as vinylidene cyanide, methyl methacrylate and butyl methacrylate.
  • vinyl cyanide such as vinylidene, acrylonitrile and methacrylonitrile
  • alkyl methacrylate such as vinylidene cyanide, methyl methacrylate and butyl methacrylate.
  • the total amount of all monomers in the first-stage is 20 wt.
  • the ratio is not more than / 0 , a polymer having high impact resistance can be obtained by using a small amount of a crosslinking monomer and a grafting monomer.
  • the cross-linkable monomer include aromatic divinyl monomer such as divinylbenzene, ethylene glycol resin acrylate, ethylene glycol resin methacrylate, butylene glycol monoacrylate, and hexanediol diacrylate.
  • Hexanediol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethyl methacrylate / repropane diacrylate, trimethylolpropane dimethacrylate, Bok Rimechirorupu Lono, 3 down Toriaku Li rate there may be mentioned a preparative trimethylolpropane Torimetaku Li rate such alkanes polyol poly Accession Li rate or alkane polio one Ruporimetaku re, single bets, etc., especially Buchirenguri co one Le ⁇ click Li rate, hexane Jiorujiaku Re, single Bok is preferably used to.
  • daraftized monomer examples include, for example, unsaturated carboxylic acid aryl esters such as diaryl acrylate, aryl methacrylate, diaryl maleate, diaryl fumarate, and diaryl itaconate. Among them, aryl methacrylate is particularly preferably used.
  • Such a crosslinkable monomer and a grafting monomer each occupy 0 to 5 weight of the total monomer amount in the first stage. / 0 , preferably in the range of 0.1 to 2% by weight.
  • the core of this rubbery polymer weighs 50-90 of the core-shell polymer. /. Is preferred. When the weight of the core is less than this range or more than this range, the effect of improving the impact resistance of the resin composition obtained by melt-mixing the produced core shell polymer may not be sufficient. If the glass transition temperature of the core is higher than 130 ° C, the effect of improving the low-temperature impact resistance may not be sufficient.
  • the outermost shell layer (shell phase) is formed of a glassy polymer.
  • the monomer constituting the glassy polymer is methyl methacrylate, a mixture of monomers copolymerizable with methyl methacrylate, and a glassy polymer having a glass transition temperature of 60 ° C or higher.
  • monomers copolymerizable with the acrylate include, for example, ethyl methacrylate.
  • Alkyl methacrylate such as acrylate, butyl methacrylate, etc., alkyl acrylate such as ethyl acrylate, butyl acrylate, styrene, vinyl toluene, ⁇ -methyl styrene, etc., aromatic vinyl, aromatic vinylidene, Examples thereof include vinyl cyanide such as acrylonitrile and methacrylonitrile, and vinyl polymerizable monomers such as vinylidene cyanide.Ethyl acrylate, styrene, and acrylonitrile are particularly preferable. Are used.
  • the outermost shell layer (shell phase) is Koashi Eruporima one entire 10-50 wt 0 /. Is preferable.
  • an intermediate phase may exist between the first stage and the final polymerization phase.
  • a polymerizable monomer having a functional group such as glycidyl methacrylate, methacrylic acid, or hydroxyshethyl methacrylate
  • a polymerizable monomer such as methyl methacrylate that forms a glassy polymer
  • An intermediate phase is formed by side emulsion polymerization of a polymerization monomer or the like that forms a rubbery polymer such as a rate.
  • Such an intermediate phase can be selected variously depending on the desired properties of the core-shell polymer. Further, the polymerization ratio may be appropriately selected depending on the monomer used. For example, when a glassy polymer is used as the intermediate layer, its polymerization ratio may be calculated as a part of the shell, and when it is a rubbery polymer, it may be calculated as a part of the core.
  • the structure of the core seal polymer having such an intermediate phase is, for example, a multi-layer structure in which another layer exists between the core and the shell, or a structure in which the intermediate phase becomes fine particles in the core.
  • Those having a dispersed salami structure can be mentioned.
  • the mesophase to be dispersed may form a new core in the center of the core.
  • a core seal polymer having such a structure may occur when a monomer represented by styrene is used as a monomer constituting the intermediate phase.
  • the amount of the core-shell polymer (II) of the present invention relative to the total composition is 3 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 5 to 30% by weight. If the amount of the core-shell polymer is too small, the necessary clip properties and hinge properties cannot be obtained, and even if added unnecessarily, mechanical properties, particularly rigidity, are greatly reduced.
  • the present invention is characterized in that a polyethylene resin (C) is further added to the above components (A) and (B), and the three components (A), (B) and (C) are added.
  • the above-mentioned problems can be overcome without deteriorating the balanced properties inherent in the polyacetal resin by blending the polyacetal resin. It has been found that the material is effective for improving the clip insertion force and that the material has good hinge characteristics, so that it is possible to provide a preferable material for clip and hinge.
  • the (0 polyethylene-based resin used for such purposes an ethylene homopolymer such, or ethylene and professional propylene, butene one 1, 4 - polymethylpentene one 1, hexene one 1, Okuten one 1, nonene-11, decene-11, dodecene-11, etc., and copolymers with ⁇ -olefins, butyl esters, unsaturated carboxylic acids, unsaturated carboxylic esters, etc.
  • Examples include low-density polyethylene, medium- to low-pressure method high-density, medium- and low-density polyethylene, ethylene-propylene copolymer, ethylene-butyl acetate copolymer, ethylene-acrylate copolymer, and the like.
  • the copolymer may be one or more selected from the group consisting of resins modified with functional groups such as groups, etc.
  • the copolymer is a random copolymer, a block copolymer, or a graft. Copolymers and mixtures thereof are also meant.
  • Polyethylene resin has its melt index strength; ASTM D1238 (J IS IS67 As a value measured according to 60), a value of 1.0 to 250 gZ i0 min is preferable :: In particular, a value of 5.0 to i 50 g / 10 min is preferable:
  • the ethylene-acrylate copolymer is an ester with an alcohol selected from the alcohol components alkyl alcohol and arylanol, and preferably has 1 to 4 carbon atoms.
  • an alcohol having atoms include Mechinoreanoreko - Honoré, E Ji / Reanorekonore, n- Purohi Reanoreko one deviation, i - Pro Pino Les alcohol, n - Buchinoreanoreko - le, 1 - Petit / Rearukonore, t Buchinorea alcohol, Are typical. All alcohol components in the molecule may be the same, some alcohols may be different alcohols, and some may be vinyl groups or hydroxyl groups.
  • an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer are preferred.
  • the weight ratio of ethylene to acrylate is preferably in the range of 1:10 to 10: 1, particularly preferably in the range of ⁇ : 5 to 5: 1.
  • the number average molecular weight of the ethylene-acrylate copolymer is preferably in the range of 1500 to 8000. When the number average molecular weight exceeds 8000, the effect of improving the fluidity is small, and when the number average molecular weight is less than 00, the solvent resistance and the mechanical strength decrease are not suitable.
  • the amount of the polyethylene resin is 1 to 10% by weight based on the total composition. / o is appropriate, especially 2 to 8 weight.
  • the preferred weight is 1. When the amount is less than / 0 , the effect of improving clip characteristics and hinge characteristics is small, and the weight is 10%. /. If the amount is larger, the improvement effect reaches saturation, which may adversely affect the inherent properties of the polyacetal resin, and is inappropriate because the surface of the molded product may be peeled off.
  • composition of the present invention may further include various known stabilizers to enhance thermal stability.
  • various known stabilizers to enhance thermal stability.
  • additives such as a lubricant, a nucleating agent, a release agent, an antistatic agent and other surfactants, or components other than the component (C)
  • a lubricant such as a lubricant, a nucleating agent, a release agent, an antistatic agent and other surfactants, or components other than the component (C)
  • the composition of the present invention can be prepared by equipment and a method generally known as a method for preparing a synthetic resin composition. That is, the necessary components are mixed, kneaded using a single-screw or twin-screw extruder, extruded to form a pellet, and then molded, and the composition is prepared by a molding machine. It is also possible to carry out simultaneously with molding. In addition, in order to improve the dispersion and mixing of each component, a method in which a part or the whole of the resin component is pulverized, mixed, and melt-extruded to form a bellet can be used.
  • the compounds such as the stabilizers and additives may be added at any arbitrary stage, and may be added or mixed immediately before obtaining a final molded article.
  • the resin composition according to the present invention can be molded by any of extrusion molding, injection molding, compression molding, vacuum molding, blow molding, and foam molding, but generally, the crib is molded by injection molding. Is done.
  • FIG. 1 is a view showing the shape of a clip test piece used for evaluating the clip characteristics.
  • FIG. 2 is a diagram showing an actual test situation of the evaluation of the clip characteristics.
  • FIG. 3 is a diagram showing an actual test situation of the evaluation of the clip input.
  • Fig. 4 is a schematic diagram of the test piece used for the hinge characteristic measurement, and (a), (b), and (c) show a plan view, a side view, and an enlarged view of the hinge portion, respectively.
  • the other unit of the numerical value is sleep.
  • a clip having the shape shown in Fig. 1 was prepared as follows. Then, as shown in Fig. 2, place it on a jig with a diameter of 7.0mni (at room temperature of 23 ° C and 50% RH) and a hole of 7.5 dragon (at -10 ° C) with a diameter of 7.0mni. A drop of lkg was dropped from a height of 3icm directly above it, and the clip was hammered into the hole. The number of sample breaks in the test samples (25) was examined, and it was determined that the smaller the number of breaks, the better the clip characteristics.
  • Cylinder temperature (° C) 200 190 180 160
  • the clip insertion force test uses a clip formed in the same manner as the above-mentioned clip characteristic test, and as shown in Fig. 3, a 8.6 mm thick SUS416 sheet metallurgy with an 8.3 mm diameter hole is drilled.
  • the test pieces were placed under the conditions of room temperature 23 ° C and 50% RH according to the test method specified in K7211-1976.
  • the completion of the insertion of the test sample into the sheet metal jig is determined by whether or not all the flanges of the clip are in contact with the sheet metal jig.
  • the weight of the weight and the drop height at which the clip is completely inserted are determined. From this, the clipping input energy was determined. It was determined that the lower the clip insertion force energy, the better.
  • Cylinder temperature (.C) 200 190 180 160
  • test sample (a rectangular parallelepiped having a width of 12.7, a thickness of 6.4 mm and a length of 64 mm) was molded using an inline injection molding machine under the following conditions. A notch according to the above method was attached, and the Izod impact value was measured. The higher the Izod impact value, the better.
  • Cylinder temperature (° c) 200 190 180 160
  • Cylinder temperature (C) 200 190 180 160
  • Evaluation B The state of the hinge portion after bending 100 times was evaluated according to the following criterion and expressed as an average point (the larger the value, the better). 5: Almost no abnormality was recognized
  • a cellophane tape was adhered to the surface of the 1 32 inch test piece, peeled off, and the peeling state was visually observed to evaluate the presence or absence of a surface layer peeling state.
  • Polyacetal resin ( ⁇ ) (Polyplastics Co., Ltd., Zyuracon (trade name)) is blended with core-shell polymer B_1 and polyethylene resin C-11 in the composition shown in Tables 1 and 2, and Henschel mixer is used. After mixing, the mixture was melt-kneaded using a 30-mni twin-screw extruder to prepare a pellet-shaped composition, and then a test piece was formed from this pellet using an injection molding machine under the above-described molding conditions. Tables 1 and 2 show the results of measuring and evaluating each characteristic.
  • A-1 melt index (190.C) 2.5 (g / lOmin)
  • NUC copolymer one (trade name) NUC6570 Echiruaku Li rate 25 0/0 denatured
  • NUC copolymer brand name
  • HIZEX 5100B (trade name) C-1 polypropylene resin manufactured by Mitsui Petrochemical Industries, Ltd.
  • Eras Toranichi S80A (trade name) manufactured by Takeda Baichi Deshuretan Industry Co., Ltd.
  • Weight% 5 5 5 5 5 5 5 2 8 3 Clip characteristics / 23 ° C pieces 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

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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)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition de résine polyacétal utilisable pour réaliser des dispositifs de fixation et des charnières de qualité, ayant une fluidité améliorée, tout en conservant les propriétés mécaniques et des propriétés de moulage, de durété, etc. du polyacétal. La composition comprend (A) entre 96 et 40 % en poids de résine polyacétal (basé sur toute la composition, comme pour les autres pourcentages), (B) de 3 à 50 % en poids de polymère noyau/coque ayant le noyau fait en un polymère du type caoutchouc et la coque faite en un polymère vitreux, et (C) de 1 à 10 % en poids d'une résine polyéthylène.
PCT/JP1996/003688 1995-12-25 1996-12-18 Composition de resine polyacetal WO1997023563A1 (fr)

Applications Claiming Priority (2)

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JP7/336604 1995-12-25
JP33660495A JP3281242B2 (ja) 1995-12-25 1995-12-25 ポリアセタール樹脂組成物

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WO1997023563A1 true WO1997023563A1 (fr) 1997-07-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2817302A1 (fr) * 2000-11-28 2002-05-31 Neyr Plastiques Holding Dispositif de fixation d'un accessoire sur un vehicule

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4563004B2 (ja) * 2003-07-08 2010-10-13 ポリプラスチックス株式会社 ポリアセタール樹脂製摺動部品
JP4680523B2 (ja) * 2004-03-05 2011-05-11 三菱レイヨン株式会社 熱可塑性樹脂組成物
JP4680522B2 (ja) * 2004-03-05 2011-05-11 三菱レイヨン株式会社 熱可塑性樹脂組成物およびその製造方法
JP5248029B2 (ja) * 2007-03-27 2013-07-31 三菱レイヨン株式会社 グラフト共重合体及び樹脂組成物

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62223267A (ja) * 1986-03-07 1987-10-01 Polyplastics Co ヒンジ部品
JPH01256564A (ja) * 1988-04-06 1989-10-13 Nippon Petrochem Co Ltd 熱可塑性樹脂組成物およびその製造方法
JPH01271453A (ja) * 1988-04-22 1989-10-30 Nippon Petrochem Co Ltd 熱可塑性樹脂組成物およびその製造方法
JPH04120159A (ja) * 1989-12-22 1992-04-21 Nippon Oil & Fats Co Ltd 　熱可塑性樹脂組成物の製造方法
JPH04136061A (ja) * 1990-09-26 1992-05-11 Polyplastics Co 熱可塑性相互侵入網目構造体及びその形成法
JPH04252232A (ja) * 1991-01-28 1992-09-08 Polyplastics Co ポリアセタール樹脂組成物構造体及びその製造法
JPH06100759A (ja) * 1992-09-16 1994-04-12 Polyplastics Co クリップ用樹脂組成物
JPH06240104A (ja) * 1992-04-04 1994-08-30 Mitsubishi Gas Chem Co Inc 耐衝撃性ポリアセタール組成物
JPH08231824A (ja) * 1995-02-27 1996-09-10 Asahi Chem Ind Co Ltd 摺動性ポリアセタール樹脂組成物
JPH08325432A (ja) * 1995-05-30 1996-12-10 Polyplastics Co ポリアセタール樹脂組成物
JPH08325431A (ja) * 1995-05-30 1996-12-10 Polyplastics Co ポリアセタール樹脂製ヒンジ部品

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62223267A (ja) * 1986-03-07 1987-10-01 Polyplastics Co ヒンジ部品
JPH01256564A (ja) * 1988-04-06 1989-10-13 Nippon Petrochem Co Ltd 熱可塑性樹脂組成物およびその製造方法
JPH01271453A (ja) * 1988-04-22 1989-10-30 Nippon Petrochem Co Ltd 熱可塑性樹脂組成物およびその製造方法
JPH04120159A (ja) * 1989-12-22 1992-04-21 Nippon Oil & Fats Co Ltd 　熱可塑性樹脂組成物の製造方法
JPH04136061A (ja) * 1990-09-26 1992-05-11 Polyplastics Co 熱可塑性相互侵入網目構造体及びその形成法
JPH04252232A (ja) * 1991-01-28 1992-09-08 Polyplastics Co ポリアセタール樹脂組成物構造体及びその製造法
JPH06240104A (ja) * 1992-04-04 1994-08-30 Mitsubishi Gas Chem Co Inc 耐衝撃性ポリアセタール組成物
JPH06100759A (ja) * 1992-09-16 1994-04-12 Polyplastics Co クリップ用樹脂組成物
JPH08231824A (ja) * 1995-02-27 1996-09-10 Asahi Chem Ind Co Ltd 摺動性ポリアセタール樹脂組成物
JPH08325432A (ja) * 1995-05-30 1996-12-10 Polyplastics Co ポリアセタール樹脂組成物
JPH08325431A (ja) * 1995-05-30 1996-12-10 Polyplastics Co ポリアセタール樹脂製ヒンジ部品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2817302A1 (fr) * 2000-11-28 2002-05-31 Neyr Plastiques Holding Dispositif de fixation d'un accessoire sur un vehicule

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JP3281242B2 (ja) 2002-05-13
JPH09176444A (ja) 1997-07-08

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