WO2002050187A1 - Composition de resine polyamidique - Google Patents

Composition de resine polyamidique Download PDF

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Publication number
WO2002050187A1
WO2002050187A1 PCT/JP2001/011115 JP0111115W WO0250187A1 WO 2002050187 A1 WO2002050187 A1 WO 2002050187A1 JP 0111115 W JP0111115 W JP 0111115W WO 0250187 A1 WO0250187 A1 WO 0250187A1
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WO
WIPO (PCT)
Prior art keywords
polyamide resin
resin composition
swellable
swellable fluoromica
fluoromica
Prior art date
Application number
PCT/JP2001/011115
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English (en)
Japanese (ja)
Inventor
Akinobu Ogami
Koji Fujimoto
Kazuyuki Wakamura
Akira Yamaguchi
Rie Ito
Original Assignee
Unitika Ltd.
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Filing date
Publication date
Application filed by Unitika Ltd. filed Critical Unitika Ltd.
Publication of WO2002050187A1 publication Critical patent/WO2002050187A1/fr

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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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

Definitions

  • the present invention relates to a polyamide resin composition having excellent heat resistance, strength, and rigidity, and improved impact resistance at low temperatures.
  • a polyamide resin composition in which swellable fluorine mica is dispersed in a polyamide resin has been conventionally known, and is disclosed in, for example, JP-A-6-248176.
  • This resin composition was excellent in heat resistance and strength.-Rigidity, but insufficient elongation and impact strength.
  • JP-A-11-172100 discloses that swellable fluorine mica is uniformly dispersed at the molecular level, has high strength, high heat resistance, high toughness, excellent dimensional stability, and high elongation.
  • a reinforced polyamide resin having a high elastic modulus has been proposed. As a result, the impact strength was improved to some extent, but the impact strength in low-temperature areas was insufficient. It could not be used for exterior parts.
  • the present invention solves the above problems, and maintains the performance of a polyamide resin composition comprising a swellable fluoromica and a polyamide resin, such as high strength, high heat resistance, and high rigidity, while maintaining a low temperature range.
  • An object of the present invention is to provide a polyamide resin composition having improved impact resistance and having a property of being hardly broken even under an external force in a wide temperature range.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, using a swellable fluoromica which satisfies specific conditions as a raw material in a resin composition comprising a polyamide resin and swellable fluoromica, Finding that this goal can be achieved, The present invention has been reached.
  • the gist of the present invention is as follows.
  • a polyamide lubricating composition comprising: a polyamide lubricating oil; and a swellable fluoromica having the following structural formula and a cation exchange capacity of 80 meq.
  • the polyamide resin composition of the present invention is composed of a polyamide resin and swellable fluoromica, wherein the silicate layer of the swellable fluoromica is dispersed in a polyamide resin matrix at a molecular level. But this is good.
  • Figure 1 shows the constitutive relationship between the swellable fluorine mica and the silicate layer that composes it.
  • the silicate layer is a basic unit constituting the swellable fluoromica, and is a plate-like inorganic crystal obtained by breaking the layer structure of the swellable fluoromica (hereinafter referred to as “cleavage”).
  • the silicate layer in the present invention means a silicate layer one by one or an average of five or less layers.
  • ⁇ dispersed at the molecular level '' means that when the silicate layer of swellable fluoromica is dispersed in the polyamide resin matrix, each of them maintains an interlayer distance of 2 ntn or more on average and does not form agglomerates with each other. State.
  • the interlayer distance is the distance between the centers of gravity of the silicate layers. Such a state can be confirmed by, for example, observing a specimen of the obtained polyamide resin composition with a transmission electron microscope.
  • the polyamide resin used in the present invention is a polymer having an amide bond in its main chain, which is mainly composed of aminocarboxylic acid, ratatum or diamine and dicarboxylic acid (including a pair of salts thereof).
  • Specific examples of the raw materials include, as aminocarboxylic acids, 6-aminocaproic acid, 1-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid.
  • lactam E - force caprolactam ⁇ one ⁇ down decanoate lactam, there is a ⁇ - Lau opening Ratatamu like.
  • Jia Examples of the amine include tetramethylenediamine, hexamethylenediamine, pendecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-1, remethylhexamediamine, and metaxylylenediamine.
  • Min para-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methinole-4-aminocyclohexyl) methane, 2, 2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and the like.
  • dicarboxylic acids examples include adipic acid, spearic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalenoic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. These diamines and dicarboxylic acids can be used as a pair of salts.
  • polyamide resin examples include polycaprolamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polycaprolamide / polyhexamethylene adipamide.
  • polycaprolamide nylon 6
  • polytetramethylene adipamide nylon 46
  • polyhexamethylene adipamide nylon 66
  • polycaprolamide / polyhexamethylene adipamide Pamide copolymer
  • nylon 6/66 Polydecamide
  • Polyproamide / Polydecamide copolymer Nylon 6/11
  • Polydodecamide Nylon 12
  • Polycaproamide / Poly dodecamide copolymer Nylon 6/12
  • Polyhexamethylene rencebacamide Nylon 610
  • polyhexamethylene dodecamide Nylon 612
  • polyundecamethylene diapamide Nylon 116
  • polyhexamethylene isophthalamide Nylon 61
  • poly Hexamethylene terephthalamide Nylon 6T
  • polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer Nylon 6T / 6I
  • polyforce proamide / polyhexamethylene terephthalamide copolymer Nylon 6 / 6T
  • Polycaprolamide / polyhexene methylene isophtalua Copolymer Nycom 6/61
  • polyhexamethylene dipamide / polyhexamethylene Nylon 6/66
  • nylon 6 nylon 66, or a copolymer thereof, and more preferably Nymouth 6 or a copolymer thereof.
  • the relative viscosity of the above polyamide resin is preferably in the range of 1.5 to 5.0 as a value determined in 96 mass% sulfuric acid at a temperature of 25 ° C. and a concentration of lg / dl, preferably 2.0. Those in the range of ⁇ 4.0 are more preferred. If the relative viscosity is less than 1.5, the mechanical strength of the molded article is inferior. On the other hand, when the relative viscosity exceeds 5.0, the moldability is significantly reduced.
  • the swellable fluoromica in the present invention has a # structure composed of a negatively charged layer mainly composed of silicate and a positive charge (ionic) force interposed between the layers, and is represented by the following formula.
  • Such a production method is a swellable fluorine mica, using talc [M g 3 S i 4 0 1 () (OH) 2] as a starting material, to which was inter boyfriend child Yung alkali metal ions swelling Most preferred is a method of obtaining a fluorinated mica (Japanese Patent Application Laid-Open No. 2-149415).
  • talc is mixed with a mixture of sodium silicate and lithium silicate at a specific ratio and swelled by heat-treating at about 700 to 1200 ° C. for a short time in a magnetic tube. ⁇
  • the amount of the alkali silicate mixed with the talc is preferably in the range of 10 to 35% by mass of the whole mixture. Outside this range, the yield of swellable fluoromica tends to decrease.
  • the mixing ratio of sodium silicate and lithium silicate added during the production is reflected as the // j3 ratio in the above composition formula.
  • the cation exchange capacity (CEC) can be controlled.
  • This is lithium derived from lithium silicofluoride Is essentially a constituent element of the silicate layer, which partially neutralizes and reduces some of the negative charges in the silicate layer, resulting in an interlayer that is ionically paired with the silicate layer. This is due to the reduction of the total positive charge of the exchangeable cations.
  • Most of the sodium ions derived from sodium silicofluoride are exchangeable cations and some are non-exchangeable ions, but the details of their form are unknown.
  • CEC needs to be 80 meq / 100 g or less, and preferably 50-70 meq / 100 g.
  • the improvement rate of toughness is small compared to the large improvement of strength and rigidity, and the effect of improving the impact strength especially at low temperature is poor.
  • the CEC is less than 50 meq / 100 g, the dispersibility is reduced, and the reinforcing effect of the swellable fluoromica on the polyamide resin is reduced, and the effect of improving the heat resistance, strength, and rigidity is not recognized. .
  • the mixing ratio of sodium silicate and silica silicate is preferably 80 to 20/35/65 in molar ratio, and 55/45 to 35/65. More preferably, it is 65.
  • the swellable fluoromica produced from talc and alkali silicate may have a different CEC value between Method A and Method B. For example, it is obtained in ⁇ Swellable fluoromica production example 3 '' described later.
  • (M-3) is 70 meq / 100 g for Method B and 110 meq / 100 g for Method A.
  • the initial particle size of the swellable fluorine mica can be controlled by appropriately selecting the particle size of the raw material talc, or by pulverizing or classifying after production.
  • the impact strength is further improved by setting the average particle size measured by a laser diffraction method in a methanol dispersion medium to 2.5 ⁇ m or less, more preferably 1.5 / m or less. be able to.
  • a treatment for exchanging the exchangeable cation of fl pentafluorofluoric mica with an organic substance such as an onium salt may be performed in advance, but the swellable fluoromica is a polyamide monomer. Since it has excellent dispersibility when added during polymerization in the presence of, a good effect can be obtained without treatment with a salt or the like when added during polymerization. In addition, purification by removing non-swelling trace components can be performed in advance by elutriation.
  • the amount of the swellable fluoromica is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyamide resin. It is particularly preferred that the amount is from 5 to 5 parts by mass. If the amount of the swellable fluoromica-based mineral is less than 0.01 parts by mass, the heat resistance, strength and rigidity of the molded article tend to be insufficient. When the amount of the swellable fluoromica exceeds 50 parts by mass, not only is the toughness inferior and sufficient impact strength is not obtained, but also the polyamide resin composition of the present invention is produced as described later. In doing so, for example, the polymerization tends to be difficult.
  • the compounding amount of the swellable fluorine mica is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the monomer forming the polyamide resin. It is particularly preferred that the amount be 1 to 5 parts by mass. If the amount of the swellable fluoromica is less than 0.01 parts by mass, the heat resistance, strength, and rigidity of the molded article tend to be insufficient in minutes.
  • the amount of the swellable fluoromica exceeds 50 parts by mass, not only is the toughness inferior, sufficient impact strength is not obtained, but also the polymerization of the polyamide resin tends to be difficult.
  • a known polymerization method of a polyamide can be employed. Among them, a melt polycondensation method is preferable regardless of a batch type or a continuous type. Specifically, the necessary raw materials are charged into an autoclave, and the reaction can be performed in the presence of an initiator such as water at a temperature of 240 to 300 ° C and a pressure of 0.2 to 3 MPa for 1 to 15 hours.
  • the polymerization is preferably performed at a temperature of 250 to 280 ° C, a pressure of 0.5 to 2 MPa, and a time of 3 to 5 hours. Further, in order to remove the monomers of the polyamide remaining in the polyamide resin composition after polymerization, it is preferable to go through a scouring step using hot water. In this case, treatment is preferably performed in hot water at 90 to 100 ° C. for 5 hours or more.
  • a step of mixing the swellable fluoromica and the polyamide monomer in a dispersion medium such as water, methanol, ethanol, or ethylene glycol may be provided.
  • a dispersion medium such as water, methanol, ethanol, or ethylene glycol
  • the temperature condition may be room temperature or, if necessary, higher than room temperature and lower than the boiling point of the dispersion medium.
  • a homomixer, an ultrasonic disperser, a high-pressure disperser, or the like may be used as a means for increasing the stirring efficiency.
  • the compounding amount of the swellable fluorine mica is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyamide resin. Is particularly preferred. If the amount of the swellable fluoromica is less than 0.01 parts by mass, the heat resistance and strength of the molded article tend to be insufficient. If the amount of the swellable fluorine mica exceeds 50 parts by mass, the toughness is poor, and sufficient impact strength tends not to be obtained.
  • the swellable phlogopite mica may be mixed with the resin in a solid / powder state, or may be mixed in a state of being dispersed in a polar solvent such as water polyethylene glycol. In the latter case, it is preferable to use a melt kneading apparatus having an appropriately designed exhaust device in order to remove solvent vapor generated during melt kneading. Prior to mixing, exchangeable cations present between the layers are exchanged with organic cations such as onium ions. It is preferable to provide a step for dispersing the swellable fluoromica in the polyamide resin at the molecular level during kneading.
  • the polyamide resin containing swellable fluoromica prepared by each of the above methods may be appropriately selected from the above-mentioned various polyamide resins, irrespective of the same type or different types, and mixed.
  • the polyamide resin selected at this time may or may not contain swellable fluoromica.
  • a heat stabilizer an antioxidant, a reinforcing material, a pigment, a deterioration inhibitor, a weathering agent, a flame retardant, a plasticizer, a release agent, A lubricant or the like may be added, and these are added at the time of production by polymerization or melt kneading, or at the time of melt kneading or melt molding the obtained polyamide resin composition.
  • heat stabilizer examples include hindered phenols, phosphorus compounds, hindered amines, thio compounds, copper compounds, alkali metal halides, and mixtures thereof.
  • Reinforcing materials include, for example, clay, talc, calcium carbonate, zinc carbonate, wallacetonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, glass black, oxide
  • examples include zinc, zeolite, hydrotanolecite, metal fiber, metal whiskers, ceramic whiskers, potassium titanate whiskers, boron nitride, graphite, glass, and carbon.
  • the polyamide resin composition may contain a small amount of another thermoplastic polymer as long as the effect of the present invention is not impaired. These resins may be obtained by melt-kneading or melting the obtained polyamide resin composition. It is added when molding.
  • a thermoplastic polymer include polybutadiene, butadiene / styrene copolymer, acrylic rubber, ethylene / propylene copolymer, ethylene / propylene / gen copolymer, natural rubber, chlorinated butyl rubber, and chlorinated polyethylene.
  • maleic anhydride styrene / maleic anhydride copolymer
  • styrene / maleimide copolymer polyethylene, polypropylene, butadiene // atari mouth ethryl copolymer
  • Poly Shiojiri Bull Polyethylene Terephthalate, Polybutylene terephthalate, polyacetal, polyvinylidene fluoride, polysulfone, polyphenylene sulfide, polyethersnolephone, phenoxy resin, polyphenylene ether, polymethyl metathalylate, polyether ketone, polycarbonate, polytetraborate
  • examples include polyethylene and polyarylate.
  • thermoplastic polymers may contain fl-perfluorofluoromica or other layered silicates such as montmorillonite, vermiculite, smectite and the like.
  • the polyamide resin composition of the present invention can be made into a target molded article by a usual molding method.
  • various molded articles can be formed by a hot melt molding method such as injection molding, extrusion molding, and blow molding.
  • the polyamide resin composition of the present invention is obtained by dispersing a silicate layer of a swellable layered silicate at the molecular level in a polyamide resin.
  • a silicate layer of a swellable layered silicate at the molecular level in a polyamide resin.
  • it has excellent impact resistance especially at low temperatures, and its surface impact strength measured at -30 ° C is 10J or more. Due to this characteristic, it can be suitably used for exterior parts such as automobiles and machines that have been considered difficult to use in cold regions.
  • impact strength is improved even at room temperature, so it can be used in a wide range of fields requiring heat resistance, strength, rigidity, impact strength, etc., including interior and exterior parts of other automobiles, housings of home appliances and electronic devices, etc. Apply to
  • the polyamide resin composition of the present invention can be melt-spun into a filament by an ordinary method.
  • the film or sheet can be formed by a tubular method, a T-die method, a solution casting method, or the like.
  • the obtained film has excellent elongation characteristics and gas barrier properties, and thus can be suitably used as a packaging film.
  • the measuring method of the physical property test used in the example and the comparative example is as follows.
  • CEC ation exchange capacity
  • the swellable fluorine mica in the present invention has a cation exchange capacity of 1 mm since all cations having ion exchange capacity are sodium ions. It is equivalent to one millimol Zioog.
  • the polyamide component was prepared to have a concentration of Slg / dl using 96% by mass of sulfuric acid as a solvent, and measured at 25 ° C. using an Ube-Ede type viscometer.
  • the surface impact strength G is the energy of energy obtained by the following equation.
  • G (J) G 0 + (G-G 0 ) / 2
  • G. (Maximum height at which molded piece does not break) X (Gravity acceleration) X (Plumbing load) (Minimum height at which molded piece breaks down) X (Gravity acceleration) X (Loading weight drop)
  • the production example of the swellable fluorine mica is as follows.
  • a mixture of sodium silicate and lithium silicate having an average particle size of 10 / zm in a molar ratio of 45/55 was mixed so as to be 15% by mass of the total amount. This was placed in a magnetic crucible and reacted at 850 ° C. for 1 hour in an electric furnace to obtain a swellable fluoromica (M-1) having an average particle size of 1.0 m.
  • the composition of this swellable fluoromica is Na. 29 (M g 2 92 L i . 36) S i 4 O 10 F L 57, CEC was filed by 66 meq / 100 g.
  • a mixture of sodium silicate and lithium silicate having an average particle size of 10 ⁇ and a molar ratio of 45 to 55 was mixed to a total mass of 15% by mass. This was placed in a magnetic 1-tuple and allowed to react in an electric furnace at 850 ° C for 1 hour to obtain swellable fluoromica (M-2) with an average particle size of 4.5 m.
  • M-2 swellable fluoromica
  • the composition of this swellable fluoromica is Na. 29 (Mg 2 92 L i. 36 ) S i 4 O 10 FL 57 , CEC was 68 meq ZlOO g. Production example 3 of swellable fluoromica
  • talc To talc with an average particle size of 6.0 ⁇ m, mix sodium silicate with an average particle size of 10 ⁇ m to make up 15% by mass of the total amount, put this in a magnetic crucible, and use an electric furnace. By reacting at 850 ° C for 1 hour, swellable fluoromica (M-3) having an average particle diameter of 6. was obtained.
  • the composition of the swellable fluorinated mica was N a 0. 60 M g 2 . 63 S i 4 0 10 F 77, CEC 110 meq / 100 g.
  • the swellable fluorine mica has the same composition as that used in the examples of JP-A-11-172100 except for the average particle size.
  • Wide angle X-ray diffraction measurement (using RAD-rB type wide angle X-ray diffractometer, manufactured by Rigaku Corporation) was performed on M-1 to M-3 obtained above. The peak corresponding to the thickness of 9.2 A disappeared, and a peak corresponding to 12 to 13 A indicating the formation of swellable fluoromica was observed.
  • Table 1 shows the composition and properties of the obtained swellable fluoromica.
  • pellets were scoured with hot water of 95 ° C. for 8 hours, and this operation was repeated twice, followed by vacuum drying to obtain a dried bellet of the polyamide resin composition.
  • the dried pellets were injection molded using an injection molding machine (made by Toshiba, IS80G type) at a cylinder temperature of 260 ° C and a mold temperature of 70 ° C to produce various test pieces.
  • the polymerization was carried out in the same manner as in Example 1 except that the charged amount of the swellable fluoromica (M-1) was changed to 0.1 kg, followed by scouring, drying, and injection molding to obtain a dried and dried polyamide resin composition. Letts and test pieces were obtained.
  • Drying pellets of the polyamide resin composition were obtained by performing polymerization, scouring, drying and injection molding in the same manner as in Example 1 except that the amount of swellable fluoromica (M-1) was changed to 0.4 kg. And a test piece were obtained.
  • swellable fluorine mica lg (equivalent to 0.1%) of talc was charged as a crystal nucleating agent, polymerization was carried out in the same manner as in Example 1, and scouring, drying and injection molding were carried out to obtain a polyamide resin composition. Dried pellets and test pieces were obtained.
  • PCM-30 twin-screw extruder
  • the resulting mixture was melt-kneaded with C, discharged in a strand shape, cooled, solidified, and then cut to obtain a pellet of a polyamide resin composition. After drying the pellets, injection molding was performed in the same manner as in Example 1, and various tests were performed. Pieces were made.
  • Each of the polyamide resin compositions obtained in Examples 1 to 6 was excellent in heat resistance, strength, and stiffness, and had high surface impact strength at 23 ° C and 130 ° C.
  • the polyamide resin composition obtained in Comparative Example 1 was excellent in heat resistance, strength, rigidity and surface impact strength at 23 ° C, but was inferior in surface impact strength at ⁇ 30 ° C. Was something.
  • the polyamide resin composition obtained in Comparative Example 2 has a standard composition of non-reinforced nylon 6 for injection molding, and has no heat resistance, strength and rigidity because nylon swellable fluoromica is not added.
  • Heat resistance and strength, Oka lj resistance was high, 23 ° C, - in the 3 0 ° C any temperature inferior in surface impact strength Was.
  • Fig. 1 Diagram for explaining the structural relationship between fl Peng-lun fluoromica and the silicate layer that composes it.
  • the polyamide resin composition of the present invention is applicable to a wide range of fields, such as interior and exterior parts of automobiles, housings of home electric appliances and electronic equipment, and exterior parts of machines and the like. Therefore, it is suitable for use in, for example, automotive exterior parts that require high impact resistance in cold regions.

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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 concerne une composition de résine polyamidique présentant d'excellentes caractéristiques de thermorésistance et de résistance/rigidité, et notamment une haute résistance aux chocs en surface à de faibles températures. Cette composition de résine polyamidique se caractérise en ce qu'elle comprend une résine polyamidique et un fluoromica dilatable de formule structurale (I), et présente une capacité d'échange cationique inférieure ou égale à 80 meq/100 g. En outre, ladite composition présente une résistance aux chocs en surface à 30° supérieure ou égale à 10 J. Dans cette formule, 0 < α ≤ 0,50 < β ≤ 0,50, 2,5 ≤ x ≤ 3, 10 ≤ y ≤ 11, et 1,0 ≤ z ≤ 2,0, à condition que 90/10 ≤ α / β ≤ 10/90.
PCT/JP2001/011115 2000-12-20 2001-12-19 Composition de resine polyamidique WO2002050187A1 (fr)

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JP2000387189 2000-12-20

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02149415A (ja) * 1988-01-21 1990-06-08 Agency Of Ind Science & Technol フッ素雲母の製造方法
JPH0680820A (ja) * 1992-08-31 1994-03-22 Koopu Chem Kk 樹脂改質剤、帯電防止性樹脂組成物およびそれを用いた樹脂成形体
US5414042A (en) * 1992-12-29 1995-05-09 Unitika Ltd. Reinforced polyamide resin composition and process for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02149415A (ja) * 1988-01-21 1990-06-08 Agency Of Ind Science & Technol フッ素雲母の製造方法
JPH0680820A (ja) * 1992-08-31 1994-03-22 Koopu Chem Kk 樹脂改質剤、帯電防止性樹脂組成物およびそれを用いた樹脂成形体
US5414042A (en) * 1992-12-29 1995-05-09 Unitika Ltd. Reinforced polyamide resin composition and process for producing the same

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