WO2010041327A1 - Composition de résine de polyamide et article moulé - Google Patents

Composition de résine de polyamide et article moulé Download PDF

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Publication number
WO2010041327A1
WO2010041327A1 PCT/JP2008/068417 JP2008068417W WO2010041327A1 WO 2010041327 A1 WO2010041327 A1 WO 2010041327A1 JP 2008068417 W JP2008068417 W JP 2008068417W WO 2010041327 A1 WO2010041327 A1 WO 2010041327A1
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Prior art keywords
polyamide resin
resin composition
mass
component
parts
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PCT/JP2008/068417
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English (en)
Japanese (ja)
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伸吾 久我
洋 小山田
哲生 伊勢谷
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旭化成ケミカルズ株式会社
パナソニック株式会社
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Priority to PCT/JP2008/068417 priority Critical patent/WO2010041327A1/fr
Publication of WO2010041327A1 publication Critical patent/WO2010041327A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K3/34—Silicon-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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds

Definitions

  • the present invention relates to a polyamide resin composition and a molded product.
  • polyamide resins are widely used in various parts such as automobile parts, electronic / electric parts, and industrial machine parts because they are excellent in various characteristics including mechanical characteristics, such as molding processability.
  • polyamide resins have been required to have various properties that have not been conventionally required.
  • one of the specifications required for polyamide resins is a specification that is excellent in chemical resistance such as alkali resistance and calcium chloride resistance. More specifically, the molded product obtained from the polyamide resin has a mechanical strength equivalent to or higher than that of the conventional one, and there is little decrease in mechanical strength due to the chemical in an environment where the molded product is excessively in contact with the chemical. There is a demand for a polyamide resin composition that is less affected by mechanical strength and appearance due to moisture in the atmosphere and moisture in the atmosphere.
  • An object of the present invention is to provide a polyamide resin composition and a molded product thereof that are sufficiently small and sufficiently small in mechanical strength and appearance due to chemicals, moisture in the chemicals and moisture in the atmosphere.
  • a polyamide resin composition containing (A) a polyamide resin comprising polyhexamethylene sebacamide and / or polyhexamethylene dodecamide, (B) boron nitride, and (C) calcined kaolin.
  • a polyamide resin composition containing 0.0001 to 3 parts by mass of component (B) and 0.01 to 20 parts by mass of component (C) with respect to 100 parts by mass of component (A).
  • Composition Composition.
  • the polyamide resin composition according to [1] or [2], wherein (D) the polyamide resin different from the component (A) is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
  • the obtained molded article has a mechanical strength equivalent to or higher than that of the conventional one, and in an environment where the molded product is excessively contacted with the chemical, the decrease in mechanical strength due to the chemical is sufficiently small. It is possible to provide a polyamide resin composition that is sufficiently small in mechanical strength and appearance change due to moisture in the chemical and moisture in the atmosphere.
  • SYMBOLS 1 Battery gasket, 2 ... Positive electrode, 3 ... Gel-like negative electrode, 4 ... Separator, 5 ... Battery case, 6 ... Negative electrode collector, 7 ... Negative electrode terminal board, 8 ... Exterior label, 9 ... Sealing unit, 10 ... Alkaline battery, 20 ... mold, 28 ... molded product.
  • the present embodiment will be described in detail with reference to the drawings as necessary.
  • the same elements are denoted by the same reference numerals, and redundant description is omitted.
  • the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified.
  • the dimensional ratios in the drawings are not limited to the illustrated ratios.
  • the polyamide resin composition of this embodiment contains (A) a polyamide resin composed of polyhexamethylene sebacamide and / or polyhexamethylene dodecamide, (B) boron nitride, and (C) calcined kaolin. It is.
  • A a polyamide resin composed of polyhexamethylene sebacamide and / or polyhexamethylene dodecamide
  • B boron nitride
  • C calcined kaolin
  • the component (A) is a polyamide resin composed of polyhexamethylene sebacamide and / or polyhexamethylene dodecamide.
  • Polyhexamethylene sebacamide is also referred to as “polyamide 610”
  • polyhexamethylene dodecamide is also referred to as “polyamide 612”.
  • the component (A) preferably contains at least polyhexamethylene dodecamide, and more preferably consists of polyhexamethylene dodecamide. Thereby, the change of the mechanical strength and external appearance by a chemical
  • the degree of polymerization of the polyamide resin as component (A) is preferably such that the relative viscosity at 25 ° C. is 1.8 to 3.8, more preferably 1.9 to 3.5. More preferably, the degree of polymerization is 2.0 to 3.3.
  • the “relative viscosity” is measured using an Ostwald viscometer in a 98% concentrated sulfuric acid solution containing 1% by mass of a polyamide resin.
  • the boron nitride component (B) is represented by the chemical formula “BN”. This boron nitride is obtained by heating boron at a high temperature in a nitrogen stream, heating ammonia and boron oxide, or heating ammonium chloride and borax. The boron nitride thus obtained is a fine powder.
  • the powder average particle size of boron nitride is preferably 10 ⁇ m or less, and more preferably 0.1 to 10 ⁇ m.
  • “powder average particle size” means the particle size distribution of powder measured using a commercially available particle size distribution measuring device (for example, a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation, trade name “SALD-2200”).
  • D50 a particle size
  • the object of the present invention can be achieved more reliably and effectively, and productivity can be improved by improving moldability.
  • the polyamide resin composition of the present embodiment contains a change in mechanical strength due to moisture in the medicine or in the medicine or in the atmosphere when in contact with the medicine, particularly impact strength. Can be suppressed. Such a suppression effect can be clearly recognized when compared with the case where the polyamide resin composition contains a crystal nucleating agent different from boron nitride.
  • (B) component has the effect
  • the calcined kaolin as the component (C) is metakaolin (Al 2 O 3 .2SiO 2 ) obtained by calcining kaolinite and dehydrating, and is amorphous in terms of X-rays.
  • the shape of the calcined kaolin is not particularly limited, but is preferably a non-fibrous shape such as a plate shape, a rod shape, or a spherical shape.
  • the average particle diameter of the calcined kaolin is preferably 0.05 to 10 ⁇ m from the viewpoint of more effectively achieving the object of the present invention.
  • the calcined kaolin can be obtained by obtaining a commercially available product, by synthesizing by a conventional method, or by obtaining commercially available kaolinite and dehydrating it by a conventional method.
  • the calcined kaolin as the component (C) preferably contains calcined kaolin surface-treated with a silane coupling agent from the viewpoint of more effectively achieving the object of the present invention.
  • silane coupling agent examples include organic silane compounds, and more specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl).
  • Epoxy group-containing alkoxysilane compounds typified by ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds typified by 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, Ureido group-containing alkoxysilane compounds represented by 3-ureidopropyltrimethoxysilane, 3- (2-ureidoethyl) aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopro Rutrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldimethoxysilane, 3-isocyanatopropylethyldiethoxys
  • silane coupling agents in particular, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) ) Aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-aminotrimethoxysilane, ⁇ -aminotriethoxysilane, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are preferably used.
  • a silane coupling agent is used alone or in combination of two or more.
  • the composition ratio of the above components is not particularly limited as long as it does not impair the object of the present invention, but is preferably as follows. That is, the polyamide resin composition of the present embodiment has a content of 0.0001 to 3 parts by weight of component (B) with respect to 100 parts by weight of component (A), from the viewpoint of more reliably and effectively achieving the object of the present invention. It is preferably contained in an amount of 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass.
  • the polyamide resin composition of the present embodiment is used from the viewpoint of further suppressing the change in strength due to chemicals, moisture in the chemical, moisture in the atmosphere, particularly the change in impact strength, and further improving the leakage resistance of the battery.
  • the component (C) is preferably contained in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and further preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). preferable.
  • the polyamide resin composition of the present embodiment preferably contains 100 to 20000 parts by mass of the component (C) with respect to 100 parts by mass of the component (B).
  • the content is more preferably 500 to 18000 parts by mass, and even more preferably 1000 to 15000 parts by mass.
  • the polyamide resin composition of the present embodiment may further contain a polyamide resin that is different from the component (A) as long as the object of the present invention is not impaired. Thereby, the effect that crystallinity can be improved or heat resistance can be improved is obtained.
  • polyamide resin for example, polyhexamethylene adipamide (polyamide 66), poly ⁇ capramide (polyamide 6), a copolymer of polyhexamethylene adipamide and polyisophthalamide (polyamide 6I), Examples thereof include a copolymer of polyhexamethylene adipamide and polyterephthalamide (polyamide 6T), and a terpolymer of polyhexamethylene adipamide, polyisophthalamide and polyterephthalamide.
  • polyamide resins are used alone or in combination of two or more.
  • the content is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). By adjusting the content ratio within this numerical range, the chemical resistance, mechanical properties, and heat resistance are excellent in balance, and the effect of improving moldability tends to be obtained.
  • the degree of polymerization of the different type of polyamide resin as component (D) is preferably such that the relative viscosity at 25 ° C. is 1.8 to 3.8, and the degree of polymerization is 1.9 to 3.5. More preferably, the degree of polymerization is 2.0 to 3.3. Further, the relative viscosity at 25 ° C. of the mixture of the component (A) and a polyamide resin different from this is preferably 1.8 to 3.8, more preferably 1.9 to 3.5. More preferably, it is 0.0 to 3.3. As a result, the polyamide resin composition of the present embodiment is further excellent in moldability and mechanical strength.
  • the polyamide resin composition of the present embodiment includes, in addition to the above-described components, inorganic fillers, flame retardants, and pigments contained in ordinary polyamide resin compositions, as long as they do not impair the purpose of the present invention. Or a colorant. Furthermore, the polyamide resin composition of the present embodiment may be added with various additives such as a moldability improver, a heat stabilizer, a light stabilizer, an antioxidant, and an antistatic agent in any stage within a range not impairing the object of the present invention. May be added. These are used singly or in combination of two or more.
  • the polyamide resin composition of the present embodiment may contain a polymer other than the above-described polyamide resin as long as it does not hinder the object of the present invention.
  • a polymer include polypropylene, ABS resin, polyphenylene oxide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, liquid crystal polyester, and various elastomers. These are used singly or in combination of two or more.
  • the polyamide resin composition of the present embodiment can be produced by the same method as the conventional polyamide resin composition.
  • the boron nitride of component (B) when mixing the boron nitride of component (B) with the polyamide resin of component (A), it may be added to the raw material of component (A) during the synthesis of component (A), or during melt kneading of component (A) It may be added.
  • the component (A) may be blended and added to the pellet surface after the component (A) is formed into a pellet, or the component (B) may be added as a high-concentration master batch.
  • the calcined kaolin of the component (C) may be added to the raw material of the component (A) at the time of synthesis of the component (A), or may be added at the time of melt kneading of the component (A).
  • the component (C) is added when the component (A) is melt-kneaded in the extruder, the pellets of the component (A) and the component (C) are weighed in advance and then hand-blended, and these are simultaneously fed to the extruder. You may supply.
  • the pellet of component (A) may be supplied from the upstream side of the extruder, and component (C) may be supplied to the extruder after component (A) is sufficiently melted.
  • the surface-treated calcined kaolin (C) may be pretreated with the silane coupling agent in accordance with a conventional method, and the surface-treated calcined kaolin may be mixed with the polyamide resin (A). .
  • a so-called integral blend method in which a coupling agent is added when melt kneading with the component (A) without subjecting the component (C) to surface treatment in advance may be used.
  • the polyamide resin composition of the present embodiment described above is blended with a specific ratio of boron nitride as the component (B) and calcined kaolin as the component (C) to the polyamide resin as the component (A) as a matrix. It is uniformly and finely dispersed.
  • the molded product obtained from the polyamide resin composition of the present embodiment has a mechanical strength equivalent to or higher than that of the conventional one, and the mechanical strength is sufficiently lowered by the chemical in an environment where it is in excessive contact with the chemical. And the change in mechanical strength and appearance due to chemicals, moisture in the chemicals and moisture in the atmosphere is sufficiently reduced. Therefore, the battery gasket obtained by molding the polyamide resin composition of the present embodiment has extremely excellent chemical resistance and leakage resistance.
  • the polyamide resin composition of the present embodiment has good moldability, and is particularly excellent in releasability. Therefore, when the polyamide resin composition of the present embodiment is used, a molded product having excellent mass productivity can be obtained.
  • the polyamide resin composition of the present embodiment can be particularly useful as a material for an alkaline dry battery or alkaline button battery gasket.
  • molded products are not particularly limited in shape, except that the polyamide resin composition of the present embodiment is adopted as a raw material, and may be the same as known ones, and can be manufactured by a conventionally known method.
  • the molding method there are known molding methods such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, etc. Can be mentioned. Even if these molding methods are used, good molding processing is possible, and the above-mentioned molded product can be obtained. Among these, it is preferable to form the molded product by injection molding from the viewpoint that it can be efficiently produced by utilizing the characteristics of polyamide having good fluidity and good releasability (high cycle moldability).
  • This battery gasket is a sealing part for alkaline dry batteries and alkaline button batteries that are generally widely distributed.
  • the battery gasket has a function of keeping the battery sealed by sealing an opening of a bottomed battery case containing a power generation element containing an alkaline electrolyte.
  • the battery gasket may be partially provided with a thin portion having a thickness of about 0.1 to 0.4 mm that acts as a safety valve when the battery is misused.
  • the battery gasket obtained by molding the polyamide resin composition of the present embodiment has good alkali resistance, it imparts excellent chemical resistance and liquid leakage resistance to the alkaline dry battery equipped therewith. be able to. Further, since the polyamide resin composition of the present embodiment has good moldability and particularly excellent mold release properties, it can be molded in the same excellent molding cycle as the battery gasket made of polyamide 66. Become.
  • FIG. 1 is a schematic cross-sectional front view showing an example of the battery gasket.
  • the battery gasket 1 is provided with a cylindrical outer wall 1d on the outer peripheral portion, a central boss 1a provided with a through-hole for press-fitting and inserting other parts to be described later in the center, and a connecting portion 1c provided therebetween. Are formed continuously.
  • the connecting portion 1c is provided with a thin-walled portion 1b that acts as a safety valve so as to break when a certain pressure is reached when an abnormal pressure rise occurs inside the battery.
  • the thickness of the thin portion 1b is sufficiently thin with respect to the thickness of the connecting portion 1c, and is set to 0.2 to 0.3 mm.
  • the alkaline dry battery and alkaline button type battery provided with the above-described battery gasket will be described with reference to the drawings as necessary.
  • the battery gasket provided for the alkaline dry battery and alkaline button battery is a battery gasket obtained by molding the polyamide resin composition of the present embodiment, other parts may be conventionally known.
  • FIG. 2 is a schematic half-sectional front view showing an AA alkaline battery which is an example of the above-described alkaline battery.
  • the alkaline dry battery 10 includes a bottomed cylindrical battery case 5 and a hollow cylindrical positive electrode 2 accommodated therein so as to be inscribed therein.
  • a gelled negative electrode 3 is disposed in the hollow portion of the positive electrode 2 with a bottomed cylindrical separator 4 interposed therebetween.
  • Most of the needle-shaped negative electrode current collector 6 is immersed in the gelled negative electrode 3, and one end of the negative electrode current collector 6 not immersed in the gelled negative electrode 3 is the center of the disk-shaped negative electrode terminal plate 7. It is electrically connected to the part.
  • the negative electrode current collector 6 and the negative electrode terminal plate 7 are integrated with the battery gasket 1 described above to constitute a sealing unit 9.
  • the battery gasket 1 is in contact with the opening end of the separator 4 at the connecting portion 1c, and the cylindrical outer wall portion 1d is sandwiched and fixed between the opening end of the battery case 5 and the outer edge portion of the negative electrode terminal plate 7.
  • power generation elements such as the positive electrode 2 and the gelled negative electrode 3 containing an alkaline electrolyte are accommodated, and the sealing unit 9 is arranged as illustrated, and then the opening end of the battery case 5 is opened. It is obtained by folding inward in an arc shape and sealing.
  • the outer peripheral surface of the battery case 5 is covered with an exterior label 8 to ensure insulation.
  • an aqueous solution containing 30 to 40% by mass of potassium hydroxide and 1 to 3% by mass of zinc oxide is generally used.
  • a battery gasket obtained by molding a conventional polyamide resin or a composition thereof is hydrolyzed by an alkaline electrolyte, resulting in a decrease in mechanical strength. There is also. Therefore, in order to maintain the function of the thin portion 1b for a long time after the battery is manufactured, the battery gasket is required to have high chemical resistance (strong alkali resistance).
  • the polyamide resin composition of the present embodiment has been completed in order to meet such demands, and can provide a battery gasket that is sufficiently excellent in chemical resistance (alkali resistance). Therefore, the alkaline dry battery and the alkaline button battery provided with the battery gasket obtained by molding this polyamide resin composition exhibit sufficiently good liquid leakage resistance.
  • the molded product obtained by molding has a mechanical strength equivalent to or higher than that of the conventional one, and in an environment where it is in excessive contact with the chemical, the mechanical strength is sufficiently lowered or deteriorated by the chemical. It is possible to provide a polyamide resin composition that is useful as a gasket for a battery with a small amount and sufficient change in mechanical strength and appearance due to chemicals, moisture in the chemicals, and moisture in the atmosphere.
  • Relative viscosity of polyamide resin The relative viscosity ( ⁇ r) at 25 ° C. of the polyamide resin was measured according to JIS K6810 using an Ostwald viscometer in a 98% concentrated sulfuric acid solution containing 1% by mass of the polyamide resin. .
  • Izod impact test (g) Izod impact value before chemical resistance test Notched test piece in the dry state (usually so-called absolutely dry state) before the above chemical resistance test conforms to ASTM D256 The Izod impact value (unit: J / m) was measured.
  • the polyamide resin composition was molded by injection molding to obtain a battery gasket having the same shape as in FIG. However, the thickness of the thin portion (corresponding to the portion indicated by reference numeral 1b in FIG. 1) was adjusted so that the operating pressure described later was about 8 MPa.
  • the cylinder temperature was set to 290 ° C.
  • the mold temperature was set to 80 ° C.
  • injection was set to 4 seconds
  • cooling was set to 10 seconds.
  • cover the said battery gasket was immersed, the container was sealed, and 80 degreeC was sealed. In an environmental test tank for 3 months. Thereafter, the battery gasket was taken out of the container, washed with water and dried with warm air.
  • This battery gasket was subjected to a chemical resistance test as follows. First, there is a path through which oil for oil pressure measurement flows, and a central boss part (corresponding to a part indicated by reference numeral 1a in FIG. 1) and a cylindrical outer wall part (part indicated by reference numeral 1d in FIG. 1) of the battery gasket. And a test jig for sealing the whole battery gasket was prepared. This test jig is provided with a hydraulic gauge so that the oil that has flowed in immerses the entire battery gasket, the hydraulic pressure of which is adjustable. The test gasket was stored with the battery gasket before being immersed in the aqueous solution, filled with oil, and the battery gasket was immersed in the oil.
  • the hydraulic pressure at the time of fracture corresponds to a pressure at which the thin portion of the battery gasket operates as a safety valve (hereinafter referred to as “operating pressure”).
  • operating pressure a pressure at which the thin portion of the battery gasket operates as a safety valve
  • the operating pressure of the battery gasket after drying with hot air was measured in the same manner.
  • the operating pressure (unit: MPa) for the battery gasket before immersion / the operating pressure (unit: MPa) ⁇ 100 for the battery gasket after drying with hot air was calculated as the holding ratio (unit:%) of the operating pressure. It was judged that the chemical resistance of the battery gasket was good when the retention rate was 80% or more.
  • the release force of the molded product was measured by the following method to evaluate the release property.
  • die 20 which shows a cross section in FIG. 3 was prepared.
  • the molten polyamide resin composition was injected into the mold 20.
  • the injected polyamide resin composition was filled into the box mold cavity 22 via the sprue runner 21.
  • the polyamide resin composition was sufficiently cooled in the mold 20 so that the polyamide resin was cured.
  • the mold 20 is separated between the mold part 20 a provided with the sprue runner 21 and the mold part 20 b provided with the box-shaped molding cavity 22, and the pressure sensor 25, the ejector plate 24 and the ejector are ejected by the ejector rod 26.
  • the force for projecting the molded product 28 at this time was measured by a pressure sensor 25 installed on the ejector plate 24 to obtain a release force (unit: kgf).
  • the value of the release force was recorded by a release force recorder 27.
  • the box-shaped molding cavity 22 has an inner wall on which a molded product 28 having a rectangular parallelepiped shape (bottomed container shape) having a thickness of 2 mm, a width of 32 mm, a depth of 40 mm, and a height of 21 mm can be formed. And one having a surface corresponding to the bottom side of the molded product 28 opened. Further, using an injection molding machine (trade name “SE-50D” manufactured by Sumitomo Heavy Industries, Ltd.), the mold surface temperature is 80 ° C., the polyamide resin composition temperature is 260 ° C.
  • the pressure in the autoclave was about 1.8 MPa in terms of gauge pressure, but water was discharged from the system as needed so that the pressure did not exceed 1.8 MPa. Further, the polymerization time was adjusted so that the relative viscosity of the polyamide resin became the target relative viscosity. After the polymerization in the autoclave was completed, the polyamide resin was sent out in a strand form from the lower nozzle, and after water cooling and cutting, pellet-shaped polyhexamethylene sebacamide (polyamide 610) was obtained. This polyamide resin was vacuum dried at 80 ° C. for 24 hours. When the relative viscosity ( ⁇ r) of the polyamide resin was measured as described above, it was 2.50.
  • boron nitride of the component (B) a commercial product having a powder average particle diameter of 2.5 ⁇ m measured as described above (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DENCABORON NITRIDE SP-2”) Prepared.
  • calcined kaolin of component (C) an untreated (that is, not surface-treated) calcined kaolin (trade name “SATINTONE” manufactured by Hayashi Kasei Co., Ltd.) having an average particle size of 1.5 ⁇ m as measured above. W ”) was prepared.
  • boron nitride and calcined kaolin commercially available talc having a powder average particle diameter of 4.0 ⁇ m measured as described above (trade name “Microace L-1” manufactured by Nippon Talc Co., Ltd.)
  • talc having a powder average particle diameter of 4.0 ⁇ m measured as described above
  • wollastonite trade name “Nyyard 325” manufactured by Hayashi Kasei Co., Ltd.
  • Example 1 (B) 0.1 part by mass of boron nitride and (C) 5.5 parts by mass of calcined kaolin as an aminosilane surface treatment as calcined kaolin with respect to 100 parts by mass of the pellet-like polyamide resin obtained in Production Example 1 above. They were mixed to obtain a mixture. The mixture was put into a twin screw extruder (trade name “ZSK26MC” manufactured by Coperion Co., Ltd.) and melt kneaded at 270 ° C. to obtain a polyamide resin composition. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 1 shows the composition and evaluation results of the polyamide resin composition. In the table, “PA” in the type of polyamide resin refers to “polyamide”.
  • Example 2 (B) 0.1 part by mass of boron nitride and (C) calcined kaolin are 5.5 parts with respect to 100 parts by mass of the pellet-like polyamide resin having a relative viscosity of 2.15 obtained in Production Example 2 above. They were mixed so that it might become a mass part, and the mixture was obtained. The mixture was put into a twin screw extruder (trade name “ZSK26MC” manufactured by Coperion Co., Ltd.) and melt kneaded at 250 ° C. to obtain a polyamide resin composition. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 1 shows the composition and evaluation results of the polyamide resin composition.
  • Example 2 A polyamide resin composition was obtained in the same manner as in Example 2 except that talc was used instead of boron nitride. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 1 shows the composition and evaluation results of the polyamide resin composition. From this evaluation result, it is recognized that after the chemical resistance test, the Izod impact value is remarkably increased and the releasability is lowered due to the influence of the 3% by mass calcium chloride aqueous solution, which indicates a tendency to deteriorate the moldability. . In addition, leakage from alkaline batteries was observed. This is probably because the battery gasket was too soft and deformed because the Izod impact value after the chemical resistance test was high.
  • Example 3 A polyamide resin composition was obtained in the same manner as in Example 2 except that wollastonite was used instead of calcined kaolin. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 1 shows the composition and evaluation results of the polyamide resin composition. From this evaluation result, it was confirmed that the Izod impact value significantly decreased after the chemical resistance test and leaked from the alkaline battery due to the influence of the 3 mass% calcium chloride aqueous solution.
  • Example 4 A polyamide resin composition was obtained in the same manner as in Example 2 except that boron nitride was not added. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 1 shows the composition and evaluation results of the polyamide resin composition. From this evaluation result, it was recognized that, due to the influence of 3 mass% calcium chloride aqueous solution, after the chemical resistance test, the Izod impact value was remarkably increased, the releasability was remarkably decreased, and the liquid was leaked from the alkaline battery.
  • Example 3 (B) 0.06 parts by mass of boron nitride and (C) 10 parts by mass of calcined kaolin with respect to 100 parts by mass of the pellet-like polyamide resin having a relative viscosity of 1.85 obtained in Production Example 2 above. They were mixed to obtain a mixture. The mixture was put into a twin screw extruder (trade name “ZSK26MC” manufactured by Coperion Co., Ltd.) and melt kneaded at 250 ° C. to obtain a polyamide resin composition. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 2 shows the composition and evaluation results of the polyamide resin composition.
  • Example 4 A polyamide resin composition was obtained in the same manner as in Example 3 except that a pellet-like polyamide resin having a relative viscosity of 3.20 obtained in Production Example 2 was used instead of the polyamide resin described above. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 2 shows the composition and evaluation results of the polyamide resin composition.
  • Example 5 A polyamide resin composition was obtained in the same manner as in Example 3 except that a pellet-like polyamide resin having a relative viscosity of 3.75 obtained in Production Example 2 was used instead of the polyamide resin described above. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 2 shows the composition and evaluation results of the polyamide resin composition.
  • Example 6 a pellet-like polyamide resin having a relative viscosity of 2.15 obtained in Production Example 2 was used, and the boron nitride content was changed from 0.06 parts by mass to 0.01 parts by mass.
  • a polyamide resin composition was obtained in the same manner as in Example 3 except that the content ratio of the calcined kaolin was changed from 10 parts by mass to 1.8 parts by mass.
  • Table 2 shows the composition and evaluation results of the polyamide resin composition.
  • Example 7 A polyamide resin was obtained in the same manner as in Example 6 except that the content ratio of boron nitride was changed from 0.01 parts by mass to 0.08 parts by mass, and the content ratio of calcined kaolin was changed from 1.8 parts by mass to 15 parts by mass. A composition was obtained. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 2 shows the composition and evaluation results of the polyamide resin composition.
  • Example 8 Except for changing the content ratio of boron nitride from 0.01 parts by mass to 2.5 parts by mass, and changing the content ratio of calcined kaolin from 1.8 parts by mass to 7.5 parts by mass, the same as in Example 6, A polyamide resin composition was obtained. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 2 shows the composition and evaluation results of the polyamide resin composition.
  • Example 9 A polyamide resin composition was obtained in the same manner as in Example 2 except that the content ratio of the calcined kaolin was changed from 5.5 parts by mass to 10 parts by mass. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 3 shows the composition and evaluation results of the polyamide resin composition.
  • Example 10 A polyamide resin composition was obtained in the same manner as in Example 9 except that the content of boron nitride was changed from 0.1 parts by mass to 5.0 parts by mass. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 3 shows the composition and evaluation results of the polyamide resin composition. From this evaluation result, when the content ratio of boron nitride is higher than the upper limit of the above preferable range, mechanical properties are lowered and the leakage property of the alkaline dry battery is also reduced as compared with the case where the content is within the range. A trend was observed.
  • Example 11 A polyamide resin composition was obtained in the same manner as in Example 9 except that untreated calcined kaolin was used instead of aminosilane surface-treated calcined kaolin as the calcined kaolin. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 3 shows the composition and evaluation results of the polyamide resin composition.
  • Example 12 A polyamide resin composition was obtained in the same manner as in Example 9 except that epoxysilane surface-treated calcined kaolin was used instead of aminosilane surface-treated calcined kaolin as the calcined kaolin. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 3 shows the composition and evaluation results of the polyamide resin composition.
  • Example 13 A polyamide resin composition was obtained in the same manner as in Example 9 except that the content ratio of the calcined kaolin was changed from 10 parts by mass to 25 parts by mass. Various physical properties and characteristics of the obtained polyamide resin composition were evaluated as described above. Table 3 shows the composition and evaluation results of the polyamide resin composition. From this evaluation result, when the content ratio of the calcined kaolin is higher than the upper limit of the above preferable range, the mechanical properties are lowered and the liquid leakage property of the alkaline dry battery is remarkably lowered as compared with the case where the content is within the range. A trend was observed.

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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)

Abstract

L'invention porte sur une composition de résine de polyamide qui fournit un article moulé présentant une résistance mécanique supérieure ou égale à celle d'un article classique et présentant une diminution suffisamment petite de la résistance mécanique due à un produit chimique dans un environnement de contact excessif avec le produit chimique et présentant une variation suffisamment petite de résistance mécanique et d'aspect du fait d'un produit chimique, d'eau dans un produit chimique ou d'eau dans l'air. La composition de résine de polyamide de l'invention contient (A) une résine de polyamide composée de polyhexaméthylènesébacamide et/ou de polyhexaméthylènedodécamide, (B) du nitrure de bore et (C) du kaolin cuit au four.
PCT/JP2008/068417 2008-10-10 2008-10-10 Composition de résine de polyamide et article moulé WO2010041327A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017210544A (ja) * 2016-05-25 2017-11-30 株式会社豊田中央研究所 低線膨張性ポリアミド樹脂組成物及びそれからなるポリアミド樹脂成形体
CN109075274A (zh) * 2017-04-07 2018-12-21 新生化学工业株式会社 碱性干电池用垫片及其制造方法

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JPH0927305A (ja) * 1995-07-11 1997-01-28 Unitika Ltd アルカリ電池封口ガスケット用材料
JPH10306213A (ja) * 1997-03-07 1998-11-17 Toray Ind Inc 車両外装部品用樹脂組成物
JP2002241607A (ja) * 2001-02-20 2002-08-28 Toray Ind Inc ポリアミド樹脂組成物
JP2002536484A (ja) * 1999-02-05 2002-10-29 ビーエーエスエフ アクチェンゲゼルシャフト 難燃性成形材料
JP2003261705A (ja) * 2002-03-07 2003-09-19 Nichias Corp 発泡ｐｔｆｅ樹脂組成物、ガスケット及び複合ガスケット
JP2004155948A (ja) * 2002-11-07 2004-06-03 Kanebo Ltd 中空成形体
WO2005024976A1 (fr) * 2003-09-02 2005-03-17 Fdk Energy Co., Ltd. Pile seche alcaline et joint de fermeture associe
JP2006282943A (ja) * 2005-04-04 2006-10-19 Toray Ind Inc 成形性が改良されたポリアミド樹脂組成物

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Publication number Priority date Publication date Assignee Title
JPH08189416A (ja) * 1992-01-17 1996-07-23 Nissan Motor Co Ltd 高剛性樹脂カバー
JPH0927305A (ja) * 1995-07-11 1997-01-28 Unitika Ltd アルカリ電池封口ガスケット用材料
JPH10306213A (ja) * 1997-03-07 1998-11-17 Toray Ind Inc 車両外装部品用樹脂組成物
JP2002536484A (ja) * 1999-02-05 2002-10-29 ビーエーエスエフ アクチェンゲゼルシャフト 難燃性成形材料
JP2002241607A (ja) * 2001-02-20 2002-08-28 Toray Ind Inc ポリアミド樹脂組成物
JP2003261705A (ja) * 2002-03-07 2003-09-19 Nichias Corp 発泡ｐｔｆｅ樹脂組成物、ガスケット及び複合ガスケット
JP2004155948A (ja) * 2002-11-07 2004-06-03 Kanebo Ltd 中空成形体
WO2005024976A1 (fr) * 2003-09-02 2005-03-17 Fdk Energy Co., Ltd. Pile seche alcaline et joint de fermeture associe
JP2006282943A (ja) * 2005-04-04 2006-10-19 Toray Ind Inc 成形性が改良されたポリアミド樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017210544A (ja) * 2016-05-25 2017-11-30 株式会社豊田中央研究所 低線膨張性ポリアミド樹脂組成物及びそれからなるポリアミド樹脂成形体
CN109075274A (zh) * 2017-04-07 2018-12-21 新生化学工业株式会社 碱性干电池用垫片及其制造方法
US10826031B2 (en) 2017-04-07 2020-11-03 Shinsei Kagaku Kogyo Co., Ltd. Gasket for alkaline battery and method for manufacturing same

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