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WO2009151145A1 - Nouvelle composition de résine de polyamide et produit contenant de la résine de polyamide - Google Patents

Nouvelle composition de résine de polyamide et produit contenant de la résine de polyamide Download PDF

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Publication number
WO2009151145A1
WO2009151145A1 PCT/JP2009/060979 JP2009060979W WO2009151145A1 WO 2009151145 A1 WO2009151145 A1 WO 2009151145A1 JP 2009060979 W JP2009060979 W JP 2009060979W WO 2009151145 A1 WO2009151145 A1 WO 2009151145A1
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WIPO (PCT)
Prior art keywords
polyamide resin
parts
polyamide
mass
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/060979
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English (en)
Japanese (ja)
Inventor
前田修一
倉知幸一郎
下川雅人
中川知之
奥下洋司
藤村英樹
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Ube Corp
Original Assignee
Ube Industries Ltd
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Filing date
Publication date
Priority claimed from JP2008152321A external-priority patent/JP2009298865A/ja
Priority claimed from JP2008152303A external-priority patent/JP2009298854A/ja
Priority claimed from JP2008152318A external-priority patent/JP2009298862A/ja
Priority claimed from JP2008152313A external-priority patent/JP5572922B2/ja
Priority claimed from JP2008152301A external-priority patent/JP2009298853A/ja
Priority claimed from JP2008152325A external-priority patent/JP2009298867A/ja
Priority claimed from JP2008152322A external-priority patent/JP5217660B2/ja
Priority claimed from JP2008152308A external-priority patent/JP2009298857A/ja
Priority claimed from JP2008152328A external-priority patent/JP2009298870A/ja
Priority claimed from JP2008152323A external-priority patent/JP2009299206A/ja
Priority claimed from JP2008152326A external-priority patent/JP2009298868A/ja
Priority claimed from JP2008152300A external-priority patent/JP2009298852A/ja
Priority claimed from JP2008152314A external-priority patent/JP2009298860A/ja
Priority claimed from JP2008152327A external-priority patent/JP5572923B2/ja
Priority claimed from JP2008152304A external-priority patent/JP2009298855A/ja
Priority claimed from JP2008152319A external-priority patent/JP2009298863A/ja
Priority claimed from JP2008152320A external-priority patent/JP2009298864A/ja
Priority claimed from JP2008152306A external-priority patent/JP2009298856A/ja
Priority claimed from JP2008152310A external-priority patent/JP5146124B2/ja
Priority claimed from JP2008152315A external-priority patent/JP2009298861A/ja
Priority claimed from JP2008152309A external-priority patent/JP5572921B2/ja
Priority claimed from JP2008152311A external-priority patent/JP5167965B2/ja
Priority claimed from JP2008244724A external-priority patent/JP5572935B2/ja
Priority claimed from JP2008244720A external-priority patent/JP5584966B2/ja
Priority claimed from JP2008244718A external-priority patent/JP5584965B2/ja
Priority claimed from JP2008244722A external-priority patent/JP5577574B2/ja
Priority claimed from JP2008244717A external-priority patent/JP5584964B2/ja
Priority claimed from JP2008244726A external-priority patent/JP5577577B2/ja
Priority claimed from JP2008244727A external-priority patent/JP2010077215A/ja
Priority claimed from JP2008244725A external-priority patent/JP5577576B2/ja
Priority claimed from JP2008244723A external-priority patent/JP5577575B2/ja
Priority claimed from JP2008244716A external-priority patent/JP5584963B2/ja
Priority claimed from JP2008244721A external-priority patent/JP5584967B2/ja
Priority claimed from JP2008244930A external-priority patent/JP5584968B2/ja
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Publication of WO2009151145A1 publication Critical patent/WO2009151145A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • 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
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • Crystalline polyamides such as Nylon 6 and Nylon 6 6 are widely used as textiles for clothing, industrial materials, or general-purpose engineering plastics because of their excellent characteristics and ease of melt molding.
  • problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, and deterioration in hot water have also been pointed out, leading to polyamides with better dimensional stability and chemical resistance. The demand is growing.
  • polyamide resins using oxalic acid as the dicarboxylic acid component are This is called a lyxamide resin, and it is known that it has a higher melting point and lower water absorption than other polyamide resins with the same amino group concentration (Japanese Patent Laid-Open No. 2 0 0 6 — 5 7 0 3 3 ) It is expected to be used in fields where conventional polyamides are difficult to use, where changes in physical properties due to water absorption have been a problem.
  • polyoxamide resins have been proposed that use various aliphatic straight-chain diamines as the diamine component.
  • a polyoxamide resin using 1,6-hexanediamine as the diamine component has a melting point (about 3 20) at the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 3 10). ) Since it is higher (SW Shalaby., J. Polym. Sci., 11, 1 (1973)), melt polymerization and melt molding were difficult and could not withstand practical use.
  • ⁇ ⁇ 92 Polyoxamide resin (hereinafter abbreviated as ⁇ ⁇ 92), which has 1,9-nonanediamine as the diminant component, is manufactured by L. Franco et al. The structure is disclosed (L. Franco et al., Macromolecules., 31, 3912 (1988)). ⁇ ⁇ 9 2 obtained here is a polymer with an intrinsic viscosity of 0.997 dL / g and a melting point of 2 46, but only a low molecular weight product that can not be molded into a tough molded product has been obtained. Absent. In addition, Japanese Patent Publication No.
  • 5 — 5 0 6 4 6 6 discloses a PA having an intrinsic viscosity of 0.99 dL / g and a melting point of 2 4 8 when dibutyl oxalate is used as the dicarboxylic acid ester. 9 2 has been shown to be manufactured (Special Table 5-5 500 6 6 6). In this case as well, there is a problem that only a low molecular weight body capable of forming a tough molded body can be obtained.
  • the present invention is an alternative to the conventional polyamide 6, 11 1, 12, etc., and has a particularly low water absorption while maintaining the excellent properties of the conventional polyamide resin.
  • various types of polyamide resins and polyamide resin compositions are used to develop various types of polyamide resins and polyamide resin compositions. We have eagerly studied to develop products suitable for the application.
  • the dicarboxylic acid component is oxalic acid
  • the diamine component is 1,9-nonanediamine and 2-methyl-1-, 8-octanediamine
  • PA 9 2 C can be polymerized with low water absorption, has a sufficiently large difference between the melting point and thermal decomposition temperature, has excellent melt moldability, and has various properties such as chemical resistance and hydrolysis resistance. It was found that it is an excellent polyamide resin (WO 2 0 0 8 0 7 2 7 5 4).
  • the dicarboxylic acid component is oxalic acid
  • the diamine component is a mixture of 1,9-nonanediamine and 2_methyl-1,1,8-octanediamine (hereinafter referred to as “C9 diamine mixture”).
  • C6 jamin 1, 6 —hexanediamine
  • PA 9 2/62 T Polyamide resin
  • PA 9 2 C high molecular weight is possible, melting point and thermal decomposition The difference in temperature is sufficiently large and melt moldability is excellent, and further, chemical resistance, flexibility, and water resistance are reduced compared to conventional polyamides without impairing the low water absorption seen in linear polyoxide resins.
  • This new polyamide resin (PA 9 2/6 2 T) has a higher melting point, bending elastic modulus, deflection temperature under load, etc. than PA 9 2 C. It has also been found that, while its mechanical properties are superior and cost-effective, the melting temperature range is within an acceptable range and low water absorption is not substantially lost.
  • these novel polyamide resins PA 9 2 C and PA 9 2/62 T can be used to solve various problems that are problems in the prior art. I found out that I can do it. Specifically, polyamide resin PA 9 2 C or PA 9 2/62 T added with a plasticizer, reinforcing fiber, conductivity-imparting agent, layered silicate, impact modifier, heat resistance agent, release agent.
  • Resin molding composition and polyamide resin PA 9 2 C or PA 9 2 Z 6 2 T Iramments, films, metal coating materials, binder moldings, molded articles with liquid or vapor barrier properties, fuel tanks, fuel tubes, joints for fuel piping, quick connectors, engine cooling water system parts, vehicle interior parts, Products such as vehicle exterior parts, vehicle engine room parts, cable housing, molded parts that come into direct contact with biodiesel, etc. are provided.
  • the carboxylic acid component consists of oxalic acid
  • the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2_methyl 1,8—polyamide resin having a molar ratio of octanediamine of 1: 9 9 to 99: 1, or
  • Carboxylic acid component is composed of oxalic acid
  • diamine component is a mixture of 1,9 —nonanediamine and 2 —methyl — 1,8 —octanediamine (hereinafter referred to as “C9 diamine mixture”).
  • C9 diamine mixture 1, 6—hexadamine
  • the molar ratio of the C9 jamin mixture to the C6 jamin is from 1: 9 9 to 99: 1 Polyamide resin
  • At least one additive selected from the group consisting of plasticizers, reinforcing fibers, conductivity-imparting agents, layered silicates, impact modifiers, heat-resistant agents and mold release agents
  • a polyamide resin composition comprising:
  • Polyamide resin (A) has a relative viscosity (7? R) of 1.8 to 8 measured at 25 using 96% sulfuric acid as a solvent and a polyamide resin solution with a concentration of 1.0 g / d 1. 6. Polyamide tree according to (1) above, which is 0 Fat composition.
  • Polyamide resin (A 1) is composed of a diamine component having a molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of 5:95 to 95: 5. (1)-The polyamide resin composition as described in any one of (3).
  • Polyamide resin (A 2) has a molar ratio of C 9 -diamine mixture to C 6 -diamine of 5.1: 9 4. 9 to 80: 20, in the above (1) to (4) The polyamide resin composition according to any one of the above.
  • the polyamide resin (A 2) is a polyamide resin according to the above (5), wherein the molar ratio of the C 9 jam mixture to the C 6 jam is 10:90 to 70:30. Composition.
  • the content of the layered silicate is 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin, according to any one of the above (1) to (6).
  • Polyamide resin composition is 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin, according to any one of the above (1) to (6).
  • the layered silicate is aluminum silicate phyllosilicate or magnesium silicate phyllosilicate, according to any one of (1) to (6) and (10) to (11) Polyamide resin composition.
  • the release agent is a polyalkylene glycol end-modified product, phosphoric acid ester or phosphorous acid ester, higher fatty acid monoester, higher fatty acid or metal salt thereof, ethylene bisamide compound, low molecular weight polyethylene
  • Injection molding materials injection molded products, hollow molded parts, filaments, films, metal coating materials, polyimide resin molded parts with liquid or vapor barrier properties, fuel tank parts, fuel tubes, fuel piping joints Hands, quick connectors, fuel piping parts, engine cooling water system parts, Products selected from vehicle components, vehicle interior components, vehicle exterior components, vehicle engine compartment components, cable housings, and molded components that are in direct contact with biodiesel.
  • V r The relative viscosity (V r) of the polyamide resin measured at 25 using 96% sulfuric acid as a solvent and a polyamide resin solution with a degree of 1.0 g / d 1 is 1.8 to 6
  • thermogravimetric analysis measured at a heating rate of 10 minutes in a nitrogen atmosphere and a differential measurement measured at a heating rate of 10 / min in a nitrogen atmosphere.
  • the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 95: 5, any one of (18) to (20) above Product.
  • the polyamide resin (A 2> has a molar ratio of the C 9 -diamine mixture to the C 6 -diamine of 5.1: 9 4.9 to 80:20, the above (1 8) to (2 The polyamide resin composition according to any one of 1).
  • the polyamide resin composition (A 2) is a polyamide resin composition according to the above (2 2), wherein the molar ratio of the C 9 diamine mixture to the C 6 diamine is from 10:90 to 70:30. object.
  • the product is a hollow molded part and is layered inside the polyamide resin (A)
  • the product is a metal coating material for coating a metal pipe for automobile,
  • Said product is a fuel tank components, amino end group concentration of the polyamide-de resin is 1. 5 X 1 0- 5 eg ⁇ l. 0 X 1 0 _ 4 ei Z g, said (1 8) The product according to any one of to (2 3).
  • the product is a fuel tube, and the fuel tube includes a plasticizer for the polyamide resin layer, a fluororesin, a polyethylene resin, a polyamide 11 resin, and a polyamide 12 resin.
  • a multilayer tube comprising a resin layer selected from the resins comprising the above (18)
  • the product is a joint, and the joint material is polyamide composed of 50 to 99 parts by weight of the polyamide resin (A) and other polyamide resin and / or other thermoplastic resin 1 to 50 parts by weight.
  • joint material further includes a conductive filler.
  • joint material further includes a reinforcing material and a conductive filler in a weight ratio of 1: 3 to 3: 1.
  • the quick connector is a fuel pipe component joined to the polyamide resin tube by a welding method selected from spin welding, vibration welding, laser welding, and ultrasonic welding. (18) to (23) The product according to any one of 1.
  • the product is an engine cooling water system component, and the polyamide resin (A) includes 5 to 150 parts by mass of an inorganic filler (C) with respect to 100 parts by mass of the polyamide resin (A). Any one of 1 8) to (2 3) Product described in.
  • the inorganic filler (C) is a glass fiber, the product according to the above (4 3)
  • the product is a cable housing, and the polyamide resin (A) contains a conductivity-imparting material (D) and an impact modifier (E), according to any one of the above (18) to (23) Product.
  • Impact modifier (E) Force and density 0.89-9.94 gZcc LLDPE is an acid-modified ethylene copolymer obtained by modifying with acid anhydride, (46) to (48) The product according to any one of (1).
  • the cable housing is made of polyamide resin (A) 65 to 75% by weight, carbon fiber 3 to 15% by weight as conductivity imparting material (D) and bonbon 2 to 10% by weight, impact improvement
  • the material (E) is composed of a polyamide resin composition containing 10 to 20% by weight, the above (4 6) to (49 ) Product described in any one of the paragraphs Brief description of drawings
  • Figure 2 is a cross-sectional view of the fuel tank.
  • Figure 3 is a cross-sectional view of a resin-coated metal tube.
  • Fig. 4 is a schematic cross-sectional view of a resin-bonded magnet.
  • FIG. 5 is a cross-sectional view of the multilayer tube.
  • Figure 6 is a cross-sectional view of the quick connector.
  • FIG. 7 is a perspective view showing a sample for measuring the releasability of the resin composition and the deformation of the molded body.
  • FIG. 8 is a diagram for explaining the measurement of the warpage of the injection molded article.
  • Polyamide resin PA 9 2 C has low water absorption, chemical resistance, flexibility, hydrolysis resistance, high molecular weight, moldable temperature range of 50 or more, and even 60 It is a resin that is wide and excellent in melt moldability.
  • Component of polyamide resin PA 9 2 C is a resin that is wide and excellent in melt moldability.
  • shinomic acid diester is used, and there is no particular limitation as long as it has reactivity with an amino group. Dimethyl oxalate, Diethyl oxalate, oxalic acid ⁇ mono (or i —) propyl, oxalic acid di n _ (or i mono, or ti) butyl and other aliphatic monovalent oxalic acid diesters, oxalic acid dihexyl Oxalic acid ester of alicyclic alcohol
  • 1,9-nonanediamine and 2-methyl-1,8-octanediamine use a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
  • 1,9-nonanediamine component and 2_methyl_1,8-octanediamine component The mole ratio of 1: 9 9-9 9: 1 is preferred ⁇ 5: 9 5-9 5 • 5, more preferably 5: 9 5-40: 60: 60: 4 0 to 9 5 • 5, especially 5: 9 5 to 30: 70 or 70: 0 90: 10 1, 9-nonanediamine and 2-methyl-18 monooctanediamine are copolymerized in the above specified amounts to provide a wide moldable temperature range, excellent melt moldability, low water absorption, chemical resistance, and resistance. Hydrolyzable, transparent Polyamides with excellent lightness can be obtained.
  • the polyamide resin PA 92C used in the present invention can be produced by any method known as a method for producing a polyamide. According to the study by the present inventors, it is possible to protect diamine and oxalate ester by polycondensation reaction in batch or continuous manner.
  • Pre-polycondensation step First, the inside of the reactor is purged with nitrogen, and then diamine (diamin component) and oxalic acid diester (oxalic acid source) are mixed. When mixing, a solvent in which both diamine and oxalic acid diester are soluble may be used. Solvents in which both the diamine component and the oxalic acid source are soluble are not particularly limited, but toluene, xylene, trichlorodiethylbenzene, phenol, trifluoroethanol, etc. can be used, and in particular, toluene is preferably used. be able to.
  • the temperature inside the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen publishing.
  • the reaction temperature is preferably controlled so that the final temperature reached is 80 1 5 0, preferably in the range of 1 0 0 1 4 0. Reaction time at the final temperature reached is 3-6 hours
  • the preferred final pressure for vacuum polymerization is less than 0.1 M P 3
  • the raw oxalic acid diester is charged into the container.
  • the container is not particularly limited as long as it can withstand the temperature and pressure of the polycondensation reaction to be performed later. After that, the temperature of the container is raised to a temperature at which it is mixed with the starting jam, and then the jam is injected to start the polycondensation reaction.
  • the temperature at which the raw materials are mixed is a temperature not lower than the melting point of the oxalic acid diester and diamine and lower than the boiling point of the raw material, and if the polyoxide produced by the polycondensation reaction of oxalic acid diester and diamine does not thermally decompose. Not limited to.
  • a mixture of 1,9-nonanediamine and 2-methyl-1,1,8-octanediamine, and the molar ratio of 1,9-nonanediamine to 2_methyl_1,8-octanediamine is 1: 9 9
  • the mixing temperature is preferably 15 to 240.
  • the molar ratio of 1,9-nonanediamine to 2_methyl-1,8-year-old kutandiamin is 5:95 to 90:10: liquid at room temperature or warmed to about 40 It is more preferable because it liquefies only by being easily handled.
  • the charge ratio of oxalic acid diester to diane is from 0.8 to 1.2 (molar ratio), preferably 0.91 to 1 in the above diamine diester Z
  • the temperature inside the container is raised to a temperature not lower than the melting point of the polycarbonate resin and not thermally decomposed.
  • 1, 9-nonanediamine and 2-methyl-1,8-octanediamine are used.
  • a polyoxamide resin made from diamine and dibutyl oxalate having a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine of 85: 1o, h h, t Since it is 2 3 5, it is preferable to raise the temperature from 2 4 to 2 80 X: (the pressure is from 2 MPa to 4 MPa).
  • the polycondensation reaction While distilling off the alcohol produced, the polycondensation reaction is carried out under a normal nitrogen flow or under reduced pressure as necessary.
  • the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary.
  • the preferred final pressure when performing vacuum polymerization is
  • the temperature is preferably from 2400 to 2800.
  • the alcohol is cooled with a water-cooled condenser and liquefied for recovery.
  • the molecular weight of the polyamide resin PA 92 C used in the present invention is not particularly limited, but a 96% concentrated sulfuric acid solution containing 96% concentrated sulfuric acid as a solvent and a polyamide resin concentration of 1.0 g / d 1.
  • the relative viscosity? R measured at 25 is in the range of 1.8 to 6.0. Preferably between 2.0 and 5.5 Yes, 2.5 to 4.5 is particularly preferred. If the force is lower than 1.8, the molded product becomes brittle and the physical properties deteriorate. On the other hand, if r? R is higher than 6.0, the melt viscosity becomes high and the molding processability deteriorates.
  • Polyamide resin PA 9 2 C used in the present invention uses oxalic acid as the carboxylic acid component, and copolymerizes 1,9-nonanediamine and 2 monomethyl-1,8-octanediamine as the diamine component. Compared with a polyamide composed of oxalic acid and 1,9-nonanediamine, it is possible to increase the relative viscosity, that is, increase the molecular weight.
  • the moldable temperature range represented by the difference (T d – Tm) between the 1% weight loss temperature (hereinafter abbreviated as T d) and the melting point (hereinafter abbreviated as T m), which is a substantial pyrolysis index, is Expanded compared to polyamides consisting of oxalic acid and 1,9-nonanediamine, preferably 50 or more, more preferably 60 or more, and even 80 or more It is.
  • the polyamide resin used in the present invention is characterized in that Td is preferably 2 80 or more, more preferably 3 00 or more, and further preferably 3 20 ⁇ or more, and has high heat resistance. To do.
  • Polyamide resin PA 9 2 Z 6 2 T like PA 9 2 C, has low water absorption, chemical resistance, flexibility, hydrolysis resistance, high molecular weight, and molding temperature Wide range, excellent melt formability, higher melting point than PA 9 2 C, better mechanical properties such as flexural modulus, deflection temperature under load, etc. However, it is advantageous in that the melting temperature range is within the allowable range, and the low water absorption is not substantially lost.
  • Polyamide PA 9 2/62 T used in the present invention is a dicarboxylic acid compound.
  • the component is oxalic acid
  • the diminant component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine (C9 diamine mixture) and 1,6-hexanehexane, C9 diamine mixture and 1 , 6 — Hexadiamine is a polyamide resin which is a diammine mixture having a molar ratio of 1:99 to 99: 1.
  • oxalic acid diesters are used, and these are not particularly limited as long as they have reactivity with an amino group.
  • examples thereof include oxalic acid esters of alicyclic alcohols and oxalic acid diesters of aromatic alcohols such as diphenyl oxalate.
  • oxalic acid diesters of aliphatic monohydric alcohols having more than 3 carbon atoms oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols are preferred, among which dibutyl oxalate and diphenyl oxalate Is particularly preferred.
  • the molar ratio of the 1,9-nonanediamine component to the 2-methyl-1,8-octanediamine component in the C 9 diamine mixture used in the polyamide resin PA 9 2/6 2 T of the present invention is generally 1 : 9 9-9 9: 1, preferably 5: 95-95: 5, more preferably 5: 95- 40: 60 or 60: 40-95: 5, especially 5 : 9 5 to 3 0: 7 0 or 7 0: 3 0 to 9 0: 10
  • the moldable temperature range is wide, and melt moldability is excellent.
  • polyamides with excellent water absorption, chemical resistance, hydrolysis resistance, and transparency can be obtained.
  • PA 9 2/62 T of the present invention as a diminant component, 1 is added to the above C 9 diamine mixture (a mixture of 1,9-nonanediamine and 2_methyl-1-1,8-octanediamine).
  • 6 A mixture of hexane diamine is used.
  • the molar ratio of the C 9 diamine mixture to 1,6-hexanediamine is from 1:99 to 99: 1.
  • oxalic acid is used as the dicarboxylic acid component and C 9 diamine mixture is used as the diamine component.
  • the melting point of the polyamide resin is increased and the mechanical properties are particularly improved.
  • the molar ratio of the C 9 diamine mixture to 1, 6-hexane diamine is preferably 5.1: 9 4. 9-9 9: 1, more preferably 10: 90-99: 1, More preferably, it is 20: 80-99: 1.
  • the change to the melting point appears clearly by copolymerization of 1,6-hexanediamine in a molar ratio of 1-9 99 or more with respect to the C 9 diamine mixture, and the melting point of the resin If the increasing force 1, 6-hexanediamine is within 9 91 in molar ratio, melt formability is acceptable. In addition, if 1,6-hexanediamine is within 80/20 in molar ratio, the melting point of the polyamide resin is 30 or less and the polymerization and molding process (melt moldability) are easier. If it is within 70 0 30, the melting point is 2 80 t: it is more preferable because the melt moldability becomes easier.
  • the polyamide resin PA 9 2/62 T used in the present invention can be produced by any method known as a method for producing a polyamide. You can. According to the study by the present inventors, it can be obtained by subjecting diamine and oxalate diester to a polycondensation reaction in a batch or continuous manner. Specifically, it is preferable to carry out in the order of (i) pre-polycondensation step and (ii) post-polycondensation step as shown in the following operations.
  • the charging ratio of the oxalic acid diester to the above-mentioned diamine is from 0.8 to 1.5 (molar ratio), preferably from 0.91 to 1.1 (molar ratio), It is preferably 0.99 to 1.01 (molar ratio).
  • the temperature inside the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen publishing.
  • the reaction temperature is preferably controlled so that the final reached temperature is in the range of 80 to 150, preferably in the range of 100 to 140. Reaction time at the final temperature reached is 3-6 hours
  • (ii) Post-polycondensation step In order to further increase the molecular weight, the temperature of the polymer produced in the pre-polycondensation step is gradually raised in the reactor under normal pressure. In the temperature raising process, from the final ultimate temperature of the pre-polycondensation step, that is, from 80 to 1550, finally from 220 to more than 30, preferably from 230 to more than 2800, Preferably, the temperature ranges from 2 40 to 2 70 and to the following temperature range. 1-8 hours, including heating time, preferred It is preferable to carry out the reaction by holding for 26 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary.
  • the raw oxalic acid diester is charged into the container.
  • the container is not particularly limited as long as it can withstand the temperature and pressure of the polycondensation reaction to be performed later. After that, the container is raised to a temperature at which the vessel is mixed with the raw material jam, and then the diene is injected to start the polycondensation reaction.
  • the temperature is not particularly limited as long as the temperature is lower than the boiling point and the small oxide produced by the polycondensation reaction of oxalic acid diester and diane is not thermally decomposed. For example, 1 9 -nonanediamine 2 -methyl-1,
  • C 9 jamming (1, 9-nonane jamming and
  • Dioxalic acid The charge ratio of ester to diamine is oxalic acid diester Z above diamine, 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio), more preferably 0. 9 8 to 1.0 2 (molar ratio).
  • the temperature inside the container is raised to a temperature not lower than the melting point of the polyoxide resin and not higher than the temperature at which it does not decompose.
  • it consists of C 9 diamine (a mixture of 1,9-nonanediamine and 2-methyl-1,1,8-octanediamine) and 1,6 hexanediamine, and C 9 diamine (1,9-nonane).
  • Polyamide resin PA 9 2 Z 6 2 T used in the present invention uses oxalic acid as the carboxylic acid component, and copolymerizes 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component. Compared to polyamides composed of oxalic acid and 1,9-nonanediamine, it is possible to increase the relative viscosity, that is, increase the molecular weight.
  • the polyamide resin PA 9 2/62 T used in the present invention uses oxalic acid as the carboxylic acid component, and 1,9-nonanediamine and 2-methyl-1,1,8-octanediamine as the diminant component.
  • Copolymerization of 1,6-hexamethylenediamine increases the melting point of the resin compared to polyamides consisting of oxalic acid and 1,9-nonanediamine and 2-methyl-1,1,8-octanediamine. It is possible.
  • the polyamide resins PA 92 C and PA 92/62 T used in the present invention can contain other dicarboxylic acid components as long as the effects of the present invention are not impaired.
  • Other dicarboxylic acid components other than succinic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2, 2-dimethyldal Aliphatic acid, 3, 3 — Aliphatic dicarboxylic acids such as jetyl succinic acid, azeleic acid, sebacic acid, suberic acid, 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.
  • 6 2 T can contain other diamine components as long as the effects of the present invention are not impaired.
  • 1, 9 Non-diamine and other diamine components other than 2-methyl-1,8-octanediamine include ethylene-diamine, propylene-diamine, 1,4-one-butanediamine, 1,8-one-octanediamine, 1, 1 0 —decane amine, 1, 1 2 —do, decane amine, 3 —methyl 1, 2, 5 —pentamine, 2, 2, 4 1 trimethyl 1, 6 —hexane, 2, Aliphatic amines such as 4,4-limethyl 1,6_hexanediamine, 5-methyl-1,9-nonanediamine, and fats such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine Cyclic diamine, p_phenylenediamine, m-phenylenediamine, p-xylenediamine, m-dried diamine, 4,
  • Part of the polyamide resins PA 9 2 C and PA 9 2/62 T used in the present invention are within the range that does not impair the effects of the present invention, other polyoxides, aromatic polyamides, aliphatic polyamides. It is possible to substitute with polyamides such as alicyclic polyamides.
  • thermoplastic resin such as polyvinyl chloride, polyurethane, polyester, ABS resin, acid-modified polyethylene, acid-modified polypropylene, or other thermoplastic resin, or an elastomer.
  • the amount of the resin to be replaced is preferably 50% by mass or less of the entire resin.
  • polyamide resins P A 92 C and P A 92/62 T of the present invention can be partially replaced with other polymer components as long as the effects of the present invention are not impaired.
  • Other polymer components include, for example, other polyamides such as polyoxides, aromatic polyamides, aliphatic polyamides, alicyclic polyamides, and polymers other than polyamides, such as heat.
  • Plastic polymer, Elastomer are examples of polyamides such as polyoxides, aromatic polyamides, aliphatic polyamides, alicyclic polyamides, and polymers other than polyamides, such as heat.
  • Plastic polymer, Elastomer such as polyoxides, aromatic polyamides, aliphatic polyamides, alicyclic polyamides, and polymers other than polyamides, such as heat.
  • the method for adding the other polymer and the additive is not particularly limited as long as each of them can be dispersed in the polyamide resin. Can be added to amide resins.
  • the other polymer and additive can be added immediately after the post polycondensation step of the polyamide resin. 1. 4 Polyamide Other resins that can be mixed with PA 9 2 C or PA 9 2 6 2 T
  • the polyamide P A 92 C or PA 92/62 T of the present invention is a homopolymer of polyamide P A 92 C or PA 92/2/62 T or a mixture thereof.
  • polyamide resin PA 9 2 C or PA 9 2/6 2 is also used in various polyamide resin compositions and product resins or resin compositions provided by the present invention described below in the present specification.
  • Other polyamide resins or other thermoplastic resins can be added to T as necessary.
  • polyamide resins that can be preferably used in combination with polyamide PA 9 2 C or PA 9 2/62 T include, for example, other polyamides such as polyoxides and aromatic polyamides. Aliphatic polyamides, alicyclic polyamides, and the like, and polymers other than polyamides such as thermoplastic polymers and elastomers.
  • polyamides include polyethylene adipamide (Nylon 26), polytetramethylene adipamide (Nylon 46), polyhexamethylene adipamide (Nylon 66), poly Oxamethylene azepam (nylon 6 9), polyhexamethylene sebamide (nylon 6 10), polyhexamethylene decamide (nylon 6 1 1), polyhexamethylene dodecamide (nai Ron 6 1 2), Poly-Proamide (Nylon 6), Polydecanamide (Nylon 1 1), Polydodecanamide (Nylon 1 2), Polyhexamethylene Terephthalamide (Nylon 6 T), Polyto Xamethyleneisophthalamide (nylon 61), polynonamethylene dodecamide (nylon 9 1 2), polydecamethylene dodecamide ( Lee Ron 1 2 1 2), Polymetaxylylene adipamide (Nylon MXD 6), Polytrimethylhexamethylene terephthalamide (TMHT), Polybis (4-aminocyclohexyl) Methane
  • Nylon 6, Nylon 11, Nylon 12, Nylon 61, Nylon 61, or a copolymer thereof is preferably used for improving moldability and adhesion.
  • thermoplastic resins include high-density polyethylene (HDPE), low-density polyethylene (LDPE), ultrahigh molecular weight polyethylene (UHMWP E), isoactic polypropylene, and ethylene propylene copolymer (EPR).
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • UHMWP E ultrahigh molecular weight polyethylene
  • EPR ethylene propylene copolymer
  • Polyester resins such as aromatic polyesters such as polymers, polyarylate ⁇ (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide polybutyrate terephthalate copolymer, poly Acetal (POM), Polyphenylene Oxide (PPO), Polyphenylene Sulfide (PPS)
  • PES Polyether resins such as polysulfone (PSF) and polyether-terketone (PEEK), polyacrylonitrile (PAN), polychlorinated nitrile, acrylonitrile / styrene Polymer (AS), nylon styrene copolymer, acrylonitrile / vadagen / styrene copolymer (ABS), nylon styren
  • the plasticizer-containing polyamide resin composition of the present invention contains other polyamide resin and / or other thermoplastic resin together with the polyamide resin PA 9 2 C or PA 9 2/62 T
  • the blending amount thereof Is not limited, and ranges from 5 to 99 parts by mass of polyamide resin PA 9 2 C or PA 9 2/62 T and 1 to 95 parts by mass of other polyamide resins and / or other thermoplastic resins
  • Polyamide resin PA 9 2 C or PA 9 2/6 2 T 30 to 99 parts by mass, other polyamide resin and Z or other thermoplastic resin 1 to 70 More preferably, it consists of 1 part by mass of other polyamide resins and / or other thermoplastic resins.
  • the effect of the present invention is not impaired in the composition containing the polyamide resins PA 9 2 C and PA 9 2/62 T or the polyamide resins PA 9 2 C and PA 9 2/6 2 T of the present invention.
  • other additives can be added.
  • the PA 9 2 C and PA 9 2 Z 6 2 T resin compositions added with plasticizers, conductivity-imparting agents, reinforcing fibers, layered silicates, impact modifiers, and heat-resistant agents are important for the present invention. This will be described in detail below.
  • an unprecedented unique polyamide resin composition can be provided by adding various additives to the above-mentioned polyamide resins PA92C and PA92 / 62T. Next, the polyamide resin composition containing these additives according to the type of the additive will be described.
  • the present inventors have no plasticizer bleeding out by using the polyamide resin PA 9 2 C or PA 9 2/62 T.
  • it has a high molecular weight, has a large difference between the melting point and the thermal decomposition temperature, has excellent melt moldability, and is more resistant to conventional polyamides without impairing the low water absorption observed in linear polyoxamide resins. It has been found that a plasticizer-containing polyamide resin composition having excellent chemical properties, flexibility and hydrolysis resistance can be obtained.
  • the polyamide resin PA 9 2 Z 6 2 T has a higher melting point, better mechanical properties such as flexural modulus and deflection temperature under load than PA 9 2 C, and is cost effective.
  • the reduction of the melting temperature range is within an allowable range, and that the low water absorption is not substantially lost.
  • the plasticizer used in the present invention may be any plasticizer known to be used in polyamide resins, but is preferably one or more compounds selected from esters and alkylamides.
  • Esters referred to in the plasticizer of the present invention include fuuric acid esters, fatty acid esters, polyhydric alcohol esters, phosphoric acid esters, trimellitic acid esters, and hydroxybenzoic acid esters. It is kind. Specific examples of fumaric acid esters include dimethyl furate, dimethyl phthalate, dibutyl furate, diheptyl phthalate, di-2-ethylhexyl furate, and di-n-octyl phthalate.
  • fatty acid esters include dimethyl adipate, dibutyl adipate, diisobutyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, diisodecyl adipate, adipic acid Diisononyl, di-dipic acid di-n-mixed alkyl ester, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl azelate, di-2-ethylhexyl mixed acid ester, Dibasic saturated sulfonic acid esters such as bis-2-decylhexyl dodecanoate, dibutyl fumarate, bis-2-methylpropyl fumarate, bis-2-ethylhexyl fumarate, dimethyl maleate, malein Jety
  • polyhydric alcohol esters include 2,2,4_trimethyl-1,3-pentenediol monoisopropylate, 2,2,4_trimethyl—1,3—pen Didiol diisobutylene ⁇ , diethylene glycol dibenzoate ⁇ , triethylene glycol diol 2-ethylbutyrate, pen erythritol monooleate, pen ⁇ ⁇ erythritol monostearate ⁇ , pen tub Erythryl monoalkyl ether, behenic acid monoglyceride, 2-ethylhexyl triglyceride, glycerin triacetate and glycerin
  • One example is rib chillers.
  • phosphoric acid esters include trimethyl phosphate, trityl phosphate, triptyl phosphate, trityl phosphate 2-ethylhexyl, tributoxyl phosphate, triphenyl phosphate, n-dioctyl diphenyl phosphate, phosphate Examples include cresyl diphenyl, tricresyl phosphate, trixylenyl phosphate, and 2-ethylhexyl diphenyl phosphate.
  • trimellitic acid esters include tributyl trimellitic acid trimethyltrimellitic acid, trimethyltrimethyl acid 2-triethylhexyl, trimethyltrimethyl acid tri-n- And trimethylone tritylate, triisononyl trimellitic acid, triisodecyl trimellitic acid, and trimethyl trimethyl acid mixed alcohol ester.
  • hydroxybenzoic acid esters include o—or p—ethyl hexyl oxybenzoate, o—or p—hydroxydecyl hexyl benzoate, o—or p—ethyl decyl oxybenzoate, o — or p — octyloctyl hydroxybenzoate, o — or p — decyldodecyl hydroxybenzoate, o — or p — hydroxymethyl benzoate, o — or p — hydroxypropyl benzoate, o — or p -Hexyl hydroxybenzoate, o- or p-hydroxybenzoic acid n--octyl, o-or p-decyl hydroxybenzoate and o- or p-dodecyl hydroxybenzoate.
  • the alkylamides are toluenesulfonic acid alkylamides and benzenesulfonic acid alkylamides.
  • Specific examples of toluene sulfonic acid alkylamides include N_ethyl_o_toluenesulfonic acid butylamide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethyl ether And N-ethyl _ p-toluenesulfonic acid 2-ethyl hexylamide.
  • Benzenesulfonic acid alkylamide Specific examples of such compounds include benzene sulfonic acid propyl amide, benzene sulfonic acid butyl amide, benzene sulfonic acid 2_ethyl hexyl amide and the like.
  • the plasticizers listed above may be used alone or in appropriate combination of two or more.
  • butyl esters such as dibutyl phthalate, diisodecyl phthalate, di-2-butylhexyl butyrate, ethyl hexyl p-hydroxybenzoate, p-hydroxyl Hydroxybenzoates such as hexyldecyl benzoate, alkyl amides such as butyl benzene sulfonate and 2-ethylhexyl benzene sulfonate are preferably used.
  • Polyamide resin PA 9 2 C or PA 9 2/6 2 T used in the present invention has excellent characteristics possessed by polyamide resin PA 9 2 C or PA 9 2/6 2 T even when a plasticizer is added. (Low water absorption, chemical resistance, flexibility, hydrolytic resistance, wide moldable temperature range, mechanical strength, etc.) are basically kept as they are or relatively. Regarding the moldable temperature range, the polyamide resin is generally more flexible by adding a plasticizer, and the melting temperature is lowered because the melting point is lowered, but the polyamide resin is PA 9 2 C or PA 9 Compared with conventional PA 9 2 2/6 2 T, the wide moldable temperature range characteristics are maintained even when the plasticizer is retained.
  • the plasticity measured at a heating rate of 10 / min under a nitrogen atmosphere was obtained.
  • ⁇ 1% weight loss temperature in a gravimetric analysis of a polyamide resin without a plasticizer and differential running calorimetry of a polyamide resin composition containing a plasticizer measured at a heating rate of 10 minutes in a nitrogen atmosphere The temperature difference from the melting point measured by the above is preferably 50 or more, more preferably 60 or more, and further 90 or more.
  • the polyamide F resin PA 9 2 C or PA 9 2/62 T of the present invention has the advantage that it can be molded without pre-dough by adding a plasticizer.
  • Stabilizers such as copper compounds, pigments, dyes, colorants, UV absorbers, light stabilizers, antioxidants, weathering agents, UV absorbers, antistatic agents, flame retardants, lubricants, crystallization accelerators, Various additives such as reinforcing fibers such as glass fibers, layered silicates, reinforcing particles, fillers, lubricants, and foaming agents can be added.
  • the method of adding the additive is not particularly limited as long as each of the additives can be dispersed in the polyamide resin, and the additive is added to the polyamide resin at any time without impairing the effect thereof. be able to.
  • these additives can be added during the polycondensation reaction of the polyamide resin, immediately after the post-polycondensation step, or after that.
  • additives including a plasticizer
  • a plasticizer can be arbitrarily added to all the polyamide resin compositions and polyamide resin products of the present invention described in this specification. The same applies to the timing of additive addition.
  • the method for obtaining the polyamide resin composition of the present invention is not particularly limited, and various known methods can be used.
  • poly Predetermined amounts of amide, plasticizer and various additives are mixed in advance using a low-speed rotary mixer such as a V-type blender or tumbler, or a constrained rotary mixer such as a Henschel mixer. After melt-kneading with a screw extruder etc. and pelletizing, or pre-mixing a specified amount of polyamide, plasticizer and various additives using a constrained rotary mixer such as a low-speed rotary mixer or Henschel mixer A method of directly obtaining a molded product of a composition by using an injection molding machine or an extrusion molding machine can be applied.
  • polyamide resin composition As a method for molding the polyamide resin composition, all known molding processing methods applicable to the polyamide such as injection, extrusion, blow, hollow, press, roll, foaming, vacuum / pressure air, and stretching can be used.
  • the plasticizer-containing polyamide resin composition of the present invention can be used to obtain molded articles such as tubes, filaments, sheets, films, and fibers by the molding method as described above.
  • the plasticizer-containing polyamide resin composition of the present invention can also be used as a coating material, but as a molded product, a molding material such as an industrial material, an industrial material, or a household product, particularly an automobile member, an optical device member, an electric Electronics
  • Suitable for a wide range of applications such as information / communication-related equipment, precision equipment, civil engineering / building supplies, medical supplies, and household goods.
  • information / communication-related equipment such as sports shoes materials, ski surface materials, mechanical gears, electrical precision equipment gears, connectors, seals, automotive moldings, sealing materials, various tubes' hoses
  • the plasticizer-containing polyamide resin composition of the present invention has low water absorption, excellent melt moldability, excellent moldability, no plasticizer bleeding, and excellent impact resistance. Hydrolysis resistance and hydrolysis Excellent physical property retention after treatment, and excellent chemical resistance.
  • the plasticizer-containing polyamide resin composition of the present invention preferably has a tensile elongation at break of 90% or more, and more preferably about 100%.
  • the plasticizer-containing polyamide resin composition of the present invention has low water absorption, chemical resistance, flexibility, hydrolysis resistance, high molecular weight, and a moldable temperature range of 50 or more, Furthermore, it is a resin composition with a wide range of 60 or more, excellent melt moldability, and no plasticizer bleedout, and is widely used as a molding material for industrial materials, industrial materials, household products, etc. can do.
  • the present invention has a high molecular weight while being excellent in mechanical properties and chemical resistance by blending reinforcing fibers with polyamide resin PA 9 2 C or PA 9 2 Z 6 2 T. Therefore, the difference between the melting point and the thermal decomposition temperature is large, the melt moldability is excellent, and the hydrolysis resistance, etc. is improved compared to conventional polyamides without impairing the low water absorption observed in linear polyoxide resins.
  • the present invention also provides an excellent polyamide resin composition.
  • the present invention is characterized in that a reinforcing fiber is blended with the polyamide resin PA 9 2 C or PA 9 2/62 T.
  • a reinforcing fiber is blended with the polyamide resin PA 9 2 C or PA 9 2/62 T.
  • examples thereof include inorganic fibers such as glass fibers, carbon fibers, metal fibers, and mineral fibers, and organic fibers such as polyamide fibers that are tougher than polyamide resins.
  • the glass fiber is not particularly limited.
  • the glass fiber diameter is not limited, but is preferably 5 to 15 m.
  • the fiber length may be a short fiber or a long fiber depending on the application, but 5 to; L 2 O O O ⁇ m is preferable.
  • the mixing ratio of the glass fiber is preferably 2 to 40 parts by mass, more preferably 2 to 38 parts by mass, and more preferably 3 to 35 parts by mass with respect to 100 parts by mass of the whole resin. If the amount of glass fiber is too small, the improvement in rigidity and creep resistance will be low, and there is a risk of poor bonding with tubes. On the other hand, when the amount of the glass fiber is increased, the fluidity of the composition is deteriorated, which may cause a short shot or the surface condition.
  • the carbon fiber is not particularly limited, such as pitch-based or PAN-based, but PAN-based carbon fiber is preferable in terms of properties such as physical properties and conductivity.
  • the carbon fiber diameter is not limited, but is preferably 5 to: I 5 m. Fine carbon fibers can also be used.
  • the blending ratio of the carbon fibers is preferably 2 to 40 parts by weight, more preferably 2 to 38 parts by weight, and more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the whole resin. If the amount of carbon fiber is small, the improvement in rigidity, creep resistance, and conductivity may be lowered, so 5 parts by mass or more is preferable. On the other hand, if the amount of carbon fiber exceeds 40 parts by mass, This is not preferable because the fluidity of the liquid becomes poor, which may cause a short shot or the surface condition.
  • the polyamide resin used in the present invention has excellent mechanical strength, chemical resistance, low water absorption, hydrolysis resistance, and the like, and has a wide moldable temperature range and excellent melt moldability. Even when reinforcing fibers are blended, they are basically maintained as they are, and certain characteristics such as mechanical strength and heat resistance are significantly improved by blending the reinforcing fibers.
  • the polyamide resin of the present invention has PA 92 C or PA 92/62 T force, but is mixed with other polyamide resin or other thermoplastic resin as long as the effects of the present invention are not impaired. It is also possible to do.
  • Other polyamide resins or other thermoplastic resins that can be blended are as described above in 1.4.
  • the polyamide resin and the reinforcing fiber are blended in advance, or the reinforcing fiber is put in the middle of the molding machine, injection, extrusion, hollow, press, roll, foaming Any known molding process that can be applied to the polyamide resin composition, such as vacuum, pressure, and stretching, can be used. By these molding processes, films, sheets, molded articles, fibers, and the like can be processed.
  • Molded articles using the fiber-reinforced polyamide resin composition of the present invention are useful in various applications because of their excellent characteristics, and various molded articles in which molded articles of the polyamide resin composition have been conventionally used, Sheet, Fi Lum, pipes, tubes, monofilaments, fibers, containers, etc.
  • Automotive parts, computers and related equipment, optical equipment parts, electrical-electronic equipment, information, communication equipment, precision equipment, civil engineering, building supplies, medical supplies, homes Can be used for a wide range of applications such as goods. In particular, because it is reinforced, it is useful for applications such as automobiles and electrical / electronic equipment.
  • Fig. 1 schematically shows the structure of the fiber-reinforced polyamide resin composition.
  • 1 is a polyamide resin and 2 is a reinforcing fiber.
  • the present invention has a high molecular weight and a difference between the melting point and the thermal decomposition temperature by adding a conductivity-imparting agent to the polyamide resin PA 9 2 C or PA 9 2/62 T.
  • a conductivity-imparting agent to the polyamide resin PA 9 2 C or PA 9 2/62 T.
  • the conductivity-imparting agent used in the present invention is not particularly limited as long as it can be imparted with conductivity by being blended with polyamide resin.
  • the conductivity imparting agent is not particularly limited as long as it can impart conductivity, and examples thereof include carbon black, carbon fiber, and metal fiber, and carbon black and carbon fiber are particularly preferably used.
  • the carbon black that can be used in the present invention includes all carbon blacks that are generally used for imparting electrical conductivity.
  • Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, Ketjen black, oil black, naphthenic black, thermal black, lamp black, channel black, roll black, disc black, etc. Power ⁇ It is not limited to these. Among these, acetylene black and furnace black (Ketjen black) are particularly preferably used.
  • Carbon black is produced in various carbon powders with different characteristics such as particle size, surface area, DBP oil absorption, and ash content.
  • the carbon black has no particular limitation, but preferably has a good chain structure and a high aggregation density.
  • a large amount of carbon black is not preferable in terms of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 50 nm or less, and 5 to 10 nm. More preferably, it is more preferably 10 to 7 O nm, and the surface area (BET method) is preferably 10 m 2 or more, and preferably 300 m 2 Zg or more.
  • DBP Dynamic Hydrocarbonate
  • Oil absorption is preferably 5 O ml Z l 0 0 0 g or more, more preferably 1 0 O ml Z 1 0 0 g, 3 0 0 ml Z 1 0 0 g
  • the ash content is preferably 0.5% by weight or less, and more preferably 0.3% by weight or less.
  • the DBP oil absorption here is a value measured by the method defined in ASTM D-2 4 14. Carbon black preferably has a volatile content of less than 1.0% by weight.
  • the blending ratio of carbon black is preferably 2 to 50 parts by mass with respect to 100 parts by mass of the whole resin. If the blending ratio of the carbon black is less than 2 parts by mass, it is not preferable because sufficient conductivity cannot be obtained, and if the blending ratio exceeds 50 parts by mass, the melt viscosity is high and the fluidity is lowered, so that moldability is improved. Is not preferred because it is significantly impaired. 2 to 15 parts by mass are preferred.
  • pitch-based and PAN-based carbon fibers are used without limitation, but PAN-based carbon fibers are more preferable in view of properties such as physical properties and conductivity.
  • the carbon fiber length may be a short fiber as long as 100 O mm depending on the application, but the fiber length before kneading is preferably 0.1 to 12 mm, and preferably 1 to 8 mm. Is particularly preferred.
  • the fiber diameter of the carbon fibers is preferably 5 to 15 but fine carbon fibers can also be used.
  • the blending ratio of the carbon fibers is preferably 2 to 40 parts by mass with respect to 100 parts by mass of the whole resin. When the blending ratio exceeds 40 parts by mass, the rigidity is high and the impact resistance is inferior, and the smoothness of the surface of the molded product is poor and the slidability may be lowered.
  • the blending ratio of carbon fiber is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 7 parts by mass or more. Yes. If the blending ratio is low, the electrical conductivity is lowered and it is easy to be charged with static electricity.
  • the conductivity required for the polyamide resin composition of the present invention may vary depending on the application, and is not particularly limited.
  • the conductivity of polyamide resin is
  • conductivity-imparting agent for example, it can be reduced to about 10 12 to 10 1 Q cm or less, but depending on the application, the properties and bands required for polyamide resin products It may be determined from the balance of the purpose of preventing electricity. In general, conductivity of about 10 3 to 10 6 Q cm is considered to be one preferable range.
  • reinforcing fibers may be blended in the polyamide resin composition of the present invention.
  • the reinforcing fiber to be blended is not particularly limited, and examples thereof include inorganic fibers such as glass fiber, carbon fiber, metal fiber, and mineral fiber, and organic fibers such as polyamide fiber that is tougher than polyamide resin.
  • the effect of improving the physical properties such as the strength and creep resistance of the composition is remarkable by adding reinforcing fibers.
  • Glass fiber and carbon fiber are particularly preferred.
  • Use of carbon fiber has the effect of imparting antistatic performance. As for carbon fibers, those described above can be used.
  • the glass fiber is not particularly limited.
  • the glass fiber diameter is not limited, but is preferably 5 to 15 m.
  • the fiber length may be short fiber or long fiber depending on the application, but 5 to 100 m is preferred.
  • the polyamide resin of the present invention is composed of PA 9 2 C or PA 9 2/62 T, but other polyamide resins or other thermoplastic resins should be mixed within a range not impairing the effects of the present invention. Is also possible. Other polyamide resins or other thermoplastic resins that can be blended are as described above in 1.4.
  • the polyamide resin PA 92 C used in the present invention is preferably contained in an amount of 50% by mass or more of the resin component.
  • additives may be added to the polyamide resin composition of the present invention as required (as described above).
  • the polyamide resin and the conductivity-imparting agent are blended in advance, or the conductivity-imparting agent is introduced in the middle of the molding machine, injection, extrusion, hollow, All known molding methods that can be applied to polyamide resin compositions such as press, roll, foaming, vacuum / compressed air, stretching, etc. are possible, and they can be processed into films, sheets, molded products, fibers, etc. by these molding methods. Can do.
  • Molded articles using the conductive polyamide resin composition of the present invention include various molded articles, sheets, films, pipes, tubes, monofilaments that have conventionally been used in molded polyamide resin compositions. Used in a wide range of applications such as automobile parts, computers and related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, etc. it can. Especially, cars Useful for applications such as electrical and electronic equipment.
  • the conductive polyamide resin composition of the present invention has low water absorption
  • the present invention uses a polyamide resin PA 9 2 C or PA 9 2 6 2 T, and has high mechanical strength, heat resistance, and barrier property against liquid or vapor, Compared with conventional nylon 6-based resin compositions, it has excellent water absorption, chemical resistance, hydrolysis resistance, etc., and is a polyamide resin system that uses 1,9-nonanediamine alone as a diminant component.
  • the moldable temperature range is wider than that of the resin composition, and the melt moldability is excellent.
  • a polyamide resin composition that can be produced is provided.
  • the polyamide resin composition of the present invention contains a layered silicate dispersed in a polyamide resin P A 92 C or PA 92 2 62 T.
  • Layered silicate is a component that imparts mechanical properties and heat resistance to a polymer material.
  • the layered silicate is preferably one in which each layer maintains a distance of about 18 A or more and is uniformly dispersed when dispersed in the polyamide resin.
  • Examples of the raw material of the layered silicate include a layered fluorosilicate mineral composed of a layer of magnesium silicate or aluminum silicate, that is, an aluminum silicate phyllosilicate or a magnesium silicate phyllosilicate. Can do. Specific examples include smectite clay minerals such as montmorillonite, saponite, bidelite, nontronite, hectrite, and stevensite, vermiculite, and halloysite. These may be natural or synthesized.
  • the layered silicate is preferably pulverized using a mixer, a ball mill, a vibration mill, a pin mill, a jet mill, a beating machine, or the like, and has a desired shape and size in advance.
  • Examples of the method for uniformly dispersing the layered silicate in the polyamide resin include the following methods.
  • the raw material of the layered silicate is a multi-layered clay mineral
  • the layered silicate is ionized with hydrochloric acid, etc., and there is a swelling agent such as 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
  • a polyamide raw material can be introduced between the layers, and the raw materials can be polymerized between the layers.
  • a polymer compound may be used as a swelling agent, and the layers may be spread in advance to about 100 A or more, melted and mixed with the polyamide resin, and each layer may be dispersed in the polyamide resin.
  • the amount of the layered silicate in the resin composition of the present invention is not particularly limited as long as the mechanical properties and heat resistance of the resin composition of the present invention are improved. Preferably, it is 0.05 to: 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin. .
  • the ratio of the layered silicate decreases, the mechanical strength and heat resistance tend to be reduced.
  • the ratio increases, the physical properties of the resin composition, particularly the fluidity and impact strength, tend to decrease.
  • the layered silicate added as necessary in various polyamide resin compositions and products described below in this specification is the above-mentioned layered silicate.
  • a part of the polyamide resin P A 92 C or PA 92/62 T used in the present invention can be substituted with another polymer component as long as the effects of the present invention are not impaired.
  • polystyrene resin such as polyethylene glycol dimethacrylate copolymer
  • polyamides such as polyamide, aromatic polyamido, aliphatic polyamido, alicyclic polyamido, etc.
  • polymers other than polyamido such as thermoplastic polymers and elastomers. It is done.
  • substitution ratio with the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50% by mass, more preferably 30% by mass or less.
  • additives may be added to the polyamide resin composition of the present invention as necessary (as described above).
  • the method for producing the resin composition of the present invention is not particularly limited as long as the layered silicate can be uniformly dispersed in the polyamide resin.
  • the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as 1, Add 9-nonanediamine and 2-methyl-1,8-octanediamine to widen the space between each layer of layered silicate beforehand.
  • a polyamide raw material is introduced between the layers, and further The raw material can be polymerized between the layers.
  • an organic compound may be used as a swelling agent, and the layers may be preliminarily spread to about 100 A or more and melt-mixed with the polyamide resin to disperse each layer in the polyamide resin.
  • the polyamide resin composition of the present invention can be formed into a molded product by, for example, extrusion molding, blow molding, compression molding, injection molding or the like.
  • Molded articles molded from the resin composition of the present invention are automobile parts, industrial materials, industrial materials, electrical and electronic parts, machine parts, office equipment parts, household goods, containers, sheets, films, fibers, and any other It can be a variety of molded products of application and shape. More specifically, tubes or hoses for automobile fuel piping, automobile raje overnight hoses, brake hoses, air conditioner hoses, wires covering materials, optical fiber covering materials, hoses, agricultural films, Lining, interior materials for buildings (wallpaper, etc.), films such as laminating steel sheets, sheets, automobile raje overnight tanks, chemical bottles, chemical tanks, bags, chemical containers, tanks such as gasoline tanks, tire tires Inner liner, tank valve
  • the resin composition containing the polyamide resin and the layered silicate of the present invention has high mechanical strength, heat resistance, and liquid or vapor barrier properties, and compared with the conventional nylon 6-based resin composition. Excellent in low water absorption, chemical resistance, hydrolysis resistance, etc., and has a wider moldable temperature range than a polyamide resin-based resin composition that uses 1,9_nonanediamine alone as a diminant component. It is possible to produce a tough molded body that is excellent in moldability and can be increased in molecular weight.
  • Parts used under harsh conditions such as power tools, general industrial parts, machine parts, electronic parts, automotive interior and exterior parts, engine room parts, automotive electrical parts, etc. have low water absorption, chemical resistance and resistance. In addition to being excellent in hydrolyzability and the like, high impact resistance is demanded (for example, Japanese Patent Application Laid-Open No. 2 0 00-1 2 9 1 2 2).
  • the present invention has a high impact resistance by adding an impact modifier to the polyamide resin PA 9 2 C or PA 9 2/62 T, and the conventional nylon. Compared to Ron 6 and Nylon 66-based compositions, it is superior in low water absorption, chemical resistance, hydrolysis resistance, etc., and from a polyamide resin composition using 1,9-nonanediamine alone as a diminant component.
  • the present invention provides a polyamide resin composition having a wide moldable temperature range and excellent melt moldability, and capable of producing a tough molded body capable of increasing the molecular weight.
  • the impact modifier is a component that improves the impact resistance of the polyamide resin.
  • the impact modifier is not particularly limited as long as it improves the impact resistance of the polyamide resin.
  • an elastomer is used. Can be mentioned. It is preferable that the elastomer has a flexural modulus measured in accordance with AS TM D—790, which is not more than 500 MPa. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
  • Impact modifiers include: (Ethylene and Z or propylene) ⁇ ⁇ -olefin copolymers, (Ethylene and or propylene) ⁇ ( ⁇ ,) 8-Unsaturated carboxylic acids and soot or unsaturated carboxylic acids Ester) -based copolymers, ionomer polymers, aromatic vinyl compounds / conjugate compound-based block copolymers, and these can be used alone or in combination.
  • the polymer is ethylene and / or ⁇ pyrene and 3 or more ash atoms ⁇ ⁇
  • This is a polymer copolymerized with olefin, and olefins with one or more ash ⁇ 3 are as follows: propylene, 1-butene, 1-pentene, 1 hexene, 1-heptene, 1-octene, 1 , 1-decene, 1
  • the above-mentioned (ethylene and / or propylene) ⁇ (;, 6-unsaturated power rubonic acid and Z or unsaturated carboxylic acid ester) copolymer is ethylene and Z or propylene and ⁇ ,; 8-unsaturated carbon
  • a polymer obtained by copolymerizing an acid and ⁇ or an unsaturated carboxylic acid ester monomer, and j8 —unsaturated carboxylic acid monomer includes acrylic acid and maleic acid, ⁇ ,] 6-As unsaturated carboxylic acid ester monomers, these unsaturated carboxylic acid methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester Decyl ester, etc., or a mixture thereof.
  • the ionomer polymer mentioned above is one in which at least a part of carboxyl groups of olefin and a, iS-unsaturated rubonic acid copolymer are ionized by neutralization of metal ions.
  • Ethylene is preferably used as the olefin, and acrylic acid and maleic acid are preferably used as the ⁇ , / 3_unsaturated carboxylic acid, but are limited to those exemplified here. Instead, an unsaturated carboxylic acid ester monomer may be copolymerized.
  • the metal ions are alkali metals such as Li, Na, ⁇ , Mg, Ca, Sr, Ba, etc., earth metals, Al, Sn, Sb, Ti , M n, F e, N i, C u, Z n, C d etc. can be mentioned.
  • An aromatic vinyl compound / conjugated gen compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated gen polymer block force.
  • a block copolymer having at least one coalescence block and at least one conjugate polymer block is used. Further, in the above block copolymer, the unsaturated bond in the conjugation polymer block may be hydrogenated.
  • the aromatic vinyl compound polymer block is a polymer block mainly composed of structural units derived from an aromatic vinyl compound.
  • aromatic vinyl compounds include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2, 6-dimethylstyrene, vinyl Naphthenol, vinylanthracene, 4-propyl styrene, 4-cyclohexyl styrene, 4- dodecyl styrene, 2-ethyl benzyl styrene, 4- (butyl butyl) styrene, aromatic Vinyl compound polymer block is ⁇ *
  • the aromatic vinyl compound-based polymer block may optionally have a structural unit composed of a small amount of other unsaturated monomer.
  • Conjugated polymer block consists of 1, 3-bugen, black ⁇ prene, isoprene, 2, 3-dimethyl-1,3-buchen, 1 3 pentene, 4 1 methyl -1, 3 —
  • conjugated gen compounds such as pen phenogen, 1, 3 — hexagen, etc.
  • a hydrogenated aromatic vinyl compound conjugated gen block copolymer Some or all of the unsaturated bonds in the conjugated gen-based polymer block are saturated by hydrogenation. It is a bond.
  • the distribution in the polymer block mainly composed of conjugated gen may be random, tapered, partially blocky, or any combination thereof.
  • the molecular structure of the aromatic pinyl compound conjugated gen block copolymer and its hydrogenated product may be any of linear, branched, radial, or any combination thereof.
  • the aromatic vinyl compound Z conjugated gen block copolymer and / or its hydrogen additive one aromatic vinyl compound polymer block and one conjugated gen polymer block are linear.
  • One or more of these copolymers and their hydrogenated additives are preferably used.
  • ethylene and / or propylene ⁇ ⁇ -olefin copolymers
  • ethylene and ⁇ or propylene ⁇ (a, j3-unsaturated carboxylic acids and / or unsaturated carboxylic esters )
  • block copolymer of a copolymer an ionomer polymer, an aromatic vinyl compound and a conjugation compound, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such components, functional groups having affinity for the polyamide resin are included in the molecule.
  • the amount of the impact modifier (B) is not particularly limited as long as the impact resistance of the polyamide resin (A) is improved.
  • the polyamide resin The amount of the impact modifier (B) with respect to (A) 100 parts by mass is preferably 10 to 100 parts by mass.
  • the amount of the impact modifier (B) decreases, the impact resistance does not improve.
  • the impact modifier (B) increases, the effect of the wide moldable temperature range of the polyamide resin composition is not recognized.
  • polyamide resin (A) to 100 parts by mass The amount of the impact modifier (B) is preferably 10 to 50 parts by mass, and more preferably 10 to 30 parts by mass.
  • the polyamide resin composition of the present invention may further contain the following components as optional components in addition to the polyamide resin PA 9 2 C or PA 9 26 2 T and the impact modifier. .
  • Polyamide resin P A 92 C or PA 92/62 T used in the present invention can be partially substituted with other polymer components as long as the effects of the present invention are not impaired.
  • the other polymers are as described in 1.4 above.
  • substitution ratio with the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50% by mass, more preferably 30% by mass or less.
  • additives can be added to the polyamide resin composition of the present invention within a range not impairing the effects of the present invention (as described above, a copper-containing compound is preferable as the heat-resistant agent, Copper halides such as copper iodide and copper bromide are particularly preferred
  • the amount of the same compound added is 10 to 10 as the copper content in the polyamide resin composition of the present invention.
  • An addition amount of 0 ppm is preferable
  • an alkyl halogen compound is further added as a heat-resistant auxiliary agent.
  • a phenolic antioxidant can be added to the polyamide resin composition of the present invention.
  • the antioxidant and the heat-resistant agent can be used in combination.
  • phenolic oxidizers include: ⁇ Reethylene glycol • Bis [3— (3 — t-butyl-5-methyl-4-hydroxyphenyl) propionate ⁇ ⁇ ], 1, 6 — hexanediol 'bis [3 —
  • Phosphorus antioxidant adjuvants include, for example, tris (2,4-di-tert-butylphenyl) phosphide, 2 _ [[2,4,8,10-tetrakis (1,1-dimethyl) Dibenzo [d, f] [1,3,2] dioxaphosphine 6-yl] oxy] ⁇ N, N-bis [2 _ [[2,4,8,1 0 Trakis (1, 1-dimethylethyl) dibenzo [d, f] [1,
  • Zeo-based antioxidant adjuvants include 2,2-thiodiethylene bis [3— (3,5-di-t-butyl-4-hydroxyphenyl) pionate], tetrakis [methylene-13_ ( Dodecylthio) pionate] methane and the like.
  • the method for adding the other polymer and the additive is not particularly limited as long as each of them can be dispersed in the polyamide resin, and at any point that does not impair the effect, Can be added to amide resins.
  • the other polymer and additive can be added immediately after the post polycondensation step of the polyamide resin.
  • the production method of the polyamide resin composition of the present invention is not particularly limited, and the polyamide resin (A) and the impact modifier (B) are melt-kneaded by a single-screw, twin-screw or multi-screw extruder.
  • other kneaders can be used.
  • the above other polymers and additives may be added during the melt kneading of the polyamide resin (A) and the impact modifier (B).
  • the polyamide resin composition of the present invention can be molded into various shaped bodies by known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding, press molding and the like. Especially in the fields of injection molding and blow molding It is for.
  • the polyamide resin preferably forms a matrix phase.
  • the heat resistance and mechanical properties are excellent.
  • the polyamide resin forms a discontinuous phase the mechanical properties and heat resistance of the resulting resin composition tend to be low. is there.
  • the polyamide resin composition of the present invention has a wide moldable temperature range.
  • automobile-related parts in particular, interior / exterior parts, engine room parts, automobile electrical parts, etc., and electrical / electronic parts / power tools.
  • machine parts such as industrial parts, gears and cams.
  • the polyamide resin composition of the present invention is not particularly limited.
  • a gear, a cam, a slider, a lever, an arm, a clutch, a felt clutch, an idler gear, a pulley, a mouth ring, a roller, a key for example, a gear, a cam, a slider, a lever, an arm, a clutch, a felt clutch, an idler gear, a pulley, a mouth ring, a roller, a key.
  • Mechanical parts such as stems, key cups, shutters, reels, shafts, joints, shafts, bearings and guides, outsert molded resin parts, insert molded resin parts, chassis, tray , Side plates, printers and parts for office automation equipment represented by copiers, video tape recorders, digital video cameras, cameras and cameras or video represented by digital cameras Equipment parts, cassette player, CD player, music player such as DVD player, CD—ROM, CD-R, DVD-R ⁇ M, optical disk drive such as DVD—R, other optical disk drives, Automotive parts such as gasoline tanks, fuel pump modules, valves, gasoline tank flanges, etc., door parts such as door locks, door handles, window regulators, and grills.
  • Suitable for seat belt peripheral parts such as parts, slip belts for seat belts and press potan.
  • it can be suitably used as industrial parts such as toys, fasteners, chains, conveyors, buckles, sports equipment, vending machines, furniture, musical instruments, and housing equipment.
  • the polyamide resin composition comprising the polyamide resin of the present invention and an impact modifier has high impact resistance and is low compared to conventional nylon 6 and nylon 66 compositions. Excellent water absorption, chemical resistance, hydrolysis resistance, etc., and has a wider moldable temperature range and excellent melt moldability than a polyamide resin composition using 1,9-nonanediamine alone as a diminant component. Furthermore, it is possible to produce a tough molded body capable of increasing the molecular weight.
  • the moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature is low water absorption.
  • any one that can be used as a heat-resistance improving agent for polyamide can be used, and organic or inorganic heat-resistant agents can be used according to the purpose.
  • Examples of the organic heat-resistant dragon of the heat-resistant agent used in the present invention include hindered phenol-based, hindered dominated-based, phosphorus-based, sulfur-based, benzotriazole-based, and the like. Screw [2-[3-
  • inorganic heat-resistant agent used in the present invention is a metal compound (salt) belonging to Group I transition series elements, such as halides, sulfates, and acetates of this metal.
  • Salt a metal compound belonging to Group I transition series elements, such as halides, sulfates, and acetates of this metal.
  • Salicylate nicochi ⁇
  • the amount of the heat-resistant agent used in the present invention is preferably in the range of 0.01 to 3.0 parts by mass, more preferably 0 to 100 parts by mass of the polyamide resin used in the present invention. Within the range of 0 1 to 2.0 parts by mass.
  • the blending amount is 0.01 parts by mass or more, the effect of improving heat resistance is particularly good.
  • the blending amount is 3.0 parts by mass or less, the heat-resisting agent-containing resin composition and the molded product formed therefrom are used. The effect of adding a heat-resistant agent can be sufficiently obtained while avoiding the occurrence of coloring and bubbling.
  • various additives can be combined as needed in addition to the polyamide resin and the heat-resistant agent, and these can be combined during or after the polyamide polycondensation reaction ( As mentioned above) .
  • the present invention also provides a molded article formed from the heat-resisting agent-containing resin composition of the present invention described above.
  • Molding methods from resin compositions containing heat-resistant agents into molded products include injection, extrusion, hollow, press, roll, foaming, vacuum * pressure All known molding methods applicable to polyamide such as empty and stretched can be used, and by these molding methods, a molded product such as a film, a sheet, a molded product, and a fiber can be processed.
  • predetermined amounts of polyamide resin, heat-resistant agent and various additives used as needed are mixed into a low-speed rotary mixer such as a V-type renderer or tumbler or a high-speed rotary mixer such as a Henschel mixer. After mixing in advance, a method of directly molding a molded product using an injection molding machine or an extrusion molding machine can be applied.
  • a low-speed rotary mixer such as a V-type renderer or tumbler
  • a high-speed rotary mixer such as a Henschel mixer.
  • Molded articles obtained by the present invention are molded articles such as various extruded molded articles, various injection molded articles, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded articles have been conventionally used. It can be used for a wide range of applications such as automobile parts, computers and related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, and household goods. It can be suitably used for various automotive parts and electrical / electronic parts that require heat resistance.
  • the heat-resistant agent-containing resin composition of the present invention has low water absorption, it has a wide moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature, and is excellent in melt moldability, excellent in chemical resistance and hydrolysis resistance. Furthermore, because of its excellent heat resistance, it is widely used as a molding material for industrial materials, industrial materials, household products, etc., especially for various automotive parts, electrical and electronic parts that require heat resistance. can do.
  • the present invention uses a polyamide resin PA 9 2 C or PA 9 2/62 T in combination with a release agent, so that the melting point and the thermal decomposition temperature are reduced while having low water absorption
  • the temperature range that can be estimated from the difference in temperature is as wide as 50 or more, for example, excellent in melt moldability, excellent in chemical resistance and hydrolysis resistance, and good sliding property between the mold and the molded product during molding and / or short.
  • a polyamide resin composition capable of achieving molding time.
  • the mold release agent used in the present invention imparts excellent moldability to the polyamide resin, in particular, good slippage between the mold and the molded product during molding, and no or short molding time.
  • mold release agents include polyalkylene glycol end-modified products, phosphate esters or phosphite esters, higher fatty acid monoesters, higher fatty acids or metal salts thereof, ethylene bisamide compounds, and low molecular weight polyethylene. And compounds such as magnesium silicate and substituted benzylidene sorbitols. These can be used alone or in combination of two or more.
  • the compounding amount of the release agent is within the range of 0.001 to 5 parts by mass, and further 0.05 to 3 parts by mass with respect to 100 parts by mass of the above-mentioned polyamide resin used in the present invention. Is preferred.
  • the blending amount is 0.01 part by mass or more, and further 0.05 part by mass or more, the moldability improving effect is particularly good, and when it is 5 parts by mass or less, and further 3 parts by mass or less, the moldability While the improvement effect can be obtained sufficiently, the physical properties of the molded product are unlikely to deteriorate.
  • polyalkylene glycol end-modified products examples include polyethylene glycol end-modified products, and polypropylene glycol. And the like.
  • the terminal modification is preferably performed with an amino group, a carboxy group or a methyl group. As a more specific example, the following formula:
  • X represents NH 2 , or COOH, or H
  • R represents a linear or branched alkylene group having 1 to 10 carbon atoms
  • n represents 4 to 1 200 Number
  • X represents NH 2 , CO OH, or H
  • R represents a linear or branched alkylene group having 1 to 10 carbon atoms
  • n is a number from 1 to 20 0.
  • the blending amount of the terminal modified product of polyalkylene glycol is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the blended amount of the terminal modified product of polyalkylene glycol is not less than 0.01 part by mass, the effect of shortening the molding time by shortening the cooling time during molding is particularly good.
  • the blending amount exceeds 5 parts by mass, the effect of shortening the molding time is not greatly improved, but the mechanical properties of the molded product tend to be lowered.
  • phosphate esters examples include the following formula:
  • n 1 or 2
  • R is an alkyl group having 1 to 10 carbon atoms
  • R includes an ethyl group, Examples thereof include a butyl group, an octyl group, and an ethylhexyl group.
  • phosphites examples include the following formula:
  • R is hydrogen, or an alkyl group having 10 to 25 carbon atoms, more preferably 12 to 20 carbon atoms, or a phenyl group, or a part of these groups is substituted with a hydrocarbon group. Represents a group
  • R includes an decyl group, a lauryl group, a tridecyl group, a stearyl group, an aryl group such as an oleyl group; an aromatic group such as a phenyl group or a biphenyl group; an ethyl group, a propyl group, a t-butyl group, or a nonyl group.
  • An aromatic group having a substituent such as
  • phosphoric esters and phosphites include di (2-ethylhexyl) phosphate, tridecyl phosphite, tris (tridecyl) phosphite, tristearyl phosphate.
  • Aliphatic phosphites such as salmon and aromatic phosphites such as aliphatic phosphite esters, triphenyl phosphites, and diphenyl monodecyl phosphites.
  • the blending amount of the phosphoric acid ester and the phosphorous acid ester is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. .
  • the above-mentioned blending amount of phosphoric acid ester and phosphorous acid ester is not less than 0.1 part by mass, the slippage between the mold and the molded product during molding is particularly good and the molding cycle time is reduced. The shortening effect is particularly good.
  • the blending amount is 5 parts by mass or less, the compatibility between the phosphoric acid ester and the phosphorous acid ester and the polyamide resin is good, and the occurrence of silver (silver mark) on the surface of the molding or the molding Mechanical properties are unlikely to deteriorate.
  • Preferred higher fatty acid monoesters include the following formula: RCO— O— R 2
  • R 1 and R 2 each independently represents an alkyl group having 8 to 32 carbon atoms, preferably 10 to 30 carbon atoms
  • an ester compound of a higher fatty acid and a higher aliphatic monohydric alcohol can be used.
  • R 1 and R 2 in the above formula include aliphatic groups such as a decyl group, a lauryl group, a ridylyl group, a stearyl group, and an oleyl group.
  • Examples of the higher fatty acid include myristic acid, palmitic acid, behenic acid, oleic acid, and aragic acid.
  • Examples of higher aliphatic alcohols include myristyl alcohol, behenyl alcohol, oleyl alcohol, stearyl alcohol, and hexyldecyl alcohol.
  • higher fatty acid monoesters include higher fatty acid monoalkyl esters such as myristyl myristate, stearyl stearate, behenyl behenate, oleyl oleate, myristate. Hexyldecyl and the like can be mentioned.
  • the blending amount of the higher fatty acid monoesters is preferably from 0.01 to 5 parts by weight, more preferably from 0.05 to 3 parts by weight, based on 100 parts by weight of the polyamide resin.
  • the amount of the higher fatty acid monoester is 0.01 part by mass or more, the slip property between the mold and the molded product during molding is particularly good.
  • the amount is 5 parts by mass or less, the higher fatty acid monoester
  • the compatibility between the resin and the polyamide resin is good, and it is difficult for silver to form on the surface of the molded product and to reduce the mechanical properties of the molded product.
  • preferred higher fatty acids or salts thereof include:
  • n 9 to 25, preferably 11 to 20 and X represents H or a metal of Groups 1 to 1 II of the Periodic Table
  • higher fatty acids examples include stearic acid, palmitic acid, oleic acid, aragidic acid, and behenic acid.
  • higher fatty acid metal salts include zinc stearate, lithium stearate, calcium stearate, and aluminum palmitate.
  • the compounding amount of the higher fatty acid and its metal salt is polyamide resin. 0.01-5 mass parts is preferable with respect to mass parts, and 0.05-5 mass parts is more preferable.
  • the slip property between the mold and the molded product at the time of molding is particularly good. Good compatibility between the esters and the polyamide resin, and it is difficult for silver to form on the surface of the molded product and mechanical properties of the molded product, especially elongation at break at break and impact strength.
  • Examples of preferred ethylene bisamide compounds include the following formula: CH 3 (CH 2 ) m CONH (CH 2 ) 2 NH C 0 (CH 2 ) n CH 3 (wherein m and n are each independently 9 to 2 5, preferably a number between 10 and 20)
  • ethylene bisamide compound More specific examples of the ethylene bisamide compound include ethylene bisstearyl amide and ethylene bispalmityl amide.
  • the blending amount of the ethylene bisamide compound is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the blending amount of the ethylene bisamide compound is not less than 0.01 parts by mass, the slip property between the mold and the molded product during molding is particularly good.
  • the amount exceeds 5 parts by mass molding While the time shortening effect is not greatly improved, the surface appearance and mechanical properties of the molded product tend to decrease.
  • Preferable low molecular weight polyethylene includes those having a molecular weight in the range of 500 to 500, more preferably those having a molecular weight in the range of 100 to 300.
  • the blending amount of the low molecular weight polyethylene is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the blending amount of the low molecular weight polyethylene is not less than 0.01 part by mass, the slip property between the mold and the molded product during molding is particularly good.
  • the blending amount is 5 parts by mass or less, the compatibility between the low molecular weight polyethylene and the polyamide resin is good, and the occurrence of silver on the surface of the molding and the deterioration of the mechanical properties of the molding are unlikely to occur. .
  • Examples of preferable magnesium silicate include those having an average particle diameter of 1 to 1 O ⁇ m. When the average particle size is 1 m or more, white unevenness on the surface of the molded product hardly occurs. When the average particle size is ⁇ ⁇ ⁇ or less, the mechanical properties of the molded product, in particular, the elongation at break and the impact strength. Is difficult to decrease. For the purpose of improving the adhesion to the polyamide resin, surface treatment with magnesium silicate may be performed on magnesium silicate.
  • the compounding amount of magnesium silicate is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the above-mentioned amount of magnesium silicate is not less than 0.01 parts by mass, the effect of improving the moldability is particularly good.
  • the blending amount is 5 parts by mass or less, the mechanical properties of the molded product, particularly elongation at break at break and impact strength are hardly lowered.
  • Examples of preferable substituted benzylidene sorbitols include substituted benzylidene sorbitols synthesized by dehydration condensation of sorbitol and substituted benzaldehyde under an acid catalyst. Replacement vanes The condensation ratio of aldehyde to sorbitol is preferably 1 mol or 2 mol per 1 mol of sorbitol. Therefore, these substituted benzylidene sorbitols have the following formula:
  • R 1 represents H, a hydroxyl group, a halogen, or an alkyl group having 1 to 20 carbon atoms
  • scales 2 and 3 each independently represent H, a hydroxyl group, a halogen, or an alkyl group having 1 to 20 carbon atoms
  • substituted benzylidene sorbitols include 1, 3-benzylidene sorbitol, 1, 3, 2, 4, dibenzylidene sorbitol, 1, 3-mono (p-hydroxybenzylidene) sorbitol, 1, 3, 2, 4 — Di (p — Hydroxy. Benzylidene) sorbitol, 1, 3 — Mono (p — Black benzylidene) sorbitol, 1, 3, 2, 4 — Di (p — Black mouth benzylidene) Sorbitol, 1, 3-Mono (m_2 ⁇ benzylidene) sorbitol, 1, 3, 2
  • the amount of the substituted benzylidene sorbitols is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • o ⁇ 3 3 ⁇ 4 part is more preferable.
  • Substituted benzylidene sorbitols When the above compounding amount is 0.01 parts by mass or more, the effect of shortening the molding time by shortening the cooling time during molding is particularly good. If the blending amount exceeds 5 parts by mass, the effect of shortening the molding time is not greatly improved.
  • the polyamide resin of the present invention is composed of PA 9 2 C or PA 9 2/62 T.
  • other polyamide resins or other thermoplastic resins can be used as long as the effects of the present invention are not impaired.
  • polyamide resins or other thermoplastic resins that can be blended 1.
  • additives can be added to the polyamide resin composition of the present invention as required (as described above).
  • the layered silicic acid optionally added may be a component that imparts excellent mechanical properties and heat resistance to the pad resin.
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is not particularly limited as long as the effect of improving the mechanical strength and heat resistance is obtained. Preferably, it is 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the amide resin. .
  • the proportion of layered silicate is lowered, the improvement in mechanical strength and heat resistance tends to be reduced.
  • the proportion is increased, the fluidity of the resin composition and the physical properties of the obtained molded product, particularly the impact strength is lowered. Tend.
  • the present invention also provides a molded article formed from the above-described polyamide resin composition of the present invention.
  • a molding method from the polyamide resin composition to the molded product all known molding processing methods applicable to the polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum 'vacuum, drawing, etc. can be used. Yes, by these molding methods, it can be processed into molded products such as films, sheets, molded products, and fibers.
  • a predetermined amount of a polyamide resin, a release agent and various additives to be used as needed is mixed with a high-speed rotary mixer such as a V-type renderer or a tumbler or a Henschel mixer. It is possible to apply a method of directly molding a molded article using an injection molding machine or an extrusion molding machine after mixing in advance using a machine.
  • Molded articles obtained by the present invention are molded articles such as various extruded molded articles, various injection molded articles, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded articles have been conventionally used. It can be suitably used for a wide range of applications such as automobile parts, computers and related equipment, optical equipment parts, electrical / electronic equipment, information, communication equipment, precision equipment, civil engineering, building supplies, medical supplies, and household goods.
  • the polyamide resin composition of the present invention has a wide moldable temperature range that can be estimated from the difference between the melting point and the thermal decomposition temperature while having low water absorption, and melt moldability. Excellent in chemical resistance and hydrolysis resistance, as well as good slip between the mold and the molded product and Z or short molding time at the time of molding, so it can mold industrial materials, industrial materials, household products, etc. Can be used widely as a material.
  • Crystalline polyamides are preferably crystallized sufficiently to exhibit their properties, but crystalline polyamides such as Nylon 6 and Nylon 6 6 generally have a low crystallization rate and are molded. Depending on the conditions, there is a problem that the crystallization of the polyamide during molding is insufficient, the crystallization of the polyamide occurs after molding, and the dimensional stability is poor. Therefore, there is a need for a polyamide resin having a high crystallization rate and excellent dimensional stability even when molded under various molding conditions, and a molded body produced using the polyamide resin.
  • the present invention has less warpage and superior dimensional stability, chemical resistance and water resistance compared to injection molding materials such as nylon 6. It is an injection molding material with excellent decomposability, and has a wider moldable temperature range and better melt moldability than materials using 1,9-nonanediamine alone as the jamin component, and has a higher molecular weight. Provided is an injection molding material capable of producing a tough and strong injection molded body.
  • injection molding material refers to the production of an injection molded body. Means a material to do.
  • the injection molding material of the present invention may further contain the following components as optional components in addition to the polyamide resin P A 92 2 C or P A 9 26 2 T.
  • polyamide resins P A 92 C and P A 92/62 T used in the present invention can be partially substituted with other polymer components as long as the effects of the present invention are not impaired.
  • Other polymer components are as described above in 1.4.
  • other polyamides such as polyoxides, aromatic polyamides, aliphatic polyamides, alicyclic polyamides, etc.
  • polymers other than polyamides such as thermoplastic polymers and elastomers can be mentioned.
  • substitution ratio with the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50% by mass, more preferably 30% by mass or less.
  • injection molding material (polyamide resin composition) of the present invention can contain other additives as long as the effects of the present invention are not impaired (as described above).
  • the injection molding material of the present invention can produce an injection molded article with less warpage and excellent dimensional stability with only the above-mentioned polyamide resin. However, in applications where high-precision dimensional stability is required.
  • the injection molding material of the present invention can further contain a layered silicate.
  • the injection molding material of the present invention can improve the rigidity, weather resistance, Z or heat resistance, and barrier properties against liquids or vapors.
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but is preferably 0 with respect to 100 parts by mass of the polyamide resin. It is 0.5 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass. If the ratio of layered silicate is low, the effect of layered silicate will not be exhibited, and if the ratio is high, the melt viscosity will be extremely high, resulting in deterioration of molding processability and impact resistance. Tend to.
  • the injection-molded body of the present invention can be produced by molding an injection molding material in combination with not only injection molding but also extrusion molding, blow molding, compression molding, injection molding, and the like.
  • the injection molded body is not particularly limited, but is a molded body that is required to have low warpage and excellent dimensional stability, for example, a component having a complicated shape, for example, an oil tank for a two-wheeled or four-wheeled vehicle, an intake system. Examples of components suitable for the manufacture of parts, and their integrated parts, electrical component cases, and other containers.
  • the injection-molded body includes a welding and joining member.
  • the injection-molded body includes, for example, intake system parts such as an automobile interior hold for which high strength and durability are required, a cylinder head cover, an interior joint 2 Intake system module parts integrating hold and air cleaner, cooling system parts such as water inlet and water outlet, fuel system parts such as fuel injection and fuel delivery pipes, Oy Containers such as water tanks and electrical component cases such as switches.
  • the injection molding material of the present invention is an injection molding material with less warpage, superior dimensional stability, excellent chemical resistance and hydrolysis resistance compared to injection molding materials such as Nylon 6. Compared to materials using 1,9-nonanediamine as a component, it is possible to produce a tough molded body with a wider moldable temperature range and better melt moldability, and further capable of higher molecular weight.
  • Crystalline polyamides are widely used as materials for hollow molded parts such as bottles, tanks, air ducts and hollow pipes because of their excellent characteristics and ease of melt molding (for example, 3 — 2 4 1 5 5)), however, on the other hand, problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, and deterioration in hot water have also been pointed out. There is a growing demand for excellent polyamides.
  • the present invention uses PA 9 2 C or PA 9 2/62 T so that it has the same hollow moldability as compared with the conventional hollow molded parts using Nylon 6. It has low water absorption, chemical resistance, hydrolysis resistance, etc., and has a wider moldable temperature range than a hollow molded part that uses 1,9-nonanediamine alone as a diminant component. In addition, it provides high-molecular-weight and tough hollow molded parts.
  • the hollow molded part of the present invention is produced using a polyamide resin (A) and preferably a layered silicate (B).
  • hollow molded part means a part manufactured by hollow molding.
  • Hollow molding includes rotational molding, slush molding, sheet blow molding, injection blow molding, etc. Be turned.
  • the hollow molded part of the present invention is a part or product molded by hollow molding, for example, various tanks such as fuel tanks, for example, gasoline tanks, oil tanks, other tanks, agricultural chemical bottles, and drinking water bottles. It can be used for various machines such as air ducts, internal clearances and automobiles, as well as automobile intake / exhaust parts, air boilers, fenders, bumpers, etc. Hollow molded parts include fuel delivery pipes, throttle bodies, resonators, air cleaner boxes, suspension boots, air cleaners, air cleaners, resonance evenings, fuel rails, hose joints. Can be mentioned.
  • the hollow molded part of the present invention is characterized by using PA 9 2 C or PA 9 2/62 T, and it is preferable that the layered silicate further contains a layered silicate. It is a component that imparts viscosity when manufacturing molded parts.
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but is preferably from 0.05 to 100 parts by mass of the polyamide resin. It is 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the proportion of layered silicate is low, the effect of layered silicate is not exhibited, and when the proportion is high, the melt viscosity becomes extremely high and the moldability tends to deteriorate or the impact resistance tends to decrease. . (4) Other polymers
  • a part of the polyamide resin P A 92 C or PA 92/62 T used in the present invention can be substituted with another polymer component as long as the effects of the present invention are not impaired.
  • other polymer components described above in 1.4 include, for example, other polyamides such as polyoxamides, aromatic polyamides, aliphatic polyamides, alicyclic polyamides, and the like. Examples thereof include polymers other than glass, for example, thermoplastic polymers and elastomers.
  • substitution ratio by the other polymer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably less than 50% by mass, more preferably 30% by mass or less. is there.
  • hollow molded part of the present invention can contain other additives as long as the effects of the present invention are not impaired (as described above).
  • Fig. 2 shows a cross-sectional view of a fuel tank as an example of a hollow molded product.
  • the hollow molded part of the present invention has equivalent hollow moldability compared to the conventional hollow molded part using Nylon 6, and has low water absorption, chemical resistance, hydrolysis resistance, etc. It is a hollow molded part that is superior and has a wider moldable temperature range and better melt moldability than a hollow molded part that uses 1,9-nonanediamine alone as the jam component, and is tough with a high molecular weight.
  • Polyamide resins are widely used as fibers for clothing and industrial materials because of their excellent properties and ease of melt molding. Particularly in the case of filament cocoons, good physical strength and elongation are required. Ma In addition, these polyamide resins have been pointed out to have problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, and deterioration in hot water. Polyamide resins with superior dimensional stability and chemical resistance are also pointed out. The demand for is increasing.
  • polyamide resin composition for filaments examples include, for example, JP-A-3 1 8 1 3 6 4, Polyamide resin (A) 100 parts by weight and layered silicate (B) 0.0 5 to 3
  • a polyamide resin composition for filaments comprising 0 part by weight has been proposed.
  • this technique has a problem that it is difficult to achieve both low water absorption, chemical resistance, hydrolysis resistance, molding processability, physical strength and elongation.
  • the present invention uses a polyamide resin PA 9 2 C or PA 9 2 Z 6 2 T, is excellent in mechanical strength and elongation, and has low water absorption while being melted.
  • a high molecular weight can be obtained by polymerization, and a moldable temperature range that is estimated from the difference between the melting point and the thermal decomposition temperature is wide, and it has excellent melt moldability, and provides a film with excellent chemical resistance and hydrolysis resistance.
  • the polyamide resin of the present invention is composed of PA 9 2 C or PA 9 2/62 T, but other polyamide resins or other thermoplastic resins should be mixed within a range not impairing the effects of the present invention. Is also possible. Other polyamide resins or other thermoplastic resins that can be blended are as described in 1.4 above.
  • a layered silicate As the reinforcing agent, for example, a layered silicate can be preferably used.
  • the layered silicate imparts excellent mechanical strength obtained by good rigidity, high elasticity, high pulling force, etc., and excellent texture without impairing the elongation of the filament of the present invention. Can do.
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is not particularly limited as long as the effect of improving mechanical strength and texture is obtained, but with respect to 100 parts by mass of the polyamide resin used in the present invention.
  • the amount is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the ratio of the layered silicate is lowered, the improvement effect tends to be reduced.
  • the ratio is increased, the fluidity of the resin composition and the physical properties of the obtained molded product, particularly, the impact strength tends to be lowered.
  • the filament of the present invention can be used as various monofilaments and multifilaments, and can be used for brush prestle, fishing line, hook-and-loop fasteners, tire cords, clothing filaments, artificial turf. And carpets, seats for automobile seats, fishnets, ropes, sills, thread for filters, filaments for lawn mowers, toothbrushes, and floor mats for automobiles.
  • the method for forming the filament of the present invention is not limited to these methods.
  • the raw material composition containing a polyamide resin is melted with a melt extruder such as a single screw, and the discharge amount is set. It can be produced by extruding the melt from a spinneret through a gear pump that is controlled quantitatively, and taking it out at a predetermined take-up speed while cooling with air or water.
  • the filament thus obtained may be further stretched at various magnifications depending on the application. Also, melt spinning and drawing May be performed simultaneously.
  • the filament may be monofilament or multifilament, and may be twisted or untwisted.
  • the filament cross-section may be circular, or it may be an irregular cross-section such as a hollow or star shape.
  • the present invention has excellent barrier properties against liquids, vapors and Z or gas, and particularly excellent in gas barrier properties under high humidity. It is possible to increase the molecular weight by melt polymerization while having low water absorption, and the moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature is as wide as, for example, 50 or more, and it has excellent melt moldability. It was found that a polyamide film excellent in heat resistance and hydrolysis resistance can be obtained.
  • the polyamide resin of the present invention is composed of PA 9 2 C or PA 9 2/62 T, but other polyamide resin or other thermoplastic resin is mixed within a range not impairing the effects of the present invention. It is also possible. Other polyamide resins or other thermoplastic resins that can be blended are as described in 1.4 above.
  • various additives can be combined as needed in addition to the above-mentioned polyamide resin, and these can be combined during or after the polyamide polycondensation reaction ( As mentioned above) .
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is not particularly limited as long as the effect of improving the mechanical strength, heat resistance, and barrier properties is obtained, but with respect to 100 parts by mass of the polyamide resin used in the present invention.
  • the amount is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the ratio of the layered silicate decreases, the improvement effect tends to decrease.
  • the ratio increases, the fluidity of the resin composition and the physical properties of the obtained molded product, particularly the impact strength, tend to decrease. is there.
  • the polyamide film of the present invention may be a stretched film or an unstretched film, and can be molded using any molding method known in the field of polyamide films.
  • a predetermined amount of polyamide resin and various other components used as necessary are melt-kneaded with an extruder, the kneaded product is extruded into a film form from a T die, and a casting roll surface
  • An unstretched film can be formed by applying a T-die method in which the film cast above is cooled or a tubular method in which the kneaded product is extruded from a ring die into a cylindrical shape and then air-cooled or water-cooled.
  • the stretched film can be formed by a method of stretching the unstretched film uniaxially or biaxially and heat-setting as necessary below the melting point of the polymer constituting the unstretched film.
  • the polyamide film of the present invention is one layer of a multilayer film. You may use as what comprises the above.
  • the layers other than the polyimide film of the present invention include, for example, polyolefin films made of low density polyethylene, high density polyethylene, polypropylene, and the like, polyester films, copolymers made of ethylene-vinyl acetate copolymer, and the like. Polymer film, ionomer resin film, etc. can be used according to the purpose.
  • the laminated film can be formed using a known method such as an adhesion method or a coextrusion method.
  • the bonding method the polyimide film of the present invention and one or more other films may be bonded with an adhesive.
  • the co-extrusion method the raw material polymer melts of the polyamide film of the present invention and one or more other films are melt-coextruded from a multilayer die through an adhesive resin as necessary. That's fine.
  • the polyamide film of the present invention can be suitably used for applications such as industrial materials, industrial materials, and household goods, and more specifically for food packaging, particularly for applications where the contents are liquid, such as for retort. It can also be used to impart antifungal effects.
  • the polyamide film of the present invention has an excellent barrier property against liquids, vapors, Z or gas, and has a low water absorption, but can be made to have a high molecular weight by melt polymerization, and from the difference between the melting point and the thermal decomposition temperature.
  • Barrier film used in applications such as industrial materials, industrial materials, and household goods, such as food packaging, because it has a wide range of moldable temperatures, excellent melt moldability, and excellent chemical and hydrolysis resistance. Can be used widely.
  • polyamide resin is applied to metal substrates. Adhesion is required. In addition, problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, and deterioration in hot water have been pointed out in these polyamide resins. Polyamide resins with superior dimensional stability and chemical resistance are also pointed out. There is a growing demand for
  • a technique for providing a polyamide resin excellent in adhesion to a metal substrate is disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-034 265.
  • this technology there are problems that water absorption of the polyamide resin tends to cause changes in physical properties, generation of wrinkles on the metal base material, and deterioration in adhesion between the metal base material and the metal coating material during long-term use.
  • the metal coating material of the present invention When the metal coating material of the present invention is formed on a metal substrate without using a primer, for example, the metal coating material preferably further contains an adhesion improver.
  • an adhesion improver conventionally known ones can be used, and examples thereof include thermoplastic elastomers, particularly epoxidized styrene elastomers, modified polyolefins, and silane coupling agents.
  • conjugation compound examples include butadiene, iso
  • the molecular structure of the block copolymer is preferably linear.
  • the styrenic compound (A) and the conjugated diene compound (B) may have a structure such as A_B—A, B_A—B_A, A—B_A_B—A, or the like.
  • a monoconjugated gen compound block copolymer is preferred.
  • the block copolymer may have a multifunctional coupling agent residue at the molecular end.
  • the manufacturing method of the block copolymer may be any manufacturing method as long as the block copolymer having the above-described structure is obtained.
  • Japanese Patent Publication No. 4 0-2 3 7 9 8 Japanese Patent Publication No. 4 3-1 7 9 7 9, Japanese Patent Publication No. 4 6-3 2 4 1 5, Japanese Patent Publication No. 5 6-2 8 9 2 5
  • Japanese Patent Publication No. 4 0-2 3 7 9 8 Japanese Patent Publication No. 4 3-1 7 9 7 9, Japanese Patent Publication No. 4 6-3 2 4 1 5, Japanese Patent Publication No. 5 6-2 8 9 2 5
  • the method described in 1) it is possible to produce a styrene compound monoconjugate compound block copolymer in an inert solvent using a lithium catalyst or the like.
  • Japanese Patent Publication No. 4 2-87 0 4 Japanese Examined Publication No. 4 3-6 6 3 6, or Japanese Patent Publication No.
  • the Hyde port Paokisai earths peroxide Hydrogen evening one shear Ribuchiru Hachii Doropa one Okisai de, cumene Hachii de port C 0 one Okisai de like.
  • “peracids” include performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, and the like. Of these, peracetic acid is preferred because it is industrially produced in large quantities, can be obtained at low cost, and has high stability.
  • the amount of epoxidizing agent used is not strictly limited and can be changed depending on the individual epoxidizing agent used, the desired degree of epoxidation, and the properties of the individual block copolymers used.
  • a catalyst as necessary in the conversion.
  • an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.
  • Catalytic effect can be obtained by using in combination with each of sodium butylhydroxide.
  • peracetic acid is preferably 0 to 70. This is because decomposition of peracetic acid occurs when it exceeds 7 O t :. No special operation of the reaction mixture is required, for example, the raw material mixture may be stirred for 2 to 10 hours.
  • the reaction temperature of the epoxidation can be changed according to the reactivity of the epoxidizing agent used according to a conventional method.
  • Isolation of the epoxidized styrenic thermoplastic elastomer obtained is, for example, by precipitation with a poor solvent, epoxidized styrenic thermoplastic elastomer is poured into hot water with stirring, and the solvent is distilled off. It can be carried out by a method, a method in which the solvent is directly dried by heating and / or depressurization. Moreover, when it finally uses in a solution form, it can also be used without isolation.
  • the blending amount of the epoxidized styrenic thermoplastic elastomer is preferably 3 to 30 parts by weight, more preferably 3 to 28 parts by weight, and 3 to 25 parts by weight with respect to 100 parts by weight of the polyamide resin. Part is particularly preferred.
  • the amount is 3 parts by mass or more, the adhesion between the metal substrate and the metal coating is particularly good, and when the amount is 30 parts by mass or less, the mechanical properties and surface properties of the polyamide resin are present. Is hard to be damaged.
  • a silane coupling agent chemically bonds an organic functional group having affinity or reactivity to an organic resin to a hydrolyzable silyl group having affinity or reactivity to an inorganic material.
  • This is a silane compound having the structure described above.
  • the hydrolyzable group bonded to silicon include an alkoxy group, a halogen, and an acetonitrile group, and usually an alkoxy group, particularly a methoxy group and an ethoxy group are preferably used.
  • the number of hydrolyzable groups attached to one key atom is selected between 1 and 3.
  • organic functional group examples include an amino group, an epoxy group, a vinyl group, a strong propyl group, a mercapto group, a group, a rogen group, a methyloxy group, and an isocyanate group. It is an amino group or an epoxy group.
  • silane-powered adhesives i such as ⁇ -aminoethyl trioxysilane, ⁇ -aminopropyl bilioxysilane, single aminobutyl triethyloxysilane, ⁇ -aminoprobitrite methoxysilane, Ryoaminopropylene silane, xyaminopropyl methylne xysilane, Nylamino propylmethyl jetoxy silane, N — ⁇ — (Aminoethyl) Ichien amiaminopropyl xysilane, ⁇ -j8- (Anoethyl)-Amino-propyl dimethyloxysilane, N _ ⁇ -(Aminoethyl)-Amino-propylene oxysilane, uraido-dope pitrimethysilan, __ureidopropylene ⁇ -Silane, ⁇ -Family
  • Epoxy group-containing silanes such as ethitriethoxysilane, vinyl group-containing silanes such as vinyltrimethylsilane, vinyl-trioxysilane, vinylmethyldimethoxysilane; Lupoxyl thiol oxysilane, ⁇ -Carboxycylphenylbis (2 — methoxyxoxy) silane, ⁇ — ⁇ — ( ⁇ — carboxymethylaminoethyl) monoaminopropyl trimethoxysilane and other silanes containing loxyxyl groups Mercaptopropyl, trimethoxysilane, ⁇ -mercaptopropyl lyeoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyl methoxysilane, etc.
  • the amount of the silane coupling agent is preferably 0.11 to 0.00 parts by weight, more preferably 0.11 to 0.3 parts by weight, with respect to 100 parts by weight of the above-mentioned polyamide resin. In the case of 0.5 parts by mass or more, the adhesion of the metal coating material to the metal substrate is particularly good.
  • the metal coating material of the present invention can be applied to a wide range of metal substrates such as non-ferrous metals such as aluminum and iron.
  • Applications of metal coating materials include anti-corrosion coating for general industrial fluid metal pipes, steel pipes for fuel, oil and brake fluids for automobiles, anti-corrosion coating for metal pipes such as aluminum pipes, metal wire
  • it can be used for coating of water tanks such as coatings and aquarium tanks, and is particularly preferred for metal pipes for automobiles.
  • Figure 3 shows a cross-sectional view of an example of resin coating on a metal tube.
  • 3 1 is a metal tube and 3 2 is a coating resin.
  • the method of coating the metal substrate with the metal coating material of the present invention is not limited to these methods.
  • a polyamide resin composition that is already in a molten state such as a steel pipe coating by extrusion, is used as an adherend.
  • a method for coating a metal substrate, such as powder coating, a metal substrate that is an adherend is heated, and the solid polyamide resin composition is melted by the heat to form a metal substrate. Examples thereof include a coating method, and a method in which a metal substrate and a solid state polyimide resin composition in contact with each other are heated and coated.
  • the metal substrate Prior to coating with the metal coating material of the present invention, the metal substrate may be subjected to primer treatment using a conventionally known primer for metal.
  • the temperature of the polyamide resin composition is preferably maintained at a temperature that does not alter the polyamide resin composition.
  • the metal coating material of the present invention has low water absorption, it can be polymerized by melt polymerization, has a wide moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature, and has excellent melt moldability and chemical resistance. Because of its excellent hydrolysis resistance, it can be used for general industrial fluid metal pipes, steel pipes for automobile fuel, oil, brake fluid, etc. It can be widely used as a metal coating material in metal coating applications such as coatings for water tanks and water tanks.
  • Polyamide resin is a binder resin for resin compositions containing inorganic particles such as metals and inorganic compounds because of its excellent properties and ease of melt molding. Is also preferably used.
  • Japanese Patent Application Laid-Open No. 2000-1 640 039 proposes a thermoplastic resin composition comprising an inorganic powder having a specific gravity of less than 10; an inorganic powder having a specific gravity of 10 or more; and a thermoplastic resin. Has been.
  • the polyamide resin has problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, and degradation in hot water, and there is a need for polyamides that solve these problems. It is growing.
  • Japanese Patent Application Laid-Open No. 6-122-186 describes a metal powder, a metal oxide powder or an inorganic compound having a specific gravity of 4 or more, a polyamide resin and a phenol resin.
  • a high specific gravity plastic composition is proposed.
  • the present invention uses a polyamide resin PA 9 2 C or PA 9 2/62 T as a binder resin for organic particles, so that the binder resin has a high molecular weight by melt polymerization while having low water absorption.
  • a moldable temperature range estimated by the difference between the melting point and the thermal decomposition temperature is as wide as, for example, 50 or more, excellent in melt moldability, and excellent in chemical resistance and hydrolysis resistance. provide.
  • Examples of the inorganic particles that can be used in the present invention include particles of metals, metal oxides, inorganic compounds, and the like, which can be appropriately selected depending on the application. Specifically, for example, metals such as tungsten, iron, zinc, tin, lead and copper, metal alloys such as tungsten copper and tungsten silver, metal oxides such as iron oxide and zinc oxide, and sulfides such as molybdenum sulfide And particles.
  • metals such as tungsten, iron, zinc, tin, lead and copper
  • metal alloys such as tungsten copper and tungsten silver
  • metal oxides such as iron oxide and zinc oxide
  • sulfides such as molybdenum sulfide And particles.
  • the inorganic particles may be used alone or in combination of two or more, and may be subjected to surface treatment.
  • Examples of the surface treatment include surface treatment with a titanate-based coating agent and surface treatment with a silane-based surface treatment agent.
  • the surface treatment with a titanate coupling agent for example, the known method described in the above-mentioned Japanese Patent Laid-Open No. 2-255570, and for the surface treatment with a silane-based surface treatment agent, for example, A known method described in 0 — 1 5 8 5 0 7 can be adopted.
  • the mass ratio of the polyamide resin and the inorganic particles described above is
  • Polyamide resin Z inorganic particles can be in the range of 50 Z 50 to 5Z 95, more preferably in the range of 20/80 to 5Z 95. In this case, high specific gravity, magnetized It is possible to more easily provide the characteristics such as.
  • the polyamide resin of the present invention is composed of PA 9 2 C or PA 9 2/62 T, but other polyamide resins or other thermoplastic resins are mixed within a range not impairing the effects of the present invention. It is also possible. Other polyamide resins or other thermoplastic resins that can be blended are as described in 1.4 above.
  • various additives can be combined as necessary, and these can be combined during or after the polyamide polycondensation reaction (as described above).
  • a lubricant component such as a metal stearate.
  • a predetermined amount of polyamide resin, inorganic particles, and various additives used as needed may be added to a V-type renderer, a tumbler. It is possible to apply a method of directly molding a molded product using an injection molding machine or an extrusion molding machine after mixing in advance using a low-speed rotary mixer such as — or a high-speed rotary mixer such as a Henschel mixer.
  • Molded articles obtained by the present invention are molded articles such as various extruded molded articles, various injection molded articles, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded articles have been conventionally used. It can be used for a wide range of applications such as automobile parts, computers and related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, and household goods, among which resin It can be suitably used for applications such as magnets and high specific gravity molded products.
  • Figure 4 shows a cross section of a resin-bonded magnet as an example.
  • 4 1 is magnetic particles and 4 2 is a binder resin.
  • the polyamide resin composition of the present invention contains magnetic particles, electrical and electronic parts such as stepping motors, HDD spindles, optical drive motors, air conditioner fan motors, copiers, etc. It can be used for developing rollers, cleaning rollers, and magnetic rollers such as transport rollers in electrophotographic developing devices such as nylon and printers.
  • the polyamide resin composition and molded product of the present invention contain inorganic particles and have a low water absorption, but can be made to have a high molecular weight by melt polymerization and can be estimated from the difference between the melting point and the thermal decomposition temperature. Is widely melted Excellent moldability, chemical resistance and hydrolysis resistance.
  • the polyamide resin composition of the present invention is a resin composition in which a specific polyamide resin is used as a binder resin and inorganic particles are combined.
  • molded parts include moisture, alcohol, fluorocarbons, such as hydro mouth fluorocarbons, fuel, liquids such as gasoline, or steam. Barrier property against is required.
  • Nylon 6 has the property of permeating moisture, alcohol, fluorocarbon, gasoline, etc., it has excellent liquid or vapor barrier properties to impart liquid or vapor barrier properties to molded parts. It is essential to use a layered silicate together (for example, JP-A-2-69 5 62).
  • the invention uses a polyamide resin PA 9 2 C or PA 9 2/62 T as a molded part, so that compared with a molded part using conventional nylon 6, Polyamide resin molded parts with excellent liquid or vapor barrier properties, excellent water absorption, chemical resistance, hydrolysis resistance, etc., and 1, 9-nonanediamine as a single component
  • it provides a molded resin part that has a wider moldable temperature range, excellent melt moldability, and is tough with high molecular weight.
  • the polyamide resin is produced from the above polyamide resin, but the polyamide resin molded part may contain the following components as optional components in addition to the polyamide resin.
  • a part of the polyamide resin P A 92 C or PA 92/62 T used in the present invention can be substituted with another polymer component as long as the effects of the present invention are not impaired.
  • Examples of other polymers that can be blended as needed include those described above in 1.4.
  • polyimide resin molded part having liquid or vapor barrier properties of the present invention can contain other additives as long as the effects of the present invention are not impaired (as described above).
  • the layered silicate and its addition method are as described above.
  • the polyimide resin molded part having a liquid or vapor barrier property of the present invention can be molded by, for example, extrusion molding, blow molding, compression molding, injection molding or the like.
  • the polyimide resin molded part having a liquid or vapor barrier property of the present invention can be applied to various applications that require a liquid or vapor barrier property.
  • Polyamide resin molded part having liquid or vapor barrier properties of the present invention Compared to conventional molded parts using Nylon 6, it has excellent liquid or vapor barrier properties, low water absorption, chemical resistance, hydrolysis resistance, etc. 1 , 9-Nonandamin is a polyamide resin molded part with a wider moldable temperature range and superior melt moldability, and a high molecular weight toughness compared to a polyamide resin molded part using a single nonanediamine.
  • the present invention has excellent fuel permeation resistance, low water absorption, high molecular weight by melt polymerization, melting point
  • a fuel tank component that has a wide range of moldable temperature estimated from the difference between the thermal decomposition temperature and the thermal decomposition temperature, such as 50 or more, excellent melt moldability, and excellent chemical resistance and hydrolysis resistance.
  • polyamide resin PA 9 2 C or PA 9 2/62 T used in the present invention can be partially substituted with another polymer component as long as the effects of the present invention are not impaired.
  • examples of other polymers that can be blended as needed include those described in 1.4 above.
  • various additives can be combined as necessary, and these can be combined during or after the polyamide polycondensation reaction (as described above).
  • additives include fuel permeation improvers, fillers, reinforcing fibers
  • Examples of the fuel permeation improver include layered silicate.
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is not particularly limited as long as the effect of improving the mechanical strength, heat resistance and fuel permeability is obtained, but 100 parts by mass of the polyamide resin used in the present invention. On the other hand, it is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the proportion of layered silicate decreases, the mechanical strength, heat resistance and fuel permeation resistance tend to decrease, and when the proportion increases, the fluidity of the resin composition and the physical properties of the resulting molded product Especially, the impact strength tends to be low.
  • the fuel tank parts of the present invention have high fuel permeation resistance and low water absorption, and can be increased in molecular weight by melt polymerization. Excellent moldability, chemical resistance and hydrolysis resistance, so it can be used widely as fuel tank parts attached to fuel tanks.
  • polyamide resin has been pointed out as problems such as changes in physical properties due to water absorption, acid, high temperature alcohol, deterioration in hot water, etc., and more fuel resistance and dimensional stability. There is also a demand for polyamides with excellent chemical and chemical resistance.
  • the polyamide resin layer of the present invention has high fuel impermeability even when it does not contain a layered silicate, but the fuel impermeability can be further improved by including the layered silicate.
  • the layered silicate and its addition method are as described above.
  • the compounding amount of the layered silicate is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyamide resin. If the amount is less than 0.05 parts by mass, the fuel permeation suppressing effect is not sufficient. If the amount exceeds 10 parts by mass, molding may be difficult, and impact strength and flexibility may be reduced.
  • a plasticizer is preferably combined with the polyamide resin used in the fuel tube of the present invention.
  • the plasticizer is as described in 2.1 (2) above.
  • an ester of butyl benzene sulfonate, p-hydroxybenzoic acid and a linear or branched alcohol having 6 to 21 carbon atoms. (For example, 2_ethylhexyl, p-hydroxybenzoate) can be used.
  • the blending amount of the plasticizer is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the amount of the plasticizer exceeds 30 parts by mass, the breaking pressure of the tube is lowered, and there is a possibility that a problem of bleed out may occur.
  • Polyamide resin used in the present invention PA 9 2 C or PA 9 2/6 2 T may be partially substituted with another polymer component as long as the effects of the present invention are not impaired.
  • Examples of other polymers that can be blended as necessary include those described in 1.4.
  • the fuel tube of the present invention includes the above-mentioned polyamide resin layer, and can be used as a single-layer tube, but is laminated with a layer other than the above composition layer (hereinafter referred to as another resin layer). It is preferable to use it as a multilayer tube. Multi-layer tubes are often used in practical automotive fuel tubes.
  • a layer composed of a fluororesin, a high density polyethylene resin, a polyamide 11 resin, or a resin obtained by blending the above plasticizer with a polyamide 12 resin is preferable.
  • the layer that is the main skeleton of the outermost layer or other layers includes a novel polyamide resin (PA 9 2) provided by the present invention, or a polyamide 11 resin, a polyamide 12 resin, or this It is preferable to use a material added with a plasticizer.
  • fluororesin examples include polytetrafluoroethylene (P TE F), polyvinylidene fluoride (P V D F), and polyvinyl fluoride (P V F). Further, it may be a resin partially containing chlorine such as polychlorofluoroethylene (PCTFE), or a copolymer with ethylene or the like.
  • PCTFE polychlorofluoroethylene
  • high-density polyethylene resin those having an average molecular weight of about 200,000 to 300,000 are preferable in consideration of gas resistance.
  • High-density polyethylene resin has a low temperature embrittlement temperature of 180 or less, and low temperature impact resistance. Excellent.
  • the other resin layer may be provided via an adhesive layer when the adhesiveness with the composition layer is poor. Further, the other resin layer does not have to be a single layer, and may be a laminate of several layers.
  • the thickness of the polyamide resin layer of the present invention is preferably 20 to 80% of the wall thickness of the tube.
  • the fuel impermeability of the tube may be insufficient.
  • the upper limit is not limited, in order to satisfy many required characteristics required for fuel tubes at the same time
  • the outer diameter of the multilayer fuel tube for automobiles can be designed in consideration of the flow rate of fuel gasoline, and the wall thickness is the thickness that does not increase the permeability of gasoline and can maintain the normal tube breaking pressure. Yes, the tube can be designed to be thin enough to maintain flexibility with a good degree of ease of tube assembly and vibration resistance during use, but the outer diameter is 4 ⁇ ! ⁇ 1
  • the wall thickness is 0.5 mn! ⁇ 2mm force is preferred.
  • the fuel tube of the present invention preferably contains from 30 to 30% by weight of the composition of the layer containing at least one layer of conductive force bon black.
  • Examples of the conductive carbon black include acetylene black and ketchen black. Among them, the carbon black has a good chain structure.
  • Figure 5 shows an example of a multilayer tube in cross section.
  • 5 1 to 5 3 are resin layers constituting the multilayer tube.
  • extrusion molding is preferably used, and as a method for producing a multilayer fuel tube, for example, The molten resin extruded from the number of extruders corresponding to the number of constituent layers or the number of materials is introduced into one multi-layer tube die, and each layer is bonded in the die or immediately after exiting the die.
  • Examples thereof include a method of producing in the same manner as ordinary tube forming, and a method of once forming a single-layer tube and then coating other layers on the outside or inside of the tube.
  • the fuel tube of the present invention has excellent fuel impermeability and fuel resistance, and
  • a fuel tube that includes a polyamide resin layer with a plateau width of 50 or more, excellent melt moldability, low water absorption, chemical resistance, and hydrolysis resistance. Is done.
  • This resin tube has excellent barrier properties against gasoline and is lighter than a rubber tube.
  • a connector has been developed in the United States that can quickly join resin tubes and metal tubes. Adopted as an excellent system.
  • This connector is called Quick: ⁇ Neck, a plastic eight-fusing female type quick neck that removably engages the end of a metal or plastic male tube (for example, see Japanese Patent Application Laid-Open No. 11-29 4 6 7 6).
  • the opposite ends of the female housing have a plurality of axially spaced jaws formed on the outer peripheral surface, and the system is formed by a Nin resin or plastic tube press-fitted over them. It is joined.
  • Resin tubes have been used because of their excellent mechanical properties and chemical resistance, but they do not satisfy the hydrocarbon permeation prevention performance. Therefore, it has been proposed to use a multilayer tube in which a resin with good fuel barrier properties, such as EVOH, PBT, or fluorine resin, is arranged as a barrier layer (for example, JP 7-0 0 7 7 3). (See No. 9).
  • a resin with good fuel barrier properties such as EVOH, PBT, or fluorine resin
  • the permeation from the piping can be significantly lower than the upper limit of future hydrocarbon evaporation.
  • Nylon 12 and Nylon 6 6 resins are widely used for quick connectors.
  • the anti-permeability performance of the material itself increases the thickness of the quick connectors and reduces the number of arrangements. Control of transpiration due to may be required to meet stricter regulations in the future.
  • fuel permeation tends to increase due to a substantial rise in temperature.
  • the applicant of the present application should provide a fuel pipe joint that can reduce the amount of fuel permeated through the wall and has excellent rigidity and barrier properties even at high temperatures.
  • % Of terephthalic acid, and 60 to 100 mol% of the diamine component consists of a diamine component selected from 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
  • a joint for fuel piping made of the following polyamide (PA 9 TA) is disclosed (Japanese Patent Laid-Open No.
  • the present invention has a low fuel wall permeation amount, excellent rigidity and barrier properties at high temperature, and excellent low water absorption, chemical resistance, hydrolysis resistance, and mechanical properties.
  • the present invention provides a fuel pipe joint that has a wider moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature and that is superior in melt moldability, particularly for fuel pipes used in automobiles.
  • the present invention provides a fuel pipe joint in which the joint material is made of polyamide resin PA 9 2 C or PA 9 2 Z 6 2 T.
  • the joint material consists of polyamide resin PA 9 2 C or PA 9 2/62 T with 50 to 99 parts by weight, other polyamide resin and Z or other thermoplastic resin 1 to 5
  • a polyamide resin composition composed of 0 part by weight may also be used.
  • Polyamide PA 92 C or PA 92/62 T used for the joint material in the present invention may be a homopolymer of the aforementioned polyamide PA 92 C or PA 92/62 T. It may be a mixture with other polyamide resins or other thermoplastic resins.
  • polyamide resins or other thermoplastic resins that can be blended with polyamide P A 92 C or PA 92/2/62 T are as described in 1.4 above.
  • the joint of the present invention is produced with a polyamide resin PA 9 2 C or PA 9 2/62 T and a polyamide resin composition comprising other polyamide resin and Z or other thermoplastic resin
  • the blending amount is from polyamide resin PA 9 2 C or PA 9 2/62 T to 50 to 99 parts by mass, other polyamide resin and Z or other thermoplastic resin 1 to 50 parts by mass.
  • a polyamide resin composition comprising a polyamide resin PA 92 C or PA 92/2/62 T, another polyamide resin, and Z or another thermoplastic resin is preferably used. If the polyamide resin P A 92 C or PA 92/62 T is less than 50 parts by mass, the desired effect of the present invention may not be obtained. If the amount of other polyamide resin and Z or other thermoplastic resin is less than 1 part by mass, the effect of blending these resins cannot be obtained.
  • Reinforcing materials include glass fibers, carbon fibers, fibrous inorganic materials such as wollastonite and calcium titanate whisker, and aramid fibers.
  • Inorganic fillers such as machine fiber, montmorillonite, talc, my strength, calcium carbonate, silica, clay, kaolin, glass powder, and glass beads are used.
  • the fiber diameter is 0.01 to 20 ⁇ , preferably 0.03 to 15 m, and the fiber cut length is 0.5 to LO mm, preferably 0. 7-5 mm.
  • glass fiber has a high reinforcing effect and is preferably used.
  • the creep resistance of the fastening part is high and deformation does not occur, and permanent sealing becomes possible.
  • the amount of reinforcing material used is 5 to 65% by weight, preferably 10 to 60% by weight, and more preferably 10 to 50% by weight in the polyamide resin or composition. If it is less than 5% by weight, the mechanical strength of the polyamide is not sufficiently satisfied. 6 If it is more than 5% by weight, the mechanical strength is sufficiently satisfied, but the moldability and surface condition are deteriorated, which is not preferable.
  • a conductive filler to the polyamide resin or composition used in the joint material of the present invention.
  • Conductivity means that, for example, when a flammable fluid such as gasoline continuously contacts an insulator such as resin, static electricity can accumulate and sparks can be generated, which can ignite the fuel. However, the electrical characteristics do not accumulate this static electricity. As a result, it is possible to prevent the occurrence of sparks due to static electricity generated when transporting fluids such as fuel.
  • the conductive filler referred to in the present invention includes all fillers added for imparting conductive performance to the resin, and examples thereof include granular, flaky and fibrous fillers.
  • the granular filler carbon black, kraftite, etc. can be suitably used.
  • the flaky filler aluminum flakes, nickel flakes, nickel co-magnification force and the like can be suitably used.
  • fibrous fillers are carbon nanotubes, carbon nanofibers, carbon fibers, carbon-coated ceramic fibers, Chikuni ponskers, aluminum fibers, copper fibers, brass fibers, and stainless steel fibers. Among these, carbon black can be preferably used.
  • the carbon black that can be used is as described above in 2.3 (1).
  • These conductive fillers may be surface-treated with a surface treatment agent such as a titanium base, aluminum, or silane. It is also possible to use a granulated product to improve melt-kneading performance.
  • the compounding amount of the conductive filler varies depending on the type of conductive filler used, so it cannot be specified unconditionally, but from the viewpoint of the balance between conductivity, fluidity, mechanical strength, etc.
  • such a conductive filler has a volume resistance of 10 9 ⁇ ⁇ cm or less, particularly a molded product obtained by melt-extruding a polyamide resin composition blended with it in order to obtain sufficient antistatic performance. It is preferable to add an amount of about 10 6 ⁇ ⁇ cm or less.
  • the blending of the above conductive filler tends to deteriorate strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler is as small as possible.
  • the reinforcing material and the conductive filler are blended at a weight ratio of 1: 3 to 3: 1. And are preferred.
  • the polyamide used in the joint material of the present invention includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic fine particle, an antistatic agent, and a flame retardant as necessary. Crystallization accelerators, plasticizers, impact modifiers, etc. may be added.
  • the joint material of the present invention may be produced by any method known as an injection molding method or other method for producing a resin joint.
  • Specific examples of the fuel pipe joint of the present invention include a fuel pipe quick connector in which a cylindrical main body is formed of the joint material.
  • Figure 6 shows a cross section of a typical quick connector 61.
  • the quick connector 61 shown in the figure connects the end of the steel tube 6 2 and the end of the plastic tube 6 3 to each other.
  • Steel tube 2 is removably engaged with flange-shaped part 6 4 away from the end of connector 2 and connector 1 retainer 6 5, and fuel is sealed by rows of O-rings 6 6 To do.
  • one end of the connector forms an elongated nipple 6 7 having a plurality of jaws 6 8 protruding in the radial direction.
  • the end of the plastic tube 6 3 is tightly fitted to the outer surface of the nipple 6 7, and the fuel is sealed by mechanical joining with the jaw portion 6 8 and a ring 6 9 provided between the tube and the nipple. .
  • each part such as a cylindrical main body retainer and a ring is assembled by injection molding and then assembled in a predetermined place.
  • the quick connector is an assembly that is engaged with the resin tube. It is assembled into a brie and used as fuel piping parts.
  • the quick connector and the resin tube may be mechanically joined by fitting, but are preferably joined by a welding method such as spin welding, vibration welding, laser welding, or ultrasonic welding. This can improve hermeticity
  • the resin tube may have a corrugated region in the middle.
  • a corrugated region is a region in which an appropriate region in the middle of the tube body is formed into a corrugated shape, a bellows shape, an ardion shape, a Lugion shape, or the like.
  • the resin tube preferably has a multilayer structure including a rear layer in addition to a poly layer such as Nylon 11 and Nylon 12 ⁇ PB
  • T PBN, fluororesin, PA92, clay with nano-dispersed nylon, EVOH, etc.
  • PBN PBN
  • fluororesin PA92
  • clay with nano-dispersed nylon EVOH, etc.
  • EVOH EVOH
  • a structure in which a conductor is included in the innermost layer is preferable for preventing damage due to static electricity.
  • All or a part of the outer circumference of the above resin tube is made of epoxy rubber, NBR, NBR in consideration of wear with other parts and flame resistance.
  • a protective member can be provided.
  • the protective member may be a sponge-like porous body by a known method. By using a porous body, a light-weight protective part with excellent heat insulation can be formed. In addition, material costs can be reduced. Alternatively, the strength may be improved by adding glass fiber or the like.
  • the shape of the protective member is not particularly limited, but is usually a block-like member having a cylindrical member or a recess for receiving a multilayer tube.
  • the multilayer tube can be inserted later into a cylindrical member prepared in advance, or the cylindrical member can be coated and extruded onto the multilayer tube to adhere both together.
  • the adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and the multilayer tube is inserted or fitted into the inner surface, and the multilayer tube and the protective member are brought into close contact with each other. Form a structured structure.
  • the quick connector according to the present invention is excellent in characteristics such as resistance to creep deformation because it is combined with airtightness improving technology such as O-ring and welding, so that the amount of permeation of the fuel / gasoline mixed fuel and the like is small. Can be. Therefore, it is useful as an excellent fuel line system that can flexibly respond to strict fuel emission regulations in combination with a multilayer tube with excellent barrier properties.
  • the fuel pipe joint of the present invention has low fuel wall permeation, excellent rigidity and barrier properties at high temperatures, and low water absorption, chemical resistance, hydrolysis resistance, and mechanical properties.
  • the moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature is wider, and it can be more excellent in melt moldability.
  • R i / JP 2l ⁇ ii »/ U 6UlT / 3 Suitable for use
  • the present invention provides a conventional nylon 66-based composition using an engine cooling water system component using polyamide resin PA 92 C or PA 92/62 T. Compared to the above, it has low water absorption, excellent dimensional stability, excellent chemical resistance, hydrolysis resistance, impact strength, etc., reduced material properties, especially less stress cracking, and as a jamming component
  • Engine cooling water system that can produce a tough molded body that has a wider moldable temperature range, better melt moldability, and higher molecular weight than a polyamide resin composition that uses 1,9-nonanediamine alone Polyamide resin composition for parts and engine cooling water molded from the composition Provide system parts.
  • the engine cooling water system component of the present invention is characterized by using polyamide resin PA 9 2 C or PA 9 2/62 T, but the polyamide resin PA 9 2 C or PA 9 2/62 T It is preferably made of a polyamide resin composition containing an inorganic filler.
  • Inorganic fillers are pre-treated with coupling agents such as isocyanate compounds, acrylic compounds, organosilane compounds, organic titanate compounds, organoborane compounds, and epoxy compounds. It is preferable in terms of obtaining superior mechanical strength.
  • glass fiber or talc is preferable, and glass fiber is more preferable.
  • the fibrous filler the fiber diameter is 0.01 to 20 u rn, preferably 0.03 to L5 m, and the fiber cut length is 0.5 to LO mm, preferably 0. 7-5 mm.
  • additives can be added to the polyamide resin composition of the present invention as long as the effects of the present invention are not impaired (as described above).
  • examples of the heat-resistant agent include hindered phenols, phosphates, thioethers, copper halides, etc., and these can be used alone or in combination.
  • mold release agent examples include fatty acid metal salts, fatty acid amides and various types of auxiliaries, which can be used alone or in combination.
  • the method for producing the polyamide resin composition for engine cooling water system parts of the present invention is not particularly limited.
  • it is generally used as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll.
  • a known melt kneader is used.
  • the engine cooling water system parts of the present invention can be produced by, for example, extrusion molding, blow molding, compression molding, injection of the above-mentioned pellets of the polyamide resin composition for engine cooling water system parts by a molding method commonly used in the industry. It can be produced by molding by a method such as molding.
  • the engine cooling water system parts of the present invention include a Raje evening core, a Raje evening tank part such as a top and base of a Raje evening tank, a coolant reserve tank, a war evening pipe, a war evening pump housing, a u ⁇ Parts used in contact with cooling water in the engine room, such as pump impellers, war evening jacket spacers, valves, and thermostats.
  • the polyamide resin composition of the present invention can be suitably used for engine cooling water system parts, but other members that require similar functions, for example, hot water pipes for floor heating, water sprinkling pipes for melting road snow, and the like. It can also be suitably used for resin parts.
  • the polyimide resin composition for engine cooling water system containing the polyamide resin of the present invention and an inorganic filler is low in water absorption and excellent in dimensional stability as compared with conventional nylon 66-based compositions. Excellent resistance to chemicals, P ⁇ P, hydrolysis resistance, impact strength, etc. Deterioration of material properties, especially less stress cracking, and polyamide resin using 1,9-nonanediamine alone Wide moldable temperature range than composition ⁇ Excellent melt moldability o
  • Crystalline polyamides are: Regis evening braid ', Washer' le ha 'one, Wind regire overnight handle, Wind regile overnight handle knob, Passing lie treva, Sun visor bracket Widely used as vehicle interior parts such as firewood
  • Nylon 6 has low weather resistance and chemical resistance, and water absorption High in dimensional stability, and when placed under high temperature and high humidity conditions, there is a large decrease in rigidity and dimensional change due to high water absorption, and it is not always satisfactory as a material for interior parts. is not. Therefore, in order to use it as a material for vehicle interior parts, it is essential to use layered silicate together (for example, 2-2 0 8 3 5 7).
  • the present invention uses conventional nylon 6 and nylon 66 by using polyamide resin PA 9 2 C or PA 9 2/62 T as a vehicle interior part. Compared to interior parts, it has superior weather resistance, low water absorption, excellent dimensional stability, excellent chemical resistance and hydrolysis resistance, and vehicle interior using 1,9-nonanediamine as a single component We will provide vehicle interior parts that have a wider moldable temperature range than parts and are excellent in melt moldability, and that are high molecular weight and tough.
  • vehicle interior part loro means a part used for vehicle interior.
  • Vehicles are white cars, for example, passenger cars
  • Buses, trucks, special automobiles for example, hakuyu, road lorry, snow vehicles, fork riffs, hoy cranes, special purpose vehicles, eg ambulances, fire trucks, television relay cars
  • the power including the freezer is not limited to these.
  • vehicle interior parts include, for example, register blades, washer levers, windshield handles, wind regulation knobs, and so on. Shearing levers, visor brackets, seals, instrument panels, console boxes, gear boxes, steering wheels, steering wheels, rims, rails, rails, etc. , Seat belt anchors, Electric seat parts, Sheet
  • the vehicle interior part of the present invention includes the above-described polyamide resin, but the vehicle interior part can further include the following components as optional components in addition to the above-mentioned polyamide resin.
  • a part of the polyamide resin P A 92 C or PA 92/62 T used in the present invention can be substituted with another polymer component as long as the effects of the present invention are not impaired.
  • Other polymers that can be blended as needed are described above in 1.4.
  • substitution ratio by the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50% by mass, more preferably 30% by mass or less.
  • polyamide or “polyamide resin” simply refers to the polyamide resin P A 92 C or P A 92/2/62 T.
  • the in-vehicle component of the present invention can contain other additives as long as the effects of the present invention are not impaired (as described above).
  • an ultraviolet absorber for example, T i n u V i n 3 2 7
  • the trade name of the light stabilizer is, for example, TinuVin 1 2 3 (Ciba Specialty Chemicals Co., Ltd., hindered amine)
  • the light stabilizer is usually used at a ratio of 0.015 parts by mass with respect to 100 parts by mass of the resin.
  • the vehicle interior parts of the present invention are low in water absorption and excellent in dimensional stability with only the above-mentioned polyamide resin, but in applications where lower water absorption and dimensional stability are required, layered silicate is used as the above-mentioned polyamide resin. Can be added.
  • the layered silicate and its addition method are as described above.
  • the amount of the layered silicate is the amount that the effect of the layered silicate is exhibited. As long as it is not particularly limited, it is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 8 parts by weight with respect to 100 parts by weight of the polyamide resin. Particularly preferred is 0.05 to 5 parts by mass. If the proportion of layered silicate is low, the effect of layered silicate is not exhibited, and if the proportion is high, the melt viscosity becomes extremely high, and the moldability tends to deteriorate or impact resistance tends to decrease. .
  • Crystalline polyamides such as Nylon 6 and Nylon 6 6 are not only used for apparel, industrial materials, or general-purpose engineering plastics because of their excellent properties and ease of melt molding. It is widely used as a material for vehicle exterior parts such as motors, lamp housings, front grilles, mudguards, side bumpers, bumpers and fenders.
  • Nylon 6 has high water absorption, low chemical resistance, and dimensional stability. When used under conditions where excessive external force or heat is applied, the rigidity due to high water absorption is low. In order to use it as a material for vehicle exterior parts, it is indispensable to use a layered silicate together (for example, Japanese Patent Laid-Open No. 2-229885).
  • vehicle exterior part means a part used for the exterior of a vehicle.
  • vehicles include automobiles, such as passenger cars, buses, trucks, motorcycles, special automobiles, such as tractors, mouth-drawers, snow vehicles, forklifts, wheel cleans, special-purpose cars. Examples include, but are not limited to, ambulances, fire engines, television relay cars, refrigerated cars, and motorbikes.
  • vehicle exterior parts include moldings, lamp housings, front grills, mudguards, side bumpers, bumpers, fenders, bonnets, sunroof parts, automobile body reinforcement parts, bonnets, rear gates, exterior clips , Outer panels, various spoilers, under covers, air dams, etc., but are not limited thereto.
  • substitution ratio with the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50% by mass, more preferably 30% by mass or less.
  • the vehicle exterior part of the present invention has low water absorption and excellent dimensional stability only with the above-mentioned polyamide resin.
  • layered silicate is added to the above-mentioned polyamide silicate. It can be added to the resin.
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but is preferably 0.0 with respect to 100 parts by mass of the polyamide resin. 5 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the ratio of layered silicate is lowered, the effect of layered silicate is not exhibited.
  • the ratio is increased, not only the melt viscosity is remarkably increased but also the impact strength tends to be lowered.
  • vehicle exterior component of the present invention can contain other additives as long as the effects of the present invention are not impaired (as described above).
  • the vehicle exterior part of the present invention has low water absorption, excellent dimensional stability, excellent chemical resistance and hydrolysis resistance, as compared with conventional vehicle exterior parts using Nylon 6 or Nylon 66. Compared to vehicle exterior parts that use 1,9-nonanediamine alone as the jamming component, it is possible to produce a tougher part that has a wider moldable temperature range, better melt moldability, and higher molecular weight.
  • Polyamide resin is widely used as a starting material for injection molding of automobile parts due to its excellent mechanical properties and ease of melt molding. However, when used as an automotive engine compartment part, it has high rigidity and special characteristics. In addition, for the purpose of high rigidity at high temperatures, it has been proposed to reinforce polyamide resin with glass fiber (Japanese Laid-Open Patent Application No. 2-2410 160).
  • the polyamide resin when used as an engine compartment component, the polyamide resin has problems such as changes in physical properties due to water absorption, deterioration due to acid, high-temperature alcohol, fuel, and hot water, as well as low warpage and heat resistance. Although it is desirable that the chemical properties and chemical resistance (including anti-freezing agents) are further improved, there have been few attempts to improve the polyamide resin itself.
  • the present invention provides a polyamide resin PA 9 2
  • the interior of the automobile engine room has excellent resistance to hydrolysis.
  • the components in the automobile engine compartment of the present invention include an internal hold, an air cleaner, a resonator, a fuel rail, a throttle body and a valve, an air flow overnight, an EGR section, a harness connector, an engine cover, U-head force bar, timing belt (chain cover), timing chain (belt) tensioner and guide, alterne overnight bar, taste ⁇ review evening cover, brake master Oil pump
  • Oil filter Oil filter, Engine mount, Paper carrier, Power steering oil reservoir, Fuels ⁇ Reiner, Raje evening tank, Switch boot, Lamp cover, Neck cover, Rubber hook , Suspension bush, Suspension upper mount, Suspension bush J Sub stabilizer, Bush, Steering rack boot, Steering rack fish, U The bar tank cap, Plug cord cap, Molded packing, Battery There is a terminal force bar.
  • the automotive engine compartment component of the present invention is preferably a polyamide.
  • the fibrous reinforcement to the resin PA 9 2 C or PA 9 2/62 T, the mechanical properties (particularly rigidity) and heat resistance can be improved.
  • fibrous reinforcing materials include fibrous inorganic fillers such as glass fibers, carbon fibers, and wollastonites, and ceramic swiss strength such as silicon nitride and potassium titanate.
  • the shape of the fiber is not particularly limited.
  • the fiber diameter is preferably 2 to 20 m, more preferably 4 to 15.
  • the aspect ratio (fiber length fiber diameter) is preferably 4 to 70 in the molded body, and more preferably 5 to 50. If the fiber diameter is too small, it is difficult to produce. If the fiber diameter is too large, the mechanical properties of the molded article, particularly impact resistance, may be reduced. Also, if the aspect ratio is small, the reinforcing effect is low, and if it is too large, warpage during molding increases, which is not preferable.
  • Wollastonite is preferred to have an aspect ratio of 3 to 70, and silicon nitride and calcium titanate preferably have a fiber diameter of 0.1 to 3;
  • the blending amount of the fibrous reinforcing material is preferably 150 parts by mass or less, more preferably 100 parts by mass or less with respect to 100 parts by mass of the polyamide resin. If the amount is too large, the fluidity of the composition will decrease, making it difficult for the surface of the molded product to become slippery or causing warpage.
  • the lower limit of the amount of the fibrous reinforcing material is not limited, but in order to obtain excellent mechanical properties and thermal properties by blending the fibrous reinforcing material, 3 parts by mass or more is preferable, and 20 parts by mass or more Is more preferable.
  • the polyamide resin assembly for automotive engine compartment parts according to the present invention is also provided.
  • the composition can preferably include a layered silicate. By including a layered silicate, it is possible to impart excellent rigidity and dimensional stability to automotive engine room component materials.
  • the blending amount of the layered silicate is preferably 30 parts by mass or less with respect to 100 parts by mass of the resin. Part is more preferable, and Q 0.05 to 5 parts by mass is more preferable. If the blending amount exceeds 30 parts by mass, molding may become difficult, and impact strength and flexibility may be reduced. If the amount is less than 0.5 parts by mass, sufficient effects may not be obtained.
  • a part of the polyamide resin P A 92 C or PA 92/62 T used in the present invention can be substituted with another polymer component as long as the effects of the present invention are not impaired.
  • Examples of other polymers that can be blended as needed include those described above in 1.4.
  • additives may be added to the polyamide resin composition obtained according to the present invention as necessary (as described above).
  • the method for producing the parts in the automobile engine room from the polyamide resin or the resin composition in the present invention is not limited to a specific method, but as a specific and efficient example, the raw material polyamide resin or it and other raw materials are used.
  • the method include supplying the mixture to a generally known melt mixer such as a single or twin screw extruder, a Banbury mixer, a mixer, a mixing roll, and the like.
  • melt mixer such as a single or twin screw extruder, a Banbury mixer, a mixer, a mixing roll, and the like.
  • there is no particular restriction on the mixing order of the raw materials there is no particular restriction on the mixing order of the raw materials.
  • Melt-kneading method blending some raw materials, then melt-kneading by the above method and blending the remaining raw materials and melt-kneading, or blending some raw materials and then using a single or twin screw extruder Any method such as a method of mixing the remaining raw materials using a side feeder during melt kneading may be used.
  • the injection molding machine is used to injection-mold the polyamide resin composition, or the press molding machine. Can be used for press molding.
  • the automotive engine compartment component of the present invention uses a novel polyamide resin, has low water absorption, suppresses changes in physical properties due to water absorption, deterioration in hot water, etc., and increases the molecular weight by melt polymerization. It has a wide moldable temperature range of 50 or more, excellent melt moldability, and excellent low warpage, heat resistance, chemical resistance, and hydrolysis resistance. In addition, it is possible to further improve mechanical properties, dimensional stability, heat resistance, and the like by blending fibrous reinforcing material, layered silicate, etc. with polyamide resin.
  • Various assembly devices, etc. are designed to perform predetermined work in the work unit while moving the work unit in any direction.
  • the work unit is assembled with various elements such as a camera, a solenoid, a camera, and a light source, and these elements are connected to cables such as a power supply cable, a signal cable, and an optical cable. These cables are long, and the cables are held in the cable housing so that they can freely follow the movement of the work unit (see, for example, Japanese Patent Laid-Open No.
  • a material having electrical conductivity for example, a resin composition in which a polyimide resin is blended with polyimide resin is proposed (see, for example, Japanese Patent Publication No. Hei 1 355018).
  • This material has improved conductivity, but has the drawback that rigidity is poor in impact resistance, and a cable housing excellent in slidability and rigidity and excellent in conductivity is desired.
  • this polyamide material has problems such as changes in physical properties due to water absorption, deterioration in acid, high-temperature alcohol, and hot water, and there is a demand for a polyamide with superior dimensional stability and chemical resistance. is there.
  • a cable housing excellent in slidability, mechanical strength, conductivity, low water absorption, molding processability, chemical resistance, etc.
  • a cable housing characterized by using PA resin PA 9 2 C or PA 9 2/6 2 T.
  • the cable housing of the present invention comprises a polyamide resin composition containing a polyamide resin (A), a conductivity imparting material (B), and an impact modifier (C).
  • the conductivity imparting material ( B) is carbon fiber and Z or carbon black.
  • Preferred polyamide resin composition is: polyamide resin (A) 65 to 75% by weight, carbon fiber 3 to 15% by weight as conductivity imparting material (B) and carbon black 2 to 10% by weight, Impact modifier (C) 10 to 20% by weight.
  • the polyamide PA 92 C or PA 92/62 T used in the cable housing in the present invention may be a polyamide PA 92 C or PA 92/62 T homopolymer. It may be a mixture with other polyamide resin or other thermoplastic resin.
  • polyamide resins or other thermoplastic resins may be those previously described in 1.4.
  • Nylon 6, Nylon 11, Nylon 12, Nylon 61, Nylon 61, or a copolymer thereof is preferably used for improving moldability and adhesion.
  • Polyamide resin PA 9 2 C constituting the cable housing of the present invention may be a single resin or a polyamide resin partially substituted with another polyamide resin and / or another thermoplastic resin.
  • the resin replacing the polyamide resin PA 92 C is preferably 50% by mass or less of the total resin. If the polyamide resin P A 92 C is less than 50% by mass, the desired effect of the present invention may not be obtained.
  • the blending ratio of the polyamide resin used in the present invention is based on the entire resin composition. On the other hand, 65 to 75% by weight is preferable. If the blending ratio of the polyamide resin is less than 65% by weight, it is not preferable because the toughness is lowered and deformation or fracture occurs. On the other hand, if it exceeds 75% by weight, the impact resistance is not preferred because the slidability is lowered.
  • the polyamide resin composition of the present invention preferably contains a conductive agent for the purpose of preventing electrification.
  • the conductivity-imparting material is not limited as long as it can impart conductivity, but carbon fiber and carbon black are preferably used. Carbon fibers such as pitch and PAN are not particularly limited. Force used PAN-based carbon fiber is preferred in view of properties such as physical properties and conductivity.
  • the carbon fiber preferably has a fiber length before kneading of 0.1 to 12 mm, particularly preferably 1 to 8 mm. The fiber diameter of the carbon fiber is preferably 5 to 15 m.
  • the blending ratio of the carbon fiber is preferably 2 to 40% by weight, more preferably 3 to 35% by weight, and still more preferably 3 to 15% by weight with respect to the entire resin composition. If the blending ratio of carbon fiber is less than 2% by weight, it is not preferable because the conductivity is lowered and it is easy to be charged with static electricity, and dust is attached to the product, causing problems in precision products.
  • the blending ratio is 40% by weight. Exceeding this is not preferable because it has high rigidity and inferior impact resistance, and the smoothness of the surface of the molded product is poor and the slidability is lowered.
  • the carbon black that can be used in the present invention is as described above in 2.3 (2).
  • the blending ratio of carbon black is preferably 2 to 40% by weight, more preferably 2 to 30% by weight, and still more preferably 3 to 10% by weight with respect to the entire resin composition. 2% by weight of carbon black If the ratio is less than 40% by weight, it is not preferable because sufficient conductivity cannot be obtained. If the blending ratio exceeds 40% by weight, the melt viscosity is high, the fluidity is lowered, and the moldability is remarkably impaired.
  • the polyamide resin composition constituting the cable octacing of the present invention further includes an impact improving material.
  • the preferred impact modifier in the present invention is an acid-modified ethylene i zt coalescence.
  • the acid-modified ethylene copolymer is a copolymer of ethylene and a 1-year-old olefin having 3 or more carbon atoms (hereinafter referred to as “unmodified ethylene copolymer”).
  • the above-mentioned unmodified ethylene copolymer is composed of, for example, a thiodara-nitrate catalyst, in particular, a vanadium compound such as oxyvanadium trichloride and vanadium tetrachloride and an organoaluminum compound. As mentioned above, it is preferably obtained by copolymerizing 80 to 95 mol% of ethylene and usually 50 mol% or less, preferably 20 to 5 mol% of ⁇ -olefin having 3 or more carbon atoms.
  • Examples of ⁇ -aged olefins having 3 or more carbon atoms include propylene, butene-1, hexene-1, decene-1, 4-methylbutene-1, 4-methylpentene-1, and the like.
  • L L D is used.
  • the ⁇ , ⁇ -unsaturated carboxylic acid (hereinafter referred to as “unsaturated carboxylic acid”) to be subjected to Darraf polymerization to the above-mentioned unmodified ethene is methacrylic acid, ethacrylic acid, anhydride of Esters etc. It is done. Of these, maleic anhydride is preferred.
  • the graft amount of the unsaturated carboxylic acid is usually from 0.05 to 1: 1.5% by weight, preferably from 0.1 to :! It is in the range of% by weight.
  • the amount of the unsaturated carboxylic acid is less than 0.05% by weight, the effect of improving the slidability is reduced because the compatibility with the polyamide is deteriorated, and the amount of the unsaturated carboxylic acid is 1. If it exceeds 5% by weight, the reaction with the terminal amino group of the polyamide is excessive and the melt viscosity becomes high, or the gelling process is severely impaired due to gelation, which is not preferable.
  • Graft polymerization is carried out by adding an unsaturated carboxylic acid to an unmodified ethylene copolymer according to a conventional method, and melt-kneading usually at 150 to 300.
  • an organic peroxide such as' -bis-t-butyloxy-p-diisopropylbenzene may be used for efficient polymerization.
  • the amount of organic peroxide used in this case is usually in the range of 0.001 to 0.05% by weight with respect to the unmodified ethylene copolymer.
  • the density of the acid-modified ethylene copolymer used in the present invention is preferably 0.89 to 0.94 g Zcc, particularly preferably 0.91 to 0.94 gZcc. If the density is less than 0.89 g / cc, the elastic modulus will decrease, so the joints such as the joint will be easily deformed, and if the density does not exceed 0.94 g Zcc, This is not preferable because the impact resistance is lowered and the joints such as the squeezed part are destroyed.
  • the blending ratio of the acid-modified ethylene copolymer used in the present invention is preferably 10 to 20% by weight with respect to the entire resin composition.
  • the blending ratio of the acid-modified ethylene copolymer is less than 10% by weight, the effect of improving the slidability is reduced, and dust due to friction is generated, causing a defect in precision products.
  • it exceeds 20% by weight the elastic modulus will decrease. This is not preferable because a joint portion such as a mating portion is easily deformed.
  • the polyamide resin composition used in the present invention can contain a reinforcing material such as glass fiber.
  • a dispersant can be used for the purpose of dispersing the conductivity imparting material, the impact improving material, the reinforcing material, and the like.
  • various other additives may be added to the polyamide resin composition used in the present invention as necessary, and these are added when the resin composition is melt-kneaded or melt-molded (described above). As of) .
  • the production method of the polyamide resin composition used in the present invention is not limited to a specific method, but as a specific and efficient example, a raw material mixture is converted into a single-screw or twin-screw extruder, a Banbury-mixer, a kneader, Examples thereof include a method of supplying and kneading to a generally known melt mixer such as a mixing roll.
  • the order of mixing the raw materials is not particularly limited, and all the raw materials are mixed and then melt-kneaded by the above method, and some raw materials are mixed and then the remaining raw materials are mixed by the above method.
  • Any method may be used, such as a method of melt kneading, or a method of mixing a part of raw materials and mixing the remaining raw materials using a single feeder during melt kneading with a single or twin screw extruder. Good.
  • the method of molding the cable housing from the polyamide resin composition there is no particular limitation on the method of molding the cable housing from the polyamide resin composition, and the polyamide resin composition is injection molded using an injection molding machine, or press molded using a press molding machine. be able to.
  • a polyamide resin (PA 92 C) (A) is added to a conductivity imparting material (B) such as carbon fiber and / or carbon black, an acid.
  • a polyamide resin composition containing an impact modifier (C) such as a modified ethylene copolymer, it has excellent slidability, mechanical strength, and electrical conductivity, as well as low water absorption and moldability.
  • a cable housing with excellent chemical resistance can be obtained.
  • the volume resistivity of the polyamide resin composition in the present invention is desirably 1 ⁇ 10 4 ( ⁇ cm) or less.
  • the volume resistivity of the polyamide resin composition was measured by the method of AS TMD 2 57.
  • the flexural modulus of the polyamide resin composition is preferably 6. OGPa or more, more preferably 6.4 GPa or more.
  • the cable housing of the present invention has excellent slidability and rigidity, In addition, it has excellent electrical conductivity and is suitably used for precision machine manufacturing equipment such as semiconductor factories.
  • Nylon 1 1 and Nylon 1 2 in particular have the basic performance required for fuel component applications that are oil resistant and fuel permeation-proof. And fuel oil tanks, fuel pipes, fuel transfer units, fuel pump modules, valves and other molded parts that come into contact with fuel.
  • Biodiesel fuel is a fuel consisting of vegetable oils such as rapeseed oil, sunflower oil, soybean oil and corn oil, and fatty acid methyl esters obtained by esterifying these waste edible oils with crude oil and then separating and removing glycerin.
  • Biodiesel fuel is generally this fatty acid methyl Esters are used in a mixture with diesel oil in a certain ratio.
  • the resistance of polyamid resin to biodiesel fuel is considered to be different from the resistance of gasoline and light oil to conventional fuels, and those with conventional fuel resistance are not necessarily resistant to biodiesel fuel.
  • polyamide resins used in fuel parts also have problems such as changes in physical properties due to water absorption, deterioration in acid and high-temperature alcohol, and better dimensional stability. There is a demand for polyamide.
  • the present invention uses a polyamide resin PA 92C or PA 92/2/62 T, which is excellent in biodiesel fuel resistance and low in linear polyoxide resin.
  • Polyamide resin molded parts that are in direct contact with biodiesel fuel with excellent hydrolysis resistance, high molecular weight, large difference between melting point and thermal decomposition temperature without impairing water absorption I will provide a.
  • the layered silicate itself and the method for adding it are as described above.
  • the compounding amount of the layered silicate is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyamide resin. If it is less than 5 parts by mass, the fuel permeation inhibiting effect is — — Not enough, and if it exceeds 10 parts by mass, molding may become difficult, and impact strength and flexibility may be reduced.
  • the preferred plasticizer for use in the polyamide resin P A 9 2 C or P A 9 2/6 2 T is as described above.
  • the blending amount of the plasticizer is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the polyamide resin. If it exceeds 30 parts by mass, there is a possibility of a bridle.
  • a part of the polyamide resin P A 92 C or PA 92/62 T used in the present invention can be substituted with another polymer component as long as the effects of the present invention are not impaired.
  • Examples of other polymers that can be blended as needed include those described above in 1.4.
  • additives may be added to the molded part having excellent biodiesel fuel resistance according to the present invention as required (as described above).
  • a polyamide resin or a polyamide resin composition containing various compounding ingredients and additives is injected, extruded, hollow, pressed, or All known molding methods applicable to polyamide, such as glass, foam, vacuum / pressure air, and stretching, are possible. By these molding methods, films, sheets, molded articles, fibers, and the like can be processed.
  • the molded parts excellent in biodiesel fuel resistance obtained by the present invention can be used for any of various molded parts in which conventional polyamide resin fuel parts have been used.
  • Examples of the molded member that comes into contact with the biodiesel fuel include a fuel tank, a fuel tube, a fuel pipe, a fuel transfer unit, a fuel pump module, and a valve.
  • a polyamide resin having excellent biodiesel fuel resistance, low water absorption, excellent hydrolysis resistance, a wide moldable temperature range, and excellent directing property to biodiesel fuel. Formed parts are provided.
  • Ti r was measured at 25 using a Ostwald viscometer with a 96% sulfuric acid solution of polyamide (concentration: 1. O g / dl).
  • Tm and Tc of the plasticizer-containing sample and the sample not containing the plasticizer were measured in a nitrogen atmosphere using PYRI IS Diamond DSC manufactured by Perkin ELMer.
  • the temperature is increased from 3 0 to 2 7 0 at a rate of 1 0 / min (referred to as a temperature rising fast run), held at 2 7 0 for 3 minutes, and then — 1 0 0 until 1 0 no minute
  • the temperature was lowered at a rate of 5 ° C. (referred to as a “decreased ground ⁇ run”), and then the temperature was raised at a rate of 10 ° CZ up to 2700 (referred to as a temperature rise second run).
  • the endothermic peak temperature of the temperature rising fasttran from the DSC chart obtained, and for the sample not containing the plasticizer, the endothermic peak temperature of the temperature rising second run, respectively.
  • Td was measured by thermogravimetric analysis (TGA) using THE RMOGR AV IMM ETRIC A NA L YZ ERT GA- 50 manufactured by Shimadzu Corporation. The temperature was increased from room temperature to 50 ° C. under a nitrogen stream of 20 ml / min at a rate of temperature increase of 10 minutes, and T d was measured.
  • TGA thermogravimetric analysis
  • Melt viscosity is TI, Ainstrument, Japan
  • a 25 mm cone plate was attached to the viscoelasticity measuring device AR ES, and the measurement was performed in nitrogen at 25 ° C. and at a shear rate of 0.1 Is- 1 .

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Abstract

La présente invention concerne une composition de résine de polyamide contenant une résine de polyamide, le composant d'acide dicarboxylique étant constitué d'acide oxalique et le composant de diamine étant constitué de 1,9-nonanediamine et de 2-méthyle-1,8-octanediamine avec un rapport molaire compris entre 1,9-nonanediamine et 2-méthyle-1,8-octanediamine étant compris entre 1:99 et 99:1 ou, de façon alternative, une résine de polyamide où le composant d'acide dicarboxylique est constitué d'acide oxalique et où le composant de diamine est constitué de 1,9-nonanediamine et 2-méthyle-1,8-octanediamine (ci-après dénommé "mélange de diamine C9") et 1,6-hexanediamine (ci-après dénommé "diamine C6") avec un rapport molaire compris entre le mélange de diamine C9 et la diamine C6 étant compris entre 1:99 et 99:1, ainsi que divers additifs.
PCT/JP2009/060979 2008-06-10 2009-06-10 Nouvelle composition de résine de polyamide et produit contenant de la résine de polyamide Ceased WO2009151145A1 (fr)

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JP2008152318A JP2009298862A (ja) 2008-06-10 2008-06-10 新規なポリアミド樹脂を用いて作製された車両外装部品
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JP2008152313A JP5572922B2 (ja) 2008-06-10 2008-06-10 エンジン冷却水系部品用ポリアミド樹脂組成物、及び当該組成物から成形させたエンジン冷却水系部品
JP2008152301A JP2009298853A (ja) 2008-06-10 2008-06-10 ポリアミド樹脂組成物
JP2008152325A JP2009298867A (ja) 2008-06-10 2008-06-10 ポリアミドフィルム
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JP2008152311A JP5167965B2 (ja) 2008-06-10 2008-06-10 燃料配管用継手、燃料配管用クイックコネクター及び燃料配管部品
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JP2008152315A JP2009298861A (ja) 2008-06-10 2008-06-10 ポリアミド樹脂及び層状珪酸塩を用いて作製された中空成形部品
JP2008-152303 2008-06-10
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JP2008152310A JP5146124B2 (ja) 2008-06-10 2008-06-10 燃料チューブ
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JP2008244722A JP5577574B2 (ja) 2008-09-24 2008-09-24 新規なポリアミド樹脂を含む射出成形材料及びそれらから作製した射出成形体
JP2008-244725 2008-09-24
JP2008244717A JP5584964B2 (ja) 2008-09-24 2008-09-24 ポリアミド樹脂、層状珪酸塩を含む複合材料及び中空成形部品
JP2008244726A JP5577577B2 (ja) 2008-09-24 2008-09-24 新規なポリアミド樹脂を用いて作製された車両用部品、車両内装部品、車両外装部品、及び車両エンジンルーム内部品
JP2008244725A JP5577576B2 (ja) 2008-09-24 2008-09-24 液体又は蒸気バリア性を有するポリアミド樹脂成形部品、燃料タンク部品、燃料チューブ、燃料配管用継手、クイックコネクター、及び燃料配管部
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JP2011224988A (ja) * 2010-03-30 2011-11-10 Ube Industries Ltd 積層チューブ
JP2011231167A (ja) * 2010-04-26 2011-11-17 Ube Industries Ltd 熱処理による密度変化が小さい自動車部品又は電気・電子部品用ポリアミド樹脂
WO2012043640A1 (fr) * 2010-09-30 2012-04-05 宇部興産株式会社 Composition de résine de polyamide et objet moulé la comprenant
JP2012072339A (ja) * 2010-09-30 2012-04-12 Ube Industries Ltd ポリアミド樹脂組成物
CN102147034B (zh) * 2010-02-09 2013-01-09 李爱军 一种电缆支架立柱的制造方法
WO2013108344A1 (fr) * 2012-01-18 2013-07-25 宇部興産株式会社 Composition de résine, et composition contenant une résine polyamide et des fibres de verre
JP2013245258A (ja) * 2012-05-24 2013-12-09 Ube Industries Ltd ポリアミド樹脂とガラス繊維を含む組成物
WO2018036607A1 (fr) * 2016-08-22 2018-03-01 S-Techs Gmbh Matière polymère comprenant un ou plusieurs éléments de dopage différents, utilisations et procédé de production
WO2018147315A1 (fr) * 2017-02-09 2018-08-16 東洋紡株式会社 Composition de résine polyamide conductrice
WO2019087961A1 (fr) * 2017-10-30 2019-05-09 株式会社クラレ Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
EP3536477A4 (fr) * 2016-11-04 2020-04-29 Sanpura Co., Ltd. Procédé de production d'un élément moulé en résine imitant un métal, élément moulé en résine imitant un métal et utilisation d'un élément moulé en résine imitant un métal
WO2022001055A1 (fr) * 2020-06-29 2022-01-06 金发科技股份有限公司 Matériau composite à base de polyamide , son procédé de préparation et son application
WO2022001056A1 (fr) * 2020-06-29 2022-01-06 金发科技股份有限公司 Composition de polyamides et procédé de préparation associé et application correspondante
CN114231023A (zh) * 2021-12-27 2022-03-25 中广核俊尔(浙江)新材料有限公司 一种低成本、低吸水、易成型pa/pet合金材料及制备方法
CN115785660A (zh) * 2022-11-17 2023-03-14 广东格瑞新材料股份有限公司 应用于镜头模组防粉尘的耐高温尼龙复合材料及制备方法
CN116239885A (zh) * 2023-02-27 2023-06-09 山西泰宝密封技术有限公司 一种低翘曲聚酰胺改性材料、矿卡油缸导向环及其制备工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05506466A (ja) * 1990-02-20 1993-09-22 エクソン・ケミカル・パテンツ・インク 酸素バリヤー
JPH07228689A (ja) * 1994-02-16 1995-08-29 Kuraray Co Ltd ポリアミド樹脂
JP2004083817A (ja) * 2002-08-29 2004-03-18 Kuraray Co Ltd ポリアミド
JP2006057033A (ja) * 2004-08-23 2006-03-02 Ube Ind Ltd 低吸水性部材
WO2008072754A1 (fr) * 2006-12-11 2008-06-19 Ube Industries, Ltd. Résine de polyamide
WO2008123534A1 (fr) * 2007-03-27 2008-10-16 Ube Industries, Ltd. Matière de moulage pour composant de carburant, et composant de carburant utilisant ladite matière
WO2008123531A1 (fr) * 2007-03-27 2008-10-16 Ube Industries, Ltd. Procédé de production d'une résine polyamide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05506466A (ja) * 1990-02-20 1993-09-22 エクソン・ケミカル・パテンツ・インク 酸素バリヤー
JPH07228689A (ja) * 1994-02-16 1995-08-29 Kuraray Co Ltd ポリアミド樹脂
JP2004083817A (ja) * 2002-08-29 2004-03-18 Kuraray Co Ltd ポリアミド
JP2006057033A (ja) * 2004-08-23 2006-03-02 Ube Ind Ltd 低吸水性部材
WO2008072754A1 (fr) * 2006-12-11 2008-06-19 Ube Industries, Ltd. Résine de polyamide
WO2008123534A1 (fr) * 2007-03-27 2008-10-16 Ube Industries, Ltd. Matière de moulage pour composant de carburant, et composant de carburant utilisant ladite matière
WO2008123531A1 (fr) * 2007-03-27 2008-10-16 Ube Industries, Ltd. Procédé de production d'une résine polyamide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MACROMOLECULES, vol. 31, 1998, pages 3912 - 3924 *

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JP2011224988A (ja) * 2010-03-30 2011-11-10 Ube Industries Ltd 積層チューブ
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US9624416B2 (en) 2010-09-30 2017-04-18 Ube Industries, Ltd. Polyamide resin composition and molded article comprising the same
JP2012072339A (ja) * 2010-09-30 2012-04-12 Ube Industries Ltd ポリアミド樹脂組成物
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US9177692B2 (en) 2010-09-30 2015-11-03 Ube Industries, Ltd. Polyamide resin composition and molded article comprising the same
WO2012043640A1 (fr) * 2010-09-30 2012-04-05 宇部興産株式会社 Composition de résine de polyamide et objet moulé la comprenant
WO2013108344A1 (fr) * 2012-01-18 2013-07-25 宇部興産株式会社 Composition de résine, et composition contenant une résine polyamide et des fibres de verre
JP2013245258A (ja) * 2012-05-24 2013-12-09 Ube Industries Ltd ポリアミド樹脂とガラス繊維を含む組成物
AU2016421086B2 (en) * 2016-08-22 2021-11-18 S-Techs Gmbh Polymer material comprising at least one different doping element, uses and production method
WO2018036607A1 (fr) * 2016-08-22 2018-03-01 S-Techs Gmbh Matière polymère comprenant un ou plusieurs éléments de dopage différents, utilisations et procédé de production
RU2720785C1 (ru) * 2016-08-22 2020-05-13 С-Текс Гмбх Полимерный материал, включающий один или более различных легирующих элементов, применения и способ получения
EP3536477A4 (fr) * 2016-11-04 2020-04-29 Sanpura Co., Ltd. Procédé de production d'un élément moulé en résine imitant un métal, élément moulé en résine imitant un métal et utilisation d'un élément moulé en résine imitant un métal
WO2018147315A1 (fr) * 2017-02-09 2018-08-16 東洋紡株式会社 Composition de résine polyamide conductrice
WO2019087961A1 (fr) * 2017-10-30 2019-05-09 株式会社クラレ Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
EP3705257A4 (fr) * 2017-10-30 2021-03-03 Kuraray Co., Ltd. Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
US11969924B2 (en) 2017-10-30 2024-04-30 Kuraray Co., Ltd. Waterproof component and electronic equipment provided with same, method for waterproofing insert molded body, and method for waterproofing electronic equipment
WO2022001055A1 (fr) * 2020-06-29 2022-01-06 金发科技股份有限公司 Matériau composite à base de polyamide , son procédé de préparation et son application
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CN114231023A (zh) * 2021-12-27 2022-03-25 中广核俊尔(浙江)新材料有限公司 一种低成本、低吸水、易成型pa/pet合金材料及制备方法
CN114231023B (zh) * 2021-12-27 2023-10-31 中广核俊尔(浙江)新材料有限公司 一种低成本、低吸水、易成型pa/pet合金材料及制备方法
CN115785660A (zh) * 2022-11-17 2023-03-14 广东格瑞新材料股份有限公司 应用于镜头模组防粉尘的耐高温尼龙复合材料及制备方法
CN115785660B (zh) * 2022-11-17 2024-01-30 广东格瑞新材料股份有限公司 应用于镜头模组防粉尘的耐高温尼龙复合材料及制备方法
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