WO2013061650A1 - Composition de résine polyamide - Google Patents

Composition de résine polyamide Download PDF

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WO2013061650A1
WO2013061650A1 PCT/JP2012/065877 JP2012065877W WO2013061650A1 WO 2013061650 A1 WO2013061650 A1 WO 2013061650A1 JP 2012065877 W JP2012065877 W JP 2012065877W WO 2013061650 A1 WO2013061650 A1 WO 2013061650A1
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component
polyamide resin
resin composition
parts
examples
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PCT/JP2012/065877
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English (en)
Japanese (ja)
Inventor
前田　修一
倉知　幸一郎
知之 中川
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宇部興産株式会社
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Priority claimed from JP2011237956A external-priority patent/JP2013095803A/ja
Priority claimed from JP2011237642A external-priority patent/JP2013095789A/ja
Priority claimed from JP2011237957A external-priority patent/JP2013095804A/ja
Priority claimed from JP2011237916A external-priority patent/JP2013095800A/ja
Priority claimed from JP2011237713A external-priority patent/JP2013095790A/ja
Priority claimed from JP2011237901A external-priority patent/JP2013095798A/ja
Priority claimed from JP2011237374A external-priority patent/JP2013095778A/ja
Priority claimed from JP2011237954A external-priority patent/JP2013095801A/ja
Priority claimed from JP2011237641A external-priority patent/JP2013095788A/ja
Priority claimed from JP2011237910A external-priority patent/JP2013095799A/ja
Priority claimed from JP2011237361A external-priority patent/JP2013095777A/ja
Priority claimed from JP2011237722A external-priority patent/JP2013095792A/ja
Priority claimed from JP2011237721A external-priority patent/JP2013095791A/ja
Priority claimed from JP2011237386A external-priority patent/JP2013095780A/ja
Priority claimed from JP2011237723A external-priority patent/JP2013095793A/ja
Priority claimed from JP2011237955A external-priority patent/JP2013095802A/ja
Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Publication of WO2013061650A1 publication Critical patent/WO2013061650A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to a specific polyamide resin composition in which various additives are blended, and a specific polyamide resin composition for various uses.
  • the name of the polyamide resin may be based on JIS K 6920-1.
  • Crystalline polyamides represented by nylon 6 (PA6), nylon 66 (PA66), etc. are widely used as textiles for clothing, industrial materials, or general-purpose engineering plastics because of their excellent properties 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, and demand for polyamides with higher dimensional stability and chemical resistance is increasing. ing.
  • a polyamide resin using oxalic acid as a dicarboxylic acid component is called a polyoxamide resin, and is known to have a higher melting point and lower water absorption than other polyamide resins having the same amino group concentration (Patent Document 1). It is expected to be used in fields where the use of conventional polyamides, where changes in physical properties have become a problem, is difficult.
  • Non-Patent Document 1 discloses a polyoxamide resin using 1,6-hexanediamine as a diamine component
  • Non-Patent Document 2 discloses a polyoxamide resin (hereinafter also referred to as PA92) in which the diamine component is 1,9-nonanediamine.
  • Patent Document 2 discloses a polyoxamide resin using various diamine components and dibutyl oxalate as a dicarboxylic acid ester,
  • Patent Document 3 discloses a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as diamine components in specific ratios.
  • Patent Document 4 a molding time is shortened by using a polyamide resin composition comprising a polyamide resin or a resin composition containing the polyamide resin, and a layered silicate and a moldability improver uniformly dispersed in the polyamide resin.
  • a polyamide resin composition comprising a polyamide resin or a resin composition containing the polyamide resin, and a layered silicate and a moldability improver uniformly dispersed in the polyamide resin.
  • Patent Document 5 a copper wire is coated with a resin composition for extrusion comprising 100 parts by weight of a polyamide resin, 0.01 to 2.0 parts by weight of a heavy metal deactivator and 0 to 3.0 parts by weight of a heat-resistant agent.
  • a resin composition for extrusion comprising 100 parts by weight of a polyamide resin, 0.01 to 2.0 parts by weight of a heavy metal deactivator and 0 to 3.0 parts by weight of a heat-resistant agent.
  • An electric wire is disclosed.
  • Patent Document 6 components used under harsh conditions such as electric tools, general industrial parts, machine parts, electronic parts, automobile interior and exterior parts, engine room parts, automobile electrical parts, etc., have low water absorption, It describes that high impact resistance is required in addition to excellent chemical resistance and hydrolysis resistance.
  • Patent Document 7 there is a demand for improving mechanical strength, fuel resistance (gasoline resistance, sour gasoline resistance, etc.), chemical resistance (antifreeze resistance, resistance to various chemicals), and the like. It is described that there is.
  • Patent Document 8 discloses an example of a composite material using nylon 6 as a crystalline polyamide, and Table 2 shows that these composite materials have tensile strength and tensile elasticity compared to the original nylon 6. It is disclosed that mechanical strength such as rate and heat resistance are improved.
  • Patent Document 9 polyamide resin is used as a resin used in resinification from the viewpoint of suppressing permeation of liquid or gas and excellent mechanical properties, and various liquids, vapors and / or gases of polyamide resin are used. In order to suppress permeation of water, it has been proposed to contain a layered silicate.
  • JP 2006-57033 A Japanese National Patent Publication No. 5-506466 WO2008 / 072754 JP-A-1-301750 JP-A-7-268211 JP 2000-129122 A Patent 3036666 JP 62-74957 A Japanese Patent Laid-Open No. 11-269376
  • the problem to be solved by the present invention is: Compared with conventional polyoxamide resin, Melting point Tm (° C.) measured by differential scanning calorimetry measured at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere and measurement at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere Moldable temperature estimated from temperature difference (Td-Tm) (° C) (hereinafter also referred to as temperature difference (Td-Tm)) from 1% weight loss temperature Td (° C) (thermal decomposition temperature) in the thermogravimetric analysis Wide, Excellent heat resistance estimated from the melting point Tm, It has a moderate melt viscosity and excellent melt moldability, and can reduce the molding cycle.
  • Td-Tm temperature difference
  • Td-Tm thermogravimetric analysis Wide
  • a polyamide resin composition comprising a polyamide resin and a mold release agent, which can also achieve good sliding properties between the mold and the molded product during molding and / or a short molding time;
  • a polyamide resin composition comprising a polyamide resin and a heat-resistant agent,
  • a polyamide resin composition comprising a polyamide resin and an impact modifier,
  • a polyamide resin composition comprising a polyamide resin and a filler,
  • a polyamide resin composition comprising a polyamide resin and a layered silicate dispersed therein, a polyamide resin and a conductivity imparting agent, and
  • Melting point Tm (° C.) measured by differential scanning calorimetry measured at a rate of temperature increase of 10 ° C./min under
  • a polyamide resin composition for metal coating comprising a polyamide resin capable of forming a metal coating
  • a polyamide resin composition for injection molding comprising a polyamide resin capable of injection molding a molded body
  • a polyamide resin composition for molding vehicle parts including a polyamide resin capable of molding vehicle parts
  • a polyamide resin composition for a molded body that is in direct contact with a biodiesel fuel capable of molding a molded body having excellent resistance to biodiesel fuel A polyamide resin composition for fuel piping parts, including a polyamide resin capable of forming fuel piping parts
  • a polyamide resin composition for a printed circuit board surface mount component comprising a polyamide resin capable of forming a printed circuit board surface mount component
  • a polyamide resin composition for an electrophotographic apparatus component comprising a polyamide resin capable of forming an electrophotographic apparatus component
  • the present invention (1) A polyamide resin composition containing a polyamide resin (component A),
  • the component A is composed of a unit derived from a dicarboxylic acid and a unit derived from a diamine,
  • the dicarboxylic acid comprises oxalic acid (compound a);
  • the diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
  • the molar ratio of the compound b to the compound c is 99: 1 to 50:50
  • the polyamide resin composition further comprises Release agent (component B1), Heat-resistant agent (component B2), Impact modifier (component B3), Filler (component B4), Layered silicate dispersed in component A (component B5) and conductivity imparting agent (component B6)
  • a polyamide resin composition comprising at least one additive selected from the group consisting of: (2) A polyamide resin composition containing a polyamide resin (component A), The component A is composed
  • melt point Tm (° C.) measured by differential scanning calorimetry measured at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere and measurement at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere
  • a polyamide resin composition comprising a polyamide resin and a mold release agent, which can also achieve good sliding properties between the mold and the molded product during molding and / or a short molding time;
  • a polyamide resin composition comprising a polyamide resin and a heat-resistant agent,
  • a polyamide resin composition comprising a polyamide resin and an impact modifier,
  • a polyamide resin composition comprising a polyamide resin and a filler,
  • a polyamide resin composition comprising a polyamide resin and a layered silicate dispersed therein, a polyamide resin and a conductivity imparting agent, and
  • Melting point Tm (° C.) measured by differential scanning calorimetry measured at a rate of temperature increase of 10 ° C./min under
  • a polyamide resin composition for metal coating comprising a polyamide resin capable of forming a metal coating
  • a polyamide resin composition for injection molding comprising a polyamide resin capable of injection molding a molded body
  • a polyamide resin composition for extrusion molding comprising a polyamide resin capable of extruding a molded body
  • a polyamide resin composition for molding vehicle parts including a polyamide resin capable of molding vehicle parts
  • a polyamide resin composition for fuel piping parts including a polyamide resin capable of forming fuel piping parts
  • a polyamide resin composition for a printed circuit board surface mount component comprising a polyamide resin capable of forming a printed circuit board surface mount component
  • FIG. 2 is a cross-sectional view schematically showing an injection molding machine used in Examples 1 to 12 and Comparative Examples 2 to 3 in Table 1 in order to measure a releasing force. It is an injection-molded article molded using the pellets obtained in Examples 1 to 7 and Comparative Examples 2 and 4 in Table 17, and obtained in Examples 2-1 to 6 and Comparative Examples 2-2 and 4 in Table 19. An injection-molded article molded using the obtained pellets, Examples 5-1 to 4, 6-1, 7-1 to 5, and 8-1 to 3 in Table 28 and Comparative Examples 1-1 and 2-1 IC tray molded in 1. Quick connector example
  • Component A which is a polyamide resin in the present invention
  • the dicarboxylic acid component is succinic acid and the diamine component consists of 1,6-hexanediamine and 2-methyl-1,5-pentanediamine
  • the dicarboxylic acid comprises oxalic acid (compound a);
  • the diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
  • the molar ratio of the compound b to the compound c is 99: 1 to 50:50,
  • the relative viscosity ⁇ r measured at 25 ° C. using a solution of component A having a concentration of 1.0 g / dl in 96% sulfuric acid is 1.8 to 6.0.
  • Component A uses compounds a, b and c, preferably polycondensation using a mixture thereof, so that it has a high molecular weight, a high melting point, a large difference between the melting point and the thermal decomposition temperature, and excellent melt moldability. Furthermore, it is excellent in chemical resistance, hydrolysis resistance and fuel barrier properties as compared with conventional polyamides without impairing the low water absorption seen in linear polyoxamide resins.
  • component A has a molar ratio of compound b to compound c: Preferably, 99: 1 to 55:45 mol%, More preferably, it is 99: 1 to 60:40 mol%.
  • the molar ratio of compound b and compound c also means the molar ratio of the unit derived from compound b and the unit derived from compound c in component A.
  • compound a oxalic acid
  • compound a succinic acid
  • oxalic acid source obtained by polycondensation of oxalic acid derived from the oxalic acid source and diamine.
  • This oxalic acid is derived from an oxalic acid source such as oxalic acid diester, and any oxalic acid may be used as long as it has reactivity with an amino group.
  • oxalic acid diesters are preferable from the viewpoint of suppressing side reactions in the polycondensation reaction.
  • Dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) oxalate examples thereof include oxalic acid diesters of aliphatic monohydric alcohols such as butyl, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, and oxalic acid diesters of aromatic alcohols such as diphenyl oxalate.
  • oxalic acid diesters 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 more preferable, Among them, dibutyl oxalate and diphenyl oxalate are more preferable, More preferred is dibutyl oxalate.
  • component A Relative viscosity of component A Using oxalic acid as compound a as the carboxylic acid component, As the diamine component, 1,6-hexanediamine, which is compound b, and 2-methyl-1,5-pentanediamine, which is compound c, are polycondensed so that the melting point is preferably in the range of 200 to 330 ° C. Compared to a polyamide resin obtained by polycondensation of compound a and compound b with a melting point exceeding 330 ° C.
  • Component A2 in the melt polymerization in the post-polymerization step of component A described later, Since it is not necessary to use an excessively high temperature condition in which a side reaction occurs and inhibits high molecular weight, high molecular weight (increase relative viscosity) is possible. Therefore, Component A has an excellent melt moldability because it can increase the relative viscosity as compared with the conventional polyamide resin. From the viewpoint of avoiding the tendency for the molded product after melt molding to become brittle and lowering the physical properties, to avoid the tendency to increase the melt viscosity at the time of melt molding and to deteriorate the molding processability, the relative viscosity ⁇ r and the melt viscosity are above a certain level.
  • a 96% concentrated sulfuric acid solution having a concentration of component A of 1.0 g / dl is used.
  • the relative viscosity ⁇ r measured at 25 ° C. is preferably 1.8 to 6.0, more preferably 1.8 to 4.5, more preferably 1.8 to 3.0, and still more preferably May be 1.85 to 2.5, more preferably 1.85 to 2.2.
  • the relative viscosity ⁇ r can be increased by increasing the degree of vacuum.
  • the melt viscosity of component A is preferably 100 to 700 Pa ⁇ s, more preferably 110 to 600 Pa ⁇ s, still more preferably 120 to 500 Pa ⁇ s, still more preferably 130 to 400 Pa ⁇ s, and further
  • the pressure is preferably 150 to 300 Pa ⁇ s, more preferably 160 to 220 Pa ⁇ s, and still more preferably 170 to 200 Pa ⁇ s.
  • the number average molecular weight (Mn) of component A is preferably 10,000 to 50,000, more preferably 11,000 to 40,000, and still more preferably 11,000 to 35,000.
  • each term has the following meaning.
  • Sp The number of hydrogens (4) counted in the integral value Sp.
  • S (NH 2 ) The number of hydrogens (2) counted in the integrated value S (NH 2 ).
  • N (NHCHO) number of terminal formamide groups per molecule.
  • S (NHCHO) The number of hydrogens (one) counted in the integral value S (NHCHO).
  • N (OBu) number of terminal butoxy groups per molecule.
  • Component A further changes the polycondensation ratio of compounds b and c,
  • the temperature difference (Td ⁇ Tm) is larger than that of the comparative component A2, and smaller than the polyamide resin obtained by polycondensation of the compound a and the compound c (hereinafter also referred to as the comparative component A1).
  • the melting point Tm is low compared to the comparative component A2, high compared to the comparative component A1, 1% weight loss temperature Td is higher than the comparative component A1,
  • the saturated water absorption rate can be smaller than the comparative component A2 and larger than the comparative component A1.
  • the component A is compared with the conventional polyoxamide resin, Relative viscosity ⁇ r (high molecular weight), Moldable temperature range estimated from temperature difference (Td-Tm), Heat resistance estimated from melting point Tm, Both the melt moldability estimated from the melt viscosity and the low water absorption can be sufficiently secured.
  • Component A has sufficient chemical resistance, resistance to resistance due to the high polymerization ratio (molar ratio) of compound b after sufficiently ensuring the moldable temperature range, heat resistance, melt moldability and low water absorption. Particularly contributes to hydrolyzability and fuel barrier properties.
  • Tm is preferably 260 to 330 ° C., more preferably 265 to 330 ° C.
  • Td is preferably 341 to 370 ° C, more preferably 345 to 370 ° C, and still more preferably 350 to 365 ° C.
  • the temperature difference (Td ⁇ Tm) is preferably 10 to 95 ° C., more preferably 20 to 95 ° C., still more preferably 25 to 95 ° C.
  • the saturated water absorption is preferably 0 to 2.4, more preferably 1 to 2.4, still more preferably 2 to 2.4, and still more preferably 2.3 to 2.4.
  • Component A can be produced using any method known as a method for producing polyamide, but from the viewpoint of high molecular weight and productivity, Preferably, it is obtained by polycondensation reaction of diamine and oxalic acid diester batchwise or continuously. More preferably, the diamine and oxalic acid diester are obtained by a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step, or a pressure polymerization method described in WO2008-072754. More preferable two-stage polymerization method and pressure polymerization method are specifically shown by the following operations.
  • Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then the diamine (compounds b and c) and the oxalic acid diester which is the oxalic acid source of the compound a are mixed.
  • a solvent in which both the diamine and the oxalic acid diester are soluble may be used.
  • a solvent in which both the diamine component and the oxalic acid source component are soluble toluene, xylene, trichlorobenzene, phenol, trifluoroethanol, and the like can be used, and particularly, toluene can be preferably used.
  • the charging ratio between the oxalic acid diester and the diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio) of oxalic acid diester / the diamine from the viewpoint of increasing the molecular weight. Ratio), more 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 bubbling.
  • the reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C.
  • the reaction time at the final temperature reached is 3-6 hours.
  • (Ii) Post-polycondensation step In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. From the final temperature reached in the pre-polycondensation step, that is, preferably 80 to 150 ° C. The temperature is preferably 295 ° C. or higher and 350 ° C. or lower, more preferably 298 ° C. or higher and 345 ° C. or lower, more preferably 298 ° C. or higher and 340 ° C. or lower. The reaction is preferably carried out while maintaining the temperature raising time, preferably 1 to 8 hours, more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. A preferable final ultimate pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.
  • the reaction temperature is not particularly limited as long as the polyamide produced by the reaction of the diamine and the oxalic acid compound can maintain a slurry or solution state and does not thermally decompose.
  • the reaction temperature is preferably 150 ° C. to 250 ° C.
  • the charging ratio of dibutyl oxalate and diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), in terms of molar amount of dibutyl oxalate / total molar amount of diamine. More preferably, it is 0.99 to 1.01 (molar ratio).
  • the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of Component a, since the melting point is 245 to 300 ° C., the temperature is raised to 250 to 350 ° C., preferably 255 to 340 ° C., more preferably 260 to 335 ° C.
  • the pressure in the pressure vessel until reaching the predetermined temperature is adjusted to approximately 0.1 MPa, preferably 1 MPa to 0.2 MPa, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary.
  • a preferable final ultimate pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.
  • component A Component which can be used as dicarboxylic acid in component A
  • other dicarboxylic acid components other than compound a can be used within a range not impairing the effects of the present invention.
  • dicarboxylic acid components other than compound a oxalic acid
  • Aliphatic dicarboxylic acids such as suberic acid
  • alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid
  • terephthalic acid isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicar
  • polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible.
  • the proportion thereof is 25 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, and more preferably 5 mol% or less with respect to compound a (oxalic acid). More preferably, it is more preferably 0 mol% (that is, the dicarboxylic acid component consists only of compound a).
  • the molar ratio of the other dicarboxylic acid component to the compound a also means the molar ratio of the unit derived from the compound a and the unit derived from the other dicarboxylic acid component in the component A.
  • component A other diamine components other than compounds b and c can be used within the range not impairing the effects of the present invention.
  • Other diamine components other than 1,6-hexanediamine and 2-methyl-1,5-pentanediamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,9-nonanediamine, 2-methyl-1, 8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4- Aliphatic diamines such as trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 5-methyl-1,9-nonanediamine; Furthermore, alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine, Further aromatic diamines such as p-phen
  • the proportion thereof is 25 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, with respect to compounds b and c. More preferably, it is 0 mol% (that is, the diamine component consists only of compounds b and c).
  • the molar ratio of the other diamine component with respect to the compounds b and c also means the molar ratio of the units derived from the compounds b and c and the units derived from the other diamine components in the component A.
  • component A As the molding method of component A, all known molding methods applicable to polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching can be used. From the viewpoint of shortening the molding cycle property, the film can be processed into a film, a sheet, a molded product, a fiber and the like by these molding methods. Above all, It is suitable for metal coating processing, can coat metal articles appropriately and efficiently, is suitable for molding processing by injection molding, and can be processed into films, sheets, molded articles, fibers, etc. by these molding methods Can Suitable for molding by extrusion, can be processed into films, sheets, molded products, fibers, etc.
  • Component B1 which is a mold release agent, is a polyalkylene glycol end-modified product, phosphate ester, phosphite ester, higher fatty acid monoester, higher fatty acid, higher fatty acid metal salt, ethylene bisamide compound, low molecular weight polyethylene, At least one compound selected from the group consisting of magnesium silicate and substituted benzylidene sorbitols, It is selected from the viewpoint of stably ensuring good slipperiness between the mold and the molded product during molding and / or suppression of molding time.
  • Examples of preferable terminal modified products of polyalkylene glycol include terminal modified products of polyethylene glycol and terminal modified products of polypropylene glycol.
  • the terminal modification is preferably performed with an amino group, a carboxyl group or a methyl group.
  • the following formula (1) X—R 1 — (O—CH 2 —CH 2 ) n—O—R 2 —X (1)
  • X represents NH 2 , COOH, or H
  • R 1 and R 2 each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms
  • n represents 4 to 1200.
  • Examples of preferred phosphate esters include the following formula: (R 5 O) n PO (OH) 3-n (Wherein n is 1 or 2, and R 5 is an alkyl group having 1 to 10 carbon atoms).
  • R 5 is an alkyl group having 1 to 10 carbon atoms.
  • R include an ethyl group, a butyl group, an octyl group, and an ethylhexyl group.
  • Examples of preferred phosphites include the following formula: (R 6 O) 3 P (Wherein R 6 represents hydrogen or an alkyl group having 10 to 25 carbon atoms, more preferably 12 to 20 carbon atoms, or a phenyl group, or a group in which a part of these groups is substituted with a hydrocarbon group. ).
  • R 6 represents hydrogen or an alkyl group having 10 to 25 carbon atoms, more preferably 12 to 20 carbon atoms, or a phenyl group, or a group in which a part of these groups is substituted with a hydrocarbon group.
  • the three RO groups in the above formula may be the same or different.
  • R is an aliphatic group such as a decyl group, a lauryl group, a tridecyl group, a stearyl group or 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. Examples thereof include an aromatic group having a substituent.
  • phosphate esters and phosphite esters include aliphatic phosphate esters such as di (2-ethylhexyl) phosphate, tridecyl phosphite, tris (tridecyl) phosphite, and tristearyl phosphite. And aromatic phosphites such as aliphatic phosphites, triphenyl phosphites and diphenyl monodecyl phosphites.
  • Preferred higher fatty acid monoesters include the following formula: R 7 —CO—O—R 8 (Wherein R 7 and R 8 each independently represents an alkyl group having 8 to 32 carbon atoms, preferably 10 to 30 carbon atoms) , That is, an ester compound of a higher fatty acid and a higher aliphatic monohydric alcohol.
  • R 1 and R 2 in the above formula include aliphatic groups such as a decyl group, a lauryl group, a tridecyl group, a stearyl group, and an oleyl group.
  • examples of the higher fatty acid include myristic acid, palmitic acid, behenic acid, oleic acid, and alginic acid.
  • examples of higher aliphatic alcohols include myristyl alcohol, behenyl alcohol, oleyl alcohol, stearyl alcohol, hexyldecyl alcohol, and the like.
  • higher fatty acid monoesters include higher fatty acid monoalkyl esters such as myristyl myristate, stearyl stearate, behenyl behenate, oleyl oleate, hexyldecyl myristate, and the like.
  • Examples of preferred higher fatty acids and higher fatty acid metal salts include: CH 3 — (CH 2 ) n —COOX (Wherein n represents a number of 9 to 25, preferably 11 to 20, and X represents a metal of H or Group I to III of the periodic table).
  • higher fatty acids examples include stearic acid, palmitic acid, oleic acid, aragydic acid, and behenic acid.
  • metal salt of higher fatty acid examples include zinc stearate, lithium stearate, calcium stearate, aluminum palmitate and the like.
  • Examples of preferred ethylene bisamide compounds include: CH 3 (CH 2 ) m CONH (CH 2 ) 2 NHCO (CH 2 ) n CH 3 (Wherein, m and n are each independently a number of 9 to 25, preferably 10 to 20).
  • ethylene bisamide compound More specific examples of the ethylene bisamide compound include ethylene bisstearylamide and ethylene bispalmitylamide.
  • Preferred low molecular weight polyethylene includes those having a viscosity average molecular weight in the range of 500 to 5000, and those having a viscosity average molecular weight in the range of 1000 to 3000 are more preferred.
  • the viscosity average molecular weight is measured by measuring the solution viscosity using an Ubbelohde viscometer.
  • Preferred examples of magnesium silicate include those having an average particle diameter of 1 to 10 ⁇ m.
  • the average particle size is 1 ⁇ m or more, white unevenness is hardly generated on the surface of the molded product, and when the average particle size is 10 ⁇ m or less, the mechanical properties of the molded product, in particular, the tensile elongation at break and the impact strength are difficult to decrease.
  • the magnesium silicate may be subjected to a surface treatment with aminosilane or the like. The average particle diameter is measured by a dynamic scattering method.
  • Examples of preferable substituted benzylidene sorbitols include substituted benzylidene sorbitols synthesized by dehydration condensation of sorbitol and substituted benzaldehyde under an acid catalyst.
  • the condensation ratio of substituted benzaldehyde to sorbitol is preferably 1 mol or 2 mol with respect to 1 mol of sorbitol. Accordingly, these substituted benzylidene sorbitols have the following formula:
  • R 9 represents H, a hydroxyl group, a halogen, or an alkyl group having 1 to 200 carbon atoms
  • R 10 and R 11 each independently represent H, a hydroxyl group, a halogen, or an alkyl group having 1 to 200 carbon atoms).
  • substituted benzylidene sorbitols examples include 1,3-benzylidene sorbitol, 1,3,4,4-dibenzylidene sorbitol, 1,3-mono (p-hydroxybenzylidene) sorbitol, 1,3,2,4-di (P-hydroxybenzylidene) sorbitol, 1,3-mono (p-chlorobenzylidene) sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, 1,3-mono (m-nitrobenzylidene) sorbitol 1,3,2,4-di (m-nitrobenzylidene) sorbitol, 1,3- (p-chlorobenzylidene) 2,4- (p-ethylbenzylidene) -d-sorbitol and the like.
  • the polyamide resin composition of the present invention has a wide moldable temperature range, is excellent in heat resistance and melt moldability, and does not impair the low water absorption seen in aliphatic linear polyoxamide resins, and can be used in conventional aliphatic polyamide resins.
  • the content of component A in the polyamide resin composition excluding component B1 is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, still more preferably 60 to 100% by mass, and still more preferably 70 to 100% by mass.
  • component B1 is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, still more preferably 0.1 to 1.5 parts by mass, and more preferably 100 parts by mass of component A.
  • the amount is preferably 0.1 to 1 part by mass, more preferably 0.1 to 0.5 part by mass.
  • Component B2 which is a heat-resistant agent, can be used to improve the heat resistance of the polyamide resin, and an organic or inorganic heat-resistant agent can be used depending on the purpose, preferably a hindered phenol compound or a hindered amine compound. And at least one compound selected from the group consisting of phosphorus compounds, sulfur compounds and benzotriazole compounds. More preferred are hindered phenol compounds and / or phosphorus compounds.
  • a metal compound (salt) belonging to Group I transition series elements for example, The metal halides, sulfates, acetates, salicylates, nicotinates or stearates are mentioned. Further, alkali metal halide salts may be used alone or in combination with metal compounds (salts) belonging to the above Group I transition series elements. Specific examples thereof are potassium iodide, sodium iodide or potassium bromide. Furthermore, it is more effective when a nitrogen-containing compound such as melamine, benguanamine, dimethylolurea or cyanuric acid is used in combination.
  • a nitrogen-containing compound such as melamine, benguanamine, dimethylolurea or cyanuric acid is used in combination.
  • the polyamide resin composition of the present invention has a wide moldable temperature range, excellent heat resistance, and melt moldability, Ensures stable chemical resistance, hydrolysis resistance, fuel barrier properties, and heat resistance compared to conventional aliphatic polyamide resins without compromising the low water absorption found in aliphatic linear polyoxamide resins From the point of view
  • the content of component A in the polyamide resin composition is preferably 50 to 99.99% by mass, more preferably 70 to 99.99% by mass, still more preferably 97.0 to 99.99% by mass, and still more preferably. It is 98.0 to 99.99% by mass, more preferably 98.0 to 99.9% by mass.
  • the content of component B2 is preferably based on 100 parts by mass of component A from the viewpoint of stably expressing the effect of the heat resisting agent while suppressing the occurrence of coloring and unevenness of the polyamide resin composition and the molded product molded therefrom.
  • the amount is 0.01 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and still more preferably 0.1 to 2.0 parts by weight.
  • the polyamide resin composition of the present invention preferably contains the following as other components.
  • Polymers other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of Component A. Part, more preferably 0.5 to 30 parts by weight.
  • the impact modifier (component B3) is a component that improves the impact resistance of the polyamide resin (component A).
  • the impact modifier (component B3) is not particularly limited as long as it improves the impact resistance of the polyamide resin (component A), and examples thereof include an elastomer.
  • the elastomer preferably has a flexural modulus of 500 MPa or less as measured in accordance with ASTM D-790. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
  • component B3 (ethylene and / or propylene) ⁇ ⁇ -olefin copolymer, (ethylene and / or propylene) ⁇ ( ⁇ , ⁇ -unsaturated carboxylic acid and / or unsaturated carboxylic acid) Ester) -based copolymers, ionomer polymers, aromatic vinyl compound / conjugated diene compound-based block copolymers, and these can be used alone or in admixture.
  • the (ethylene and / or propylene) ⁇ ⁇ -olefin copolymer is a polymer obtained by copolymerizing ethylene and / or propylene and an ⁇ -olefin having 3 or more carbon atoms, and ⁇ -olefin having 3 or more carbon atoms.
  • olefins examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- - pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-do
  • the above (ethylene and / or propylene) ⁇ ( ⁇ , ⁇ -unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer is ethylene and / or propylene and ⁇ , ⁇ -unsaturated carboxylic acid and And / or a polymer obtained by copolymerizing unsaturated carboxylic acid ester monomers.
  • ⁇ , ⁇ -unsaturated carboxylic acid monomers include acrylic acid and methacrylic acid, and ⁇ , ⁇ -unsaturated monomers.
  • saturated carboxylic acid ester monomers include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, and the like of these unsaturated carboxylic acids.
  • a mixture is mentioned.
  • a maleic acid-modified ethylene-butene copolymer and / or a maleic acid-modified ethylene-propylene copolymer is preferable from the viewpoint of improving impact resistance while maintaining the strength during water absorption.
  • the above-mentioned ionomer polymer is obtained by ionizing at least part of the carboxyl group of the olefin and the ⁇ , ⁇ -unsaturated carboxylic acid copolymer by neutralization of metal ions.
  • Ethylene is preferably used as the olefin, and acrylic acid and methacrylic acid are preferably used as the ⁇ , ⁇ -unsaturated carboxylic acid.
  • the olefin is not limited to those exemplified here.
  • the body may be copolymerized.
  • metal ions include alkali metals and alkaline earth metals such as Li, Na, K, Mg, Ca, Sr, Ba, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd, etc. Can be mentioned.
  • the aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block, and the aromatic vinyl compound polymer block. And a block copolymer having at least one conjugated diene polymer block.
  • the unsaturated bond in the conjugated diene 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.
  • the aromatic vinyl compound includes styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,6-dimethylstyrene, vinylnaphthalene, vinyl Anthracene, 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenyl butyl) styrene, etc. can be mentioned. It may have a structural unit consisting of one or more of the monomers.
  • the aromatic vinyl compound-based polymer block may optionally have a structural unit composed of a small amount of other unsaturated monomer.
  • Conjugated diene polymer blocks include 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3- A polymer block formed from one or more conjugated diene compounds such as hexadiene, and hydrogenated aromatic vinyl compound / conjugated diene block copolymer is unsaturated in the conjugated diene polymer block. A part or all of the bonding portion is saturated by hydrogenation.
  • the distribution in the polymer block mainly composed of conjugated diene may be random, tapered, partially blocky, or any combination thereof.
  • the molecular structure of the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product may be any of linear, branched, radial, or any combination thereof.
  • an aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof one aromatic vinyl compound polymer block and one conjugated diene polymer block are linear.
  • Triblock copolymer in which three polymer blocks are linearly bonded in the order of bonded diblock copolymer, aromatic vinyl compound polymer block-conjugated diene polymer block-aromatic vinyl compound polymer block And one or more of these hydrogenated products are preferably used, and unhydrogenated or hydrogenated styrene / butadiene copolymer, unhydrogenated or hydrogenated styrene / isoprene copolymer, unhydrogenated or hydrogenated.
  • Styrene / isoprene / styrene copolymer unhydrogenated or hydrogenated styrene / butadiene / styrene copolymer, unhydrogenated or hydrogenated styrene / (isoprene / butylene) Diene) / styrene copolymer, and the like.
  • Carboxylic acid ester) -based copolymers, ionomer polymers, and block copolymers of aromatic vinyl compounds and conjugated diene compounds are preferably polymers modified with carboxylic acids and / or derivatives thereof. By modifying with such a component, a functional group having affinity for the polyamide resin is included in the molecule.
  • Examples of functional groups having an affinity for polyamide resin include carboxylic acid groups, carboxylic anhydride groups, carboxylic acid ester groups, carboxylic acid metal bases, carboxylic acid imide groups, carboxylic acid amide groups, and epoxy groups.
  • Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4- Cyclohexene-1,2-dicarboxylic acid, endobicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, acrylic Ethyl acetate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate,
  • the component B3 is composed of (ethylene and / or propylene) ⁇ ⁇ -olefin copolymer, (ethylene and / or propylene) ⁇ ( ⁇ , ⁇ - One or more polymers selected from the group consisting of (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) type copolymer and ionomer are preferred, maleic acid-modified ethylene-butene copolymer and maleic acid-modified ethylene One or more polymers selected from the group consisting of a propylene copolymer, an epoxy-modified styrene block copolymer and an ionomer are more preferable.
  • the polyamide resin composition of the present invention contains a polyamide resin (component A) and an impact modifier (component B3).
  • the amount of the impact modifier (component B3) is not particularly limited as long as the impact resistance of the polyamide resin (component A) is improved.
  • the amount of the impact modifier (component B3) with respect to 100 parts by mass is preferably 10 to 100 parts by mass. When the amount of the impact modifier (component B3) decreases, the impact resistance does not improve. On the other hand, when the impact modifier (component B3) increases, the effect of the wide moldable temperature range of the polyamide resin composition is not recognized.
  • the content of component A in the polyamide resin composition is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 90% by mass.
  • the amount of the impact modifier (component B3) with respect to 100 parts by mass of the polyamide resin (component A) is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 10 To 30 parts by mass.
  • Component B4 As the filler (component B4), an inorganic and / or organic filler can be used, and an inorganic filler is preferable.
  • the shape of the filler (component B4) is arbitrary, and includes fibrous, particulate and the like.
  • Examples of the filler (component B4) include reinforcing fibers and / or inorganic particles.
  • the blending amount of the filler is appropriately set depending on the application, and is, for example, 2 to 500 parts by mass with respect to 100 parts by mass of the entire polyamide resin.
  • the reinforcing fiber is not particularly limited, and examples thereof include inorganic fibers such as glass fibers, carbon fibers, metal fibers, and mineral fibers, and organic fibers such as aramid fibers that are tougher than polyamide resins.
  • inorganic fibers such as glass fibers, carbon fibers, metal fibers, and mineral fibers
  • organic fibers such as aramid fibers that are tougher than polyamide resins.
  • Glass fiber is not particularly limited.
  • the diameter of the glass fiber 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 is preferably 5 to 1000 ⁇ m.
  • the glass fiber may be crushed by blending or processing, but the crushed glass fiber preferably has the fiber length.
  • the compounding ratio of the glass fiber is preferably 2 to 40 parts by mass, more preferably 2 to 38 parts by mass, and preferably 3 to 35 parts by mass with respect to 100 parts by mass of the entire polyamide resin. If the blending amount of the glass fiber is small, the improvement in rigidity and creep resistance is lowered, and the bonding with a tube or the like may be deteriorated. On the other hand, when the compounding amount of the glass fiber is increased, the fluidity of the composition is deteriorated, which may cause a short shot or the surface state.
  • the carbon fibers are not particularly limited, such as pitch-based and PAN-based, but PAN-based carbon fibers are preferable in terms of properties such as physical properties and conductivity.
  • the fiber length before kneading of the carbon fiber may be a long fiber extending up to 1000 mm in addition to that of the short fiber depending on the use, but in the case of melt kneading for the purpose of pellet production, Preferably it is 0.1-12 mm, more preferably 1-8 mm,
  • the fiber diameter before kneading of the carbon fibers is preferably 5 to 15 ⁇ m, and carbon fibers having a finer fiber diameter can also be used.
  • the blending ratio of the carbon fiber is preferably 2 to 40 parts by mass, more preferably 2 to 38 parts by mass, and preferably 3 to 35 parts by mass with respect to 100 parts by mass of the entire polyamide resin. If the blending 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, when the blending amount of the carbon fiber exceeds 40 parts by mass, the fluidity of the composition is deteriorated, which may cause a short shot and the surface state may be deteriorated.
  • the polyamide resin used in the present invention has excellent mechanical strength, chemical resistance, low water absorption, hydrolysis resistance, etc., has a wide moldable temperature range, and excellent melt moldability.
  • blending basically, it is held as it is, and certain properties such as mechanical strength and heat resistance are remarkably improved by blending the reinforcing fibers.
  • inorganic particles examples include particles of metals, metal oxides, inorganic compounds, and the like, which can be appropriately selected depending on the application.
  • the particle size of the inorganic particles is not particularly limited and can be appropriately selected depending on the application.
  • Specific examples of inorganic particles include 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.
  • the particles include sulfides such as molybdenum.
  • inorganic particles having a density of 5 g / cm 3 or more such as tungsten particles
  • inorganic particles having a density of 5 g / cm 3 or more such as tungsten particles
  • magnetic particles such as ferrite such as barium ferrite and strontium ferrite, and rare earth magnetic materials such as samarium-cobalt and neodymium-iron-boron are used. It can be preferably used.
  • 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 coupling agent, surface treatment with a silane surface treatment agent, and the like.
  • a titanate coupling agent for example, a known method described in the above-mentioned JP-A-2-255760, and for surface treatment with a silane-based surface treatment agent, for example, in the above-mentioned JP-A-10-158507. Any known method can be employed.
  • the mass ratio of the above-mentioned polyamide resin and inorganic particles can be within the range of 50/50 to 5/95, more preferably 20/80 to 5/95 for polyamide resin / inorganic particles, In this case, it is possible to more easily provide characteristics such as higher specific gravity and magnetism.
  • the layered silicate (component B5) is a component that imparts mechanical properties and heat resistance to the polymer material.
  • the layered silicate is preferably a flat plate having a side length of 0.002 to 1 ⁇ m and a thickness of 6 to 20 mm.
  • each layer maintains the interlayer distance of about 18 mm or more, and is disperse
  • interlayer distance refers to the distance between the centroids of the layered silicate in the form of a plate
  • uniformly dispersed means that each layer exists mainly in a random state, and the layered silicate 50% by mass or more, preferably 70% by mass or more is dispersed in a single layer without forming a multilayer.
  • layered silicate examples include layered phyllosilicate minerals composed of magnesium silicate or aluminum silicate layers, that is, aluminum silicate phyllosilicate or magnesium silicate phyllosilicate.
  • layered phyllosilicate minerals composed of magnesium silicate or aluminum silicate layers, that is, aluminum silicate phyllosilicate or magnesium silicate phyllosilicate.
  • Specific examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, and halloysite. It may be what was done.
  • a swelling agent such as organic amine or organic ammonium is usually used.
  • the swelling agent has a role of expanding the interlayer of the clay mineral and a role of giving the clay mineral a force for taking up the interlayer polymer.
  • a swelling agent is usually used.
  • the swelling agent has a role of expanding the interlayer of the clay mineral and a role of giving the clay mineral a force for taking up the interlayer polymer.
  • 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 previously set in a desired shape and size.
  • the method for adding the layered silicate is not particularly limited as long as the layered silicate can be uniformly dispersed in the component A.
  • the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as, for example, 1,6-Hexanediamine and 2-methyl-1,5-pentanediamine are added to widen the space between the layers of the layered silicate in advance.
  • the raw material of component A can be introduce
  • an organic compound may be used as a swelling agent, and the layers may be spread in advance to about 100 mm or more and melt-mixed with component A to disperse each layer in a polyamide resin.
  • the polyamide resin composition of the present invention is a composite material containing the polyamide resin (component A) and the layered silicate (component B5) dispersed in the polyamide resin.
  • the amount of the layered silicate in the composite material of the present invention is not particularly limited as long as the mechanical properties and heat resistance of the composite material of the present invention are improved. 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 conductivity-imparting agent (component B6) used in the present invention is not particularly limited as long as it can be added to the polyamide resin to impart conductivity.
  • particulate filler carbon black, graphite or the like can be suitably used.
  • flaky filler aluminum flakes, nickel flakes, nickel-coated mica and the like can be suitably used.
  • fibrous filler metal fibers such as carbon nanotubes, carbon nanofibers, carbon fibers, carbon-coated ceramic fibers, carbon whiskers, aluminum fibers, copper fibers, brass fibers, and stainless fibers can be suitably used.
  • the fibrous filler is also preferable from the viewpoint of improving the mechanical properties of a molded product obtained by molding the polyamide resin composition of the present invention.
  • the amount of the conductivity imparting agent is preferably 2 to 150 parts by mass, more preferably 2 to 100 parts by mass, and more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the entire polyamide resin.
  • the carbon black that can be used in the present invention includes all carbon blacks commonly used for imparting conductivity, and preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, Examples include, but are not limited to, ketjen black, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, disc black, etc., which are manufactured from crude crude oil by furnace-type incomplete combustion. Absent. Among these, acetylene black and / or furnace black (Ketjen black) are preferably used.
  • Carbon black is produced in various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, and ash content. Although there is no restriction
  • the average particle size is preferably 500 nm or less, more preferably 5 to 100 nm, More preferably, it is 10 to 70 nm
  • the surface area (BET method) is preferably 10 m 2 / g or more, more preferably 300 m
  • the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and further preferably 300 ml / 100 g or more.
  • the ash content of carbon black is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less.
  • the DBP oil absorption referred to here is a value measured by a method defined in ASTM D-2414.
  • the carbon black preferably has a volatile content of less than 1.0% by mass.
  • carbon black various carbon powders having different characteristics such as average particle diameter, specific surface area, DBP oil absorption, and ash content are produced.
  • characteristics of the carbon black there is no particular limitation on the characteristics of the carbon black, but those having a good chain structure and a high aggregation density are preferred.
  • the size of the carbon black is Preferably it is 500 nm or less, More preferably, it is 5 to 100 nm, More preferably, it is 10 to 70 nm, Specific surface area (BET method) It is preferably 10-1500 m 2 / g or more, More preferably, it is 300-1500 m 2 / g or more, More preferably, it is 500-1500 m 2 / g, DBP (dibutyl phthalate) oil absorption is It is preferably 50 to 500 ml / 100 g or more, More preferably, it is 100 to 500 ml / 100 g, More preferably, it is 300 to 500 ml / 100 g or more.
  • the average particle size 100 arbitrary particles were selected by electron microscopy, and the arithmetic average value of these particle sizes was used.
  • the DBP oil absorption is measured by the method defined in AS
  • the blending ratio of carbon black is preferably 2 to 50 parts by mass with respect to 100 parts by mass of the entire polyamide resin.
  • the blending ratio of the carbon black is less than 2 parts by mass, it is not preferable because sufficient conductivity cannot be obtained.
  • the blending ratio exceeds 50 parts by weight, the melt viscosity is high, the fluidity is lowered, and the molding processability is significantly impaired. Therefore, it is not preferable. 2 to 15 parts by mass is preferred.
  • Carbon black is preferably 2 to 40% by mass, more preferably 2 to 30% by mass, still more preferably 2 to 15% by mass, and particularly preferably 3 to 15% by mass with respect to the entire polyamide resin composition.
  • pitch-based or 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 1000 mm long fiber as well as short fiber depending on the application, but the fiber length before kneading is preferably 0.1 to 12 mm, particularly preferably 1 to 8 mm.
  • the fiber diameter of the carbon fiber is preferably 5 to 15 ⁇ m, but fine carbon fiber 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 entire polyamide resin. When the blending ratio exceeds 40 parts by mass, the rigidity is high and the impact resistance is inferior, the smoothness of the surface of the molded product is poor, and the slidability may be lowered.
  • the blending ratio of the 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. If the blending ratio is small, the electrical conductivity is lowered and it is easy to be charged with static electricity.
  • the blending ratio of the carbon fiber is preferably 2 to 40% by mass, more preferably 2 to 35% by mass, still more preferably 2 to 15% by mass, and particularly preferably 2 to 10% by mass with respect to the entire resin composition.
  • conductivity-imparting agents may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. It is also possible to use a granulated product for improving melt kneading workability.
  • 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 the polyamide resin is about 10 15 ⁇ cm.
  • a conductivity-imparting agent By adding a conductivity-imparting agent, it can be reduced to, for example, about 10 12 to 10 1 ⁇ cm or less. do it.
  • a conductivity of about 10 3 to 10 6 ⁇ cm is considered to be one preferable range.
  • the polyamide resin composition for a cable housing of the present invention contains a polyamide resin (component A), a conductivity imparting agent (component B6), and an impact modifier (component B3).
  • This polyamide composition can contain the above-mentioned other components.
  • Polyamide resin composition for cable housing is composed of 65 to 75% by mass of polyamide resin (component A), 3 to 15% by mass of carbon fiber and 2 to 10% by mass of carbon black as conductivity imparting agent (component B6), and impact improvement. It is particularly preferable that the material (component B3) consists essentially of 10 to 20% by mass.
  • the manufacturing method of the polyamide resin composition used for manufacturing the cable housing is not limited to a specific method, but as a specific and efficient example, a mixture of raw materials is used as a single or twin screw extruder, Banbury mixer, kneader, and mixing.
  • An example is a method of supplying to a generally known melt mixer such as a roll and kneading.
  • the mixing order of the raw materials a method in which all the raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melted
  • Any method may be used, such as a method of kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt-kneading with a single or twin screw extruder.
  • the method for molding the cable housing from the polyamide resin composition is not particularly limited, and the polyamide resin composition can be injection molded using an injection molding machine or press molded using a press molding machine.
  • the cable housing of the present invention uses a polyamide resin composition obtained by blending a polyamide resin with a conductivity imparting agent such as carbon fiber and / or carbon black, and an impact modifier such as an acid-modified ethylene copolymer.
  • a conductivity imparting agent such as carbon fiber and / or carbon black
  • an impact modifier such as an acid-modified ethylene copolymer.
  • it is also excellent in low water absorption, molding processability, chemical resistance, and the like.
  • the polyamide resin composition of the present invention preferably contains the following as other components.
  • Polymers other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of Component A. Part, more preferably 0.5 to 30 parts by weight.
  • the resin composition of this invention can contain another additive in the range which does not impair the effect of this invention.
  • additives include pigments, dyes, colorants, antioxidants, weathering agents, UV absorbers, light stabilizers, lubricants, crystal nucleating agents, crystallization accelerators, heat resistance agents, antistatic agents, plasticizers, Examples thereof include stabilizers such as copper compounds, antistatic agents, flame retardants, glass fibers, lubricants, fillers, reinforcing fibers, reinforcing particles, and foaming agents.
  • Molding process from polyamide resin composition to molded body The present invention also provides a molded body molded from the above-described polyamide resin composition of the present invention.
  • the molding method from the polyamide resin composition of the present invention to a molded body all known molding methods applicable to polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching can be used. These can be processed into molded products such as films, sheets, molded products, and fibers.
  • predetermined amounts of polyamide resin, mold release agent and various additives used as necessary are reduced using a low-speed rotary mixer such as a V-type blender 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 blender or tumbler
  • a high-speed rotary mixer such as a Henschel mixer.
  • the molded product obtained by the present invention includes various extruded products, various injection molded products, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded products have been conventionally used.
  • the molded article 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 equipment, medical supplies, and household goods.
  • the polyamide resin composition for metal coating of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range, heat resistance, and melt moldability (hereinafter referred to as thermal characteristics) for improving productivity during coating processing.
  • the content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, still more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably. 80 to 100% by mass, more preferably 80 to 95% by mass.
  • 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, it is preferable that the metal coating material further includes a component for improving adhesion.
  • a component for improving adhesion As a component aiming at adhesiveness improvement, a thermoplastic elastomer (component C1) and / or a silane coupling agent (component C2) are mentioned preferably, for example.
  • component C1 is preferably an epoxidized styrene elastomer (component C1 ′) and / or a modified polyolefin.
  • Component C1 is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polyamide resin, from the viewpoint of stably securing the adhesion, mechanical characteristics and surface characteristics of the polyamide resin composition of the present invention to the metal substrate.
  • the amount is preferably 3 to 28 parts by mass, more preferably 3 to 25 parts by mass.
  • the content of component C2 is based on 100 parts by mass of component A from the viewpoint of stably securing the adhesion, fluidity and surface characteristics of the polyamide resin composition of the present invention to the metal substrate.
  • the amount is preferably 0.01 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass.
  • Epoxidized styrene-based elastomer (component C1 ′)
  • component C1 ′ which is an epoxidized styrene-based elastomer, for example, as described in JP-A-2004-346255 described above
  • An epoxidized styrene thermoplastic elastomer obtained by epoxidizing a double bond derived from a conjugated diene compound in a block copolymer comprising a styrene compound polymer block and a conjugated diene compound polymer block is preferred.
  • the styrene compound polymer block, the conjugated diene compound, and the conjugated diene compound polymer block mean the following.
  • a styrene compound polymer block is a polymer block mainly composed of a group derived from a styrene compound.
  • a structural unit derived from a styrene compound has an adhesive force with a coating object and mechanical properties.
  • the content is preferably 50 to 80% by mass, more preferably 50 to 70% by mass, and still more preferably 50 to 60% by mass.
  • the conjugated diene compound is a conjugated diene compound or a partially hydrogenated product thereof.
  • the conjugated diene compound polymer block is a polymer block mainly composed of a group derived from a conjugated diene compound, and in the polymer block, the structural unit derived from a conjugated diene compound is from the viewpoint of flexibility,
  • the amount is preferably 20 to 50% by mass, more preferably 30 to 50% by mass, and still more preferably 40 to 50% by mass.
  • Styrenic compounds used for component C1 ′ include styrene, ⁇ -methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinyl from the viewpoint of stably securing adhesive strength with the object to be coated and mechanical properties. At least one compound selected from the group consisting of benzene, p-methylstyrene, 1,1-diphenylstyrene, vinylnaphthalene and vinylanthracene is preferred, and styrene is more preferred.
  • Conjugated diene compounds used for component C1 ′ include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3 from the viewpoint of flexibility.
  • -At least one compound selected from the group consisting of octadiene and phenyl-1,3-butadiene is preferred, and butadiene and / or isoprene are more preferred.
  • the weight average molecular weight of component C1 ′ is preferably from 5,000 to 600,000, more preferably from 10,000 to 500,000, from the viewpoint of stably securing the adhesive force and mechanical properties with the coating target.
  • the molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)] is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 5. Mw can be measured by gel permeation chromatography (GPC) under the following conditions.
  • -Apparatus Waters gel permeation chromatograph (product number: GPC / V2000) Column: Shodex AT-G + AT-806 ⁇ 2 -Eluent: Orthodichlorobenzene-Eluent flow rate: 1.0 mL / min-Column temperature: 145 ° C ⁇ Detection method: Differential refractometer (RI) -Calibration curve: Prepared using standard polystyrene material. Mn is measured under the aforementioned conditions.
  • the molecular structure of component C1 ' is preferably linear.
  • the styrene compound (P) and the conjugated diene compound (Q) have a structure such as PQP, QPQP, PQPPP, or the like.
  • a compound-conjugated diene compound block copolymer is preferred.
  • the block copolymer may have a polyfunctional coupling agent residue at the molecular end.
  • the manufacturing method of component C1 ′ may be any manufacturing method as long as a material having the structure as described above is obtained.
  • a styrene compound-conjugated diene compound block copolymer can be produced in an inert solvent using a lithium catalyst or the like.
  • Hydrogenation in the presence of a hydrogenation catalyst in an inert solvent can produce a partially hydrogenated block copolymer that is a raw material for component C1 ′.
  • the degree of hydrogenation can be determined by NMR analysis of the block copolymer before and after hydrogenation.
  • the hydrogenation rate is defined as the percentage of hydrogenated double bonds derived from the conjugated diene compound of the unhydrogenated / epoxidized raw material block copolymer. From the viewpoint of stably securing the heat resistance and cohesiveness of component C1 ′, the hydrogenation rate is preferably in the range of 0 to 80%, more preferably in the range of 10 to 70%.
  • Epoxidized styrene thermoplastic elastomer can be obtained by epoxidizing the block copolymer.
  • it can be obtained by reacting the block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent.
  • the inert solvent is used for the purpose of reducing the viscosity of the raw material, stabilizing by dilution of the epoxidizing agent, and for example, hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, chloroform and the like can be used.
  • hydroperoxides among epoxidizing agents include hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and the like.
  • “peracids” include performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Among them, peracetic acid is preferred because it is produced industrially in large quantities, can be obtained at low cost, and has high stability.
  • the amount of the epoxidizing agent is not strictly limited, and can be changed depending on the individual epoxidizing agent used, the desired degree of epoxidation, and the difference in the properties of the individual block copolymers used.
  • a catalyst can be used as necessary.
  • an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.
  • hydroperoxides a catalytic effect is obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. be able to.
  • peracetic acid is preferably 0 to 70 ° C. This is because decomposition of peracetic acid occurs when the temperature exceeds 70 ° C. 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 epoxidation can be changed according to the reactivity of the epoxidizing agent used in accordance with a conventional method.
  • Isolation of the obtained epoxidized styrenic thermoplastic elastomer includes, for example, a method of precipitating with a poor solvent, a method of adding the epoxidized styrenic thermoplastic elastomer into hot water with stirring and distilling off the solvent, heating and The solvent can be directly dried by a decompression operation or the like. Moreover, when finally utilizing by a solution form, it can also be used without isolating.
  • the epoxidation rate of component C1 ′ is preferably 10 to 40%, more preferably 15 to 35, from the viewpoint of suppressing the gelation of component C1 ′ and stably ensuring the heat resistance of the polyamide resin composition of the present invention. % Is preferred.
  • the double bond derived from the conjugated diene compound remaining unsaturated without being hydrogenated or epoxidized is less than 90% of the total, More preferably, it is 40% or less.
  • Epoxidation rate ⁇ 10000 ⁇ D + 2 ⁇ H ⁇ (100 ⁇ S) ⁇ / ⁇ (N ⁇ 16) ⁇ (100 ⁇ S) ⁇ (D represents the molecular weight of the conjugated diene compound, H represents the hydrogenation rate (%), and S represents the content (mass%) of the styrene compound).
  • the weight (g) of the epoxidized styrenic thermoplastic elastomer used in the above, V is a titration amount (ml) of hydrobromic acid, and f is a factor of hydrobromic acid).
  • Component C2 which is a silane coupling agent, chemically converts an organic functional group having affinity or reactivity with an organic resin to a hydrolyzable silyl group having affinity or reactivity with an inorganic material. It is a silane compound having a bonded structure.
  • Examples of the hydrolyzable group bonded to silicon include an alkoxy group, a halogen, and an acetoxy group. Usually, an alkoxy group, particularly a methoxy group and an ethoxy group are preferably used.
  • the number of hydrolyzable groups attached to one silicon atom is selected between 1 and 3.
  • Examples of the organic functional group include an amino group, an epoxy group, a vinyl group, a carboxyl group, a mercapto group, a halogen group, a methacryloxy group, and an isocyanate group, and preferably an amino group or an epoxy group.
  • component C2 include ⁇ -aminoethyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminobutyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ - Aminopropylmethyldiethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ - (aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane
  • component C2 is based on 100 parts by mass of component A from the viewpoint of stably securing the adhesion, fluidity and surface characteristics of the polyamide resin composition of the present invention to the metal substrate. 0.01 to 0.5 parts by mass is preferable, and 0.1 to 0.3 parts by mass is more preferable.
  • Polymers other than components A and B In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than components A and B, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers outside the polyamide, such as heat Plastic polymers and elastomers can be included.
  • polyamides other than components A and B such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers outside the polyamide, such as heat Plastic polymers and elastomers can be included.
  • the polyamide resin composition of the present invention can coat a wide range of metal substrates such as non-ferrous metals such as aluminum and iron, and the coated polyamide resin composition may form a coating material, and the coated polyamide resin composition and A metal substrate forms a metal coated article.
  • metal coating include anti-rust coating for fluid metal pipes for general industrial use, anti-corrosion coating for metal pipes such as steel pipes and aluminum pipes for automobile fuel, oil, brake fluid, etc., metal wire coatings, tank tanks For example, it is possible to apply to a metal pipe for automobiles.
  • a method of coating a metal substrate with the polyamide resin composition of the present invention for example, A method of coating a metal substrate which is an adherend with a polyamide resin composition already in a molten state, such as a steel pipe coating by extrusion, As in powder coating, a method of coating a metal substrate by heating a metal substrate that is an adherend, melting the solid polyamide resin composition by the heat, and For example, a method in which a metal substrate and a polyamide resin composition in a solid state in contact with each other are heated and coated may be used. Prior to coating with the polyamide resin composition 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 of the present invention is preferably maintained at a temperature that does not denature the polyamide resin composition of the present invention.
  • the polyamide resin composition for injection molding of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range, heat resistance, and the like for improving productivity during injection molding.
  • the content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, and still more preferably 60 to 100% by mass.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, and still more preferably with respect to 100 parts by weight of component A. Is 0 to 30 parts by mass.
  • the resin composition of the present invention can produce an injection-molded body with little warpage and excellent dimensional stability with only component A.
  • the resin of the present invention may further include the above-described layered silicate (component B5). Further, by adding a layered silicate, it is possible to improve the rigidity, weather resistance and / or heat resistance, and barrier property against liquid or vapor of an injection-molded body produced from the resin composition of the present invention.
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but the rigidity, weather resistance and / or heat resistance of the injection-molded product, and liquid or vapor From the viewpoint of improving the barrier property against the above and from the viewpoint of securing the molding processability and impact resistance of the resin composition, it is preferably 0.05 to 10 parts by mass, more preferably 0. 05 to 8 parts by mass, more preferably 0.05 to 5 parts by mass.
  • injection-molded body of the present invention is a combination of not only injection molding but also, for example, extrusion molding, blow molding, compression molding, injection molding and the like. Can be produced by molding.
  • the injection molded product is not particularly limited, but a molded product that is required to have low warpage and excellent dimensional stability, for example, a component having a complicated shape, such as an oil tank for two-wheeled and four-wheeled vehicles, an intake system component, And molded articles suitable for the manufacture of integrated parts, electrical component cases, and other containers.
  • the injection-molded body also includes a welding joint member.
  • an intake system module component that integrates an intake system component such as an intake manifold of an automobile that requires high strength and durability, a cylinder head cover, an intake manifold, an air cleaner, and the like.
  • Cooling system parts such as water inlets and water outlets, fuel system parts such as fuel injection and fuel delivery pipes, containers such as oil tanks, and electrical equipment cases such as switches.
  • the polyamide resin composition for extrusion molding of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range, heat resistance, and the like for improving productivity during extrusion molding. From the viewpoint of ensuring melt moldability (hereinafter also referred to as thermal characteristics), and ensuring low water absorption, chemical resistance, hydrolysis resistance, and mechanical strength and elongation and / or barrier properties of the extruded product.
  • the content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 92 to 100% by mass, and still more preferably. 95 to 100% by mass.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of Component A. Part, more preferably 0.5 to 30 parts by weight.
  • the resin composition of the present invention can produce an extrusion-molded body excellent in mechanical strength and elongation and / or barrier properties only with Component A, but more stable mechanical strength and elongation and / or barrier. In applications where properties are required, it is preferable to further include the above-mentioned layered silicate (component B5) in the resin composition of the present invention.
  • the layered silicate as a reinforcing agent 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 can improve the mechanical strength, heat resistance, barrier properties against liquids (especially alcohol, water, etc.) and gases (especially oxygen, gasoline, etc.) as a barrier property improving component. .
  • the amount of the layered silicate is not particularly limited as long as the effect of improving mechanical strength and texture is obtained, but is preferably 0.05 with respect to 100 parts by mass of Component A used in the present invention. 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 ratio of the layered silicate decreases, the improvement effect tends to decrease, and when 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.
  • the polyamide resin composition for extrusion molding of the present invention is preferably molded using various types of extruders such as single screw and biaxial as the molding method, and melt molding is particularly preferable. Used.
  • the polyamide resin composition for extrusion molding of the present invention is a material suitable for processing various filaments, films and the like by a melt molding method.
  • the filament of the present invention can be used as various monofilaments and multifilaments.
  • applications include brush bristle, fishing line, hook-and-loop fastener, tire cord artificial turf, carpet, seat for automobile seats, Examples include fish nets, ropes, sills, filter threads, lawn mower filaments, toothbrushes, and automobile floor mats.
  • the method for forming the filament of the present invention is not limited to these.
  • the polyamide resin composition for extrusion molding containing component A is melted in a melt extruder such as a single screw, and the discharge amount is set.
  • the melt can be produced by extruding the melt from a spinneret through a gear pump that is controlled quantitatively and taking it at a predetermined take-up speed while cooling with air or water.
  • the filaments thus obtained may be further stretched at various magnifications depending on the application. Also, melt spinning and stretching may be performed simultaneously.
  • the filament may be either a monofilament or a multifilament, and may or may not be twisted.
  • the cross section of the filament may be circular, or may be an irregular cross section such as a hollow shape or a star shape.
  • the film of the present invention may be a stretched film or an unstretched film, and can be molded using any molding process known in the field of films.
  • a predetermined amount of component A and various other components used as necessary is melt-kneaded with an extruder, the kneaded product is extruded into a film form from a T-die, and cast on the casting roll surface.
  • An unstretched film can be formed by applying a T-die method for cooling the film, 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 may be used as one or more layers in a multilayer laminated film.
  • the layers other than the film of the present invention include, for example, a polyolefin film made of low density polyethylene, high density polyethylene, polypropylene, etc., a polyester film, a copolymer film made of ethylene-vinyl acetate copolymer, and an ionomer resin.
  • a film or the like can be used depending on 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 polyamide 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 may be melt-coextruded from a multilayer die via an adhesive resin as necessary.
  • the film of the present invention can be suitably used for applications such as industrial materials, industrial materials, household goods, and more specifically for food packaging, especially for retort, where the contents are liquid, and used for metal coating.
  • An antirust effect can also be imparted.
  • the polyamide resin composition for molding vehicle parts of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range and heat resistance for improving productivity during molding of vehicle parts. From the viewpoint of securing the weather resistance of the component strength of the vehicle parts, ensuring the properties, melt moldability (hereinafter also referred to as thermal characteristics),
  • the content of component A in the resin composition is It is preferably 50 to 100% by mass, preferably 70 to 100% by mass, preferably 90 to 100% by mass, more preferably 92 to 100% by mass, and still more preferably 95 to 100% by mass.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but with respect to 100 parts by mass of Component A,
  • the amount is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 0.5 to 30 parts by mass.
  • UV absorber As an ultraviolet absorber, the ultraviolet absorber conventionally used for the polyamide resin can be used.
  • the ultraviolet absorber include benzophenone, benzotriazole, triazole, imidazole, oxazole, resorcinol, salicylate, cyanoacrylate, triazine, metal complex, and the like.
  • the benzotriazole type is preferable.
  • an ultraviolet absorber for example, Tinuvin 327 (Ciba Specialty Chemicals benzotriazole), Tinuvin 234 (Ciba Specialty Chemicals benzotriazole), Sanduvor VSU (Clariant) Oxalic acid anilide type).
  • the ultraviolet absorber is preferably from 0.01 to 5 parts by weight, more preferably from 0.01 to 3.0 parts by weight, more preferably from 0.01 to 2.0 parts by weight, based on 100 parts by weight of the resin. More preferably, the content is 1 to 2.0 parts by mass.
  • Light stabilizer examples include hindered amines. Specifically, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) -2,2-bis (3 5-di-tertbutyl-4-hydroxybenzyl) malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, bis (2,2,6,6-tetramethyl-4 -Piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 4- [3- (3,5-di
  • light stabilizers include, for example, Tinuvin 123 (Ciba Specialty Chemicals Co., Ltd., hindered amine series) Chimassorb 944 (Ciba Specialty Chemicals Co., Ltd., hindered amine series), Chimassorb 119 (Ciba Specialty Chemicals Co., Ltd.) Hindered amine system).
  • the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3.0 parts by weight, and more preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of Component A. 0.1 to 2.0 parts by mass is more preferable.
  • Layered silicate (component B5) The vehicle parts of the present invention have low water absorption and excellent dimensional stability with only component A, but in applications where lower water absorption and dimensional stability are required, the layered silicate (component B5) is used as component A. Can be added. Further, by adding a layered silicate, it is possible to improve the rigidity, weather resistance and / or heat resistance, and barrier property against liquid or vapor of the vehicle component of the present invention.
  • the amount of the layered silicate is not particularly limited as long as the effect of improving mechanical strength and texture is obtained, but is preferably 0.05 with respect to 100 parts by mass of Component A used in the present invention. 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 ratio of the layered silicate decreases, the improvement effect tends to decrease, and when 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.
  • vehicle parts Examples of vehicle parts obtained by molding the polyamide resin composition for molding vehicle parts of the present invention include vehicle interior parts, vehicle exterior parts, automobile engine room interior parts, and the like.
  • Vehicle interior part means a part used for interior of a vehicle.
  • Vehicles include automobiles such as passenger cars, buses, trucks, special automobiles such as tractors, road rollers, snow vehicles, forklifts, wheel cranes, special purpose automobiles such as ambulances, fire trucks, television relay cars, and refrigerated cars. However, it is not limited to these.
  • the vehicle interior parts of the present invention include, for example, a register blade, a washer lever, a window regulator handle, a knob of a window regulator handle, a passing light lever, a sun visor bracket, an instrument panel, a console box, a glove box, a steering wheel, and a trim. It can be used for applications such as seat members such as seat rails, seat belt anchors, electric seat parts, seat heater parts, seat blowing parts, HVAC parts, steering switch parts, and the like.
  • Vehicle exterior parts means the parts used for the exterior of vehicles.
  • vehicles include automobiles such as passenger cars, buses, trucks, motorcycles, special automobiles such as tractors, road rollers, snow trucks, forklifts, wheel cranes, special purpose automobiles such as ambulances, fire trucks and television relays. Examples include, but are not limited to, cars, refrigerators, and motorbikes.
  • vehicle exterior parts include, but are not limited to, a mall, a lamp housing, a front grille, a mud guard, a side bumper, a bumper, and a fender.
  • automotive engine compartment components of the present invention include intake manifolds, air cleaners, resonators, fuel rails, throttle bodies and valves, air flow meters, EGR components, harness connectors, engine covers, cylinder head covers, Timing belt (chain cover), timing chain (belt) tensioner and guide, alternator cover, distributor cover, brake master cylinder, oil pump, oil filter, engine mount, paper canister, power steering oil reservoir, fuel strainer, radiator tank , Switch boots, lamp waterproof cover, connector cover, rubber hook, suspension There are boots, suspension upper mounts, suspension bushings, stabilizer bushings, steering rack boots, steering rack bushings, reservoir tank caps, plug cord caps, molded packing, battery terminal covers, and the like.
  • Polyamide resin composition for molded articles in direct contact with biodiesel fuel (1) Content of Component A
  • the polyamide resin composition for molded bodies (hereinafter also referred to as resin composition) that is in direct contact with the biodiesel fuel of the present invention can sufficiently ensure the relative viscosity ⁇ r and has a moldable temperature range.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but with respect to 100 parts by mass of Component A,
  • the amount is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 0.5 to 30 parts by mass.
  • the resin composition of the present invention can sufficiently secure the relative viscosity ⁇ r with only component A, has a wide moldable temperature range, is excellent in heat resistance and melt moldability, and has low water absorption as seen in aliphatic linear polyoxamide resins. It is possible to produce a molded article that stably secures chemical resistance, hydrolysis resistance, fuel barrier properties, and biodiesel fuel resistance as compared with conventional aliphatic polyamide resins without impairing properties. However, in applications where biodiesel fuel resistance is further required, it is preferable to further include the above-mentioned layered silicate in the resin composition of the present invention. In addition, by adding layered silicate, the molded body produced from the resin composition of the present invention improves the biodiesel fuel resistance, rigidity, weather resistance and / or heat resistance, and barrier property against liquid or vapor. Can be made.
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but the rigidity, weather resistance and / or heat resistance of the injection-molded product, and liquid or vapor From the viewpoint of improving the barrier property against the above and from the viewpoint of securing the molding processability and impact resistance of the resin composition, it is preferably 0.05 to 10 parts by mass, more preferably 0. 05 to 8 parts by mass, more preferably 0.05 to 5 parts by mass.
  • Plasticizer (component C5)
  • a plasticizer examples include benzenesulfonic acid butyramide, esters of p-hydroxybenzoic acid and linear or branched alcohols having 6 to 21 carbon atoms (for example, 2-ethylhexyl p-hydroxybenzoate). it can.
  • the compounding amount of the plasticizer is based on 100 parts by mass of the polyamide resin. The amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 30 parts by mass, and still more preferably 1 to 30 parts by mass.
  • Molded body in direct contact with biodiesel fuel The molded body in direct contact with the biodiesel fuel excellent in biodiesel fuel resistance of the present invention (hereinafter also referred to as molded body) is injected with the resin composition of the present invention.
  • All known molding methods applicable to polyamide, such as extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching, are possible, and these molding methods can be used to process films, sheets, molded products, fibers, etc. it can.
  • the molded article excellent in biodiesel fuel resistance obtained by the present invention can be used for any of various molded articles for which conventional polyamide resin fuel parts have been used.
  • Examples of the molded body 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.
  • the polyamide resin composition for fuel pipe parts of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range, heat resistance, and the like for improving productivity during molding. From the viewpoint of ensuring melt moldability (hereinafter also referred to as thermal characteristics), environmental resistance such as low temperature impact resistance of fuel pipe parts, chemical resistance, and liquid, vapor and / or gas impermeability,
  • the content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, and still more preferably 60 to 100% by mass.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but with respect to 100 parts by mass of Component A,
  • the amount is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and still more preferably 0 to 30 parts by mass.
  • the resin composition of the present invention can produce a fuel piping component that is excellent in environmental resistance such as low-temperature impact resistance, chemical resistance and liquid, vapor and / or gas impermeability only with Component A.
  • the resin composition of the present invention can further contain a layered silicate (component B5).
  • layered silicate by adding layered silicate, the rigidity of fuel pipe parts prepared from the resin composition of the present invention, environmental resistance such as low temperature impact resistance, chemical resistance and impermeability of liquid, vapor and / or gas Can be improved.
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited.
  • the rigidity, weather resistance and / or heat resistance of the fuel pipe component, and liquid or vapor are not limited.
  • 0.05 to 10 parts by weight More preferably 0.05 to 8 parts by mass, More preferably, it is 0.05 to 5 parts by mass.
  • plasticizer (component C5) From the viewpoint of impact resistance at low temperature and imparting flexibility, the above-described plasticizer (component C5) is preferably blended with the polyamide resin composition of the present invention.
  • the compounding amount of the plasticizer is based on 100 parts by mass of the resin component in the polyamide resin composition of the present invention.
  • the amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 15 parts by mass.
  • the polyamide resin composition of the present invention can dissipate static electricity generated when transporting fluids such as fuel by forming fuel transportation parts in the fuel piping parts, and can prevent parts from being damaged or exploding due to sparks. From the viewpoint of becoming, it is preferable to blend the above-described conductivity-imparting agent (component B6). For example, it is preferable that a fuel pipe component is joined to a conductive joint and a conductive tube to form an electric transportation circuit.
  • Examples of the conductivity imparting agent include all fillers added to impart conductive performance to the resin, and examples thereof include granular, flaky and fibrous fillers.
  • particulate filler carbon black, graphite or the like can be suitably used.
  • flaky filler aluminum flakes, nickel flakes, nickel-coated mica and the like can be suitably used.
  • fibrous filler metal fibers such as carbon nanotubes, carbon nanofibers, carbon fibers, carbon-coated ceramic fibers, carbon whiskers, aluminum fibers, copper fibers, brass fibers, and stainless fibers can be suitably used.
  • the fibrous filler is also preferable from the viewpoint of improving the mechanical properties of fuel piping parts obtained by molding the polyamide resin composition of the present invention.
  • carbon fiber and carbon black can be used suitably.
  • the blending amount of the conductivity imparting agent varies depending on the type of the conductivity imparting agent to be used, it cannot be specified unconditionally, but from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc. 2 to 30 parts by weight is preferably selected with respect to 100 parts by mass of the entire resin including the polyamide resin.
  • the amount of the fuel pipe component obtained by melt-extruding the polyamide resin composition blended therewith is preferably 10 9 ⁇ cm or less, more preferably 10 6 ⁇ cm or less.
  • Organic fiber and inorganic filler (component C6)
  • the polyamide resin composition of the present invention is preferably used in a joint for fuel piping, Or it is preferable to mix
  • organic fibers examples include aramid fibers.
  • inorganic fibers such as glass fiber, carbon fiber, wollastonite and potassium titanate whisker, Inorganic fillers such as montmorillonite, talc, mica, calcium carbonate, silica, clay, kaolin, glass powder, and glass beads are used.
  • the fiber diameter is preferably 0.01 to 50 ⁇ m, more preferably 0.03 to 30 ⁇ m, still more preferably 0.05 to 20 ⁇ m
  • the fiber length is preferably 0.1 to 15 mm, more preferably 0.5 to 15 mm, still more preferably 0.5 to 10 mm, Are preferably used.
  • the inorganic fibers are cut and the like, and within the polyamide resin composition or the fuel pipe part of the present invention,
  • the fiber diameter of the inorganic fiber is 0.01 to 50 ⁇ m, preferably 0.03 to 30 ⁇ m
  • the fiber length of the inorganic fiber may be about 0.5 to 10 mm, preferably about 0.7 to 5 mm.
  • glass fibers are preferably used because of their high reinforcing effect.
  • the creep resistance of the fastening portion of the fuel pipe component of the present invention is high and deformation does not occur, and permanent sealing becomes possible.
  • the amount of organic fiber and / or inorganic filler used is the fuel pipe part of the present invention.
  • the amount is preferably 10 to 50% by weight.
  • Fuel piping component of the present invention is applied to various applications that require barrier properties of liquid or vapor fuel obtained by molding the polyamide resin composition for fuel piping components of the present invention. be able to.
  • Applicable uses include, for example, fuel tanks such as gasoline tanks, alcohol tanks, fuel tubes, brake oil tanks, clutch oil tanks, power steering oil tanks, Fuel strainer, fluorocarbon tube for cooler, fluorocarbon tank, canister, air cleaner, intake system parts, tire inner liner, tank valve, fuel delivery pipe, quick connector, EGR parts, parts for fuel tanks such as oil strainer, fuel tube, Fuel pipe fittings are preferred, Fuel tank parts, fuel tubes, and fuel pipe joints are more preferred.
  • the fuel tank parts of the present invention are prepared by injecting, extruding, hollowing, pressing, rolls, foaming, vacuum / pressure air, stretching, etc. Molded using a conventionally known molding method according to its application, vibration welding method, die slide injection, injection welding method such as die rotary injection and two-color molding, ultrasonic welding method, spin welding method, hot plate welding method, It can be applied to an object using a hot wire welding method, a laser welding method, a high frequency induction heating welding method, or the like.
  • the temperature of the polyamide resin is preferably maintained at a temperature that does not alter the polyamide resin.
  • the fuel pipe component of the present invention is obtained by molding the polyamide resin of the present invention, and preferably comprises a layer comprising the polyamide resin composition for fuel pipe components of the present invention (hereinafter referred to as layer 1). It is preferable to have (also called).
  • the fuel pipe component of the present invention may be a single-layer tube composed of only layer 1, but is preferably used as a multilayer tube in which one or more layers other than layer 1 and layer 1 are laminated. In practical fuel piping parts, multi-layer tubes are often used.
  • the thickness of the layer 1 is determined from the viewpoint of stably ensuring the fuel impermeability and simultaneously satisfying many required characteristics required for the fuel piping component.
  • the thickness is preferably 20 to 80%, more preferably 30 to 70%.
  • the outer diameter of the fuel piping component can be designed in consideration of the flow rate of various fuels, and the wall thickness is a thickness that does not increase the permeability of various fuels and can maintain the breaking pressure of the fuel tube, and although it can be designed with a thinness that can maintain flexibility with a good degree of ease of assembly of the fuel tube and vibration resistance during use,
  • the outer diameter is preferably 4 to 15 mm, more preferably 3 to 13 mm,
  • the wall thickness is preferably 0.5 to 2 mm, more preferably 0.7 to 1.8 mm.
  • At least one resin selected from the group consisting of fluororesin, high-density polyethylene resin, PA11 resin and PA12 More preferably, it consists of a resin composition containing at least one resin selected from the group consisting of PA11 resin and PA12 and a plasticizer (preferably, the above-mentioned suitable plasticizer).
  • the content of the plasticizer ensures a stable breaking pressure of the fuel pipe component and suppresses bleed out, with respect to 100 parts by mass of the resin component of the layer other than the layer 1.
  • the amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 15 parts by mass.
  • a conductivity imparting agent (preferably, the above-described suitable conductivity imparting agent (component B6)) is added. It is preferable to mix
  • fluororesin examples include polytetrafluoroethylene (PTEF), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). Further, it may be a resin partially containing chlorine, such as polychlorofluoroethylene (PCTFE), or a copolymer with ethylene or the like.
  • PTEF polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • PCTFE polychlorofluoroethylene
  • the high density polyethylene resin those having an average molecular weight of about 200,000 to 300,000 are preferable in consideration of mechanical properties.
  • the high-density polyethylene resin has a low-temperature embrittlement temperature of ⁇ 80 ° C. or lower and excellent low-temperature impact resistance.
  • layers other than the layer 1 may be provided via an adhesive layer when the adhesiveness to the composition layer is poor.
  • Extrusion molding is preferably used as a method for producing the fuel pipe component of the present invention, and as a method for producing a multilayer fuel pipe component, for example, from the number of extruders corresponding to the number of constituent layers or the number of materials.
  • a multilayer tube such as a multilayer fuel tube
  • the molten resin extruded from a number of extruders corresponding to the number of constituent layers or the number of materials is introduced into one multilayer tube die, Bond each layer in the die or immediately after exiting the die, After that, the method of manufacturing in the same way as normal tube molding, Once the single layer tube is formed, Examples include a method of coating another layer on the outside of the tube.
  • the shape of the tube may be a straight tube or may be processed into a bellows shape.
  • a protective layer may be provided on the outside,
  • the forming material include rubbers such as chloroprene rubber, ethylene propylene diene terpolymer, epichlorohydrin rubber, chlorinated polyethylene, acrylic rubber, chlorosulfonated polyethylene, and silicon rubber.
  • the resin composition of the present invention is melted separately at an extrusion temperature of 340 ° C., the discharged molten resin is molded into a laminated tubular body, cooled by a sizing die that controls dimensions, and taken up.
  • a single-layer tube formed by molding the resin composition of the present invention can be produced.
  • Extrusion temperature of the resin composition of the present invention is 340 ° C
  • PA11 is melted separately at an extrusion temperature of 260 ° C.
  • the discharged molten resin is joined by an adapter, formed into a laminated tubular body, cooled by a sizing die that controls dimensions, and taken up.
  • Layer 1 (inner layer) formed by molding the resin composition of the present invention A two-layer hose can be manufactured as layer 2 (outer layer) formed by molding PA6.
  • Extrusion temperature of the resin composition of the present invention is 340 ° C
  • PA11 was extruded at 260 ° C
  • PA12 is melted separately at an extrusion temperature of 260 ° C.
  • the discharged molten resin is joined by an adapter, formed into a laminated tubular body, cooled by a sizing die that controls dimensions, and taken off.
  • Layer 1 (innermost layer) formed by molding the resin composition of the present invention Layer 2 (intermediate layer) formed by molding PA6, A three-layer tube having a layer 3 (outermost layer) formed by molding PA12 can be produced.
  • an innermost layer extruder, an inner layer extruder, an intermediate layer extruder and an outer layer extruder are provided, and the resin discharged from these four extruders is collected by an adapter into a tube shape.
  • an apparatus comprising a die to be formed, a sizing die that cools the tube and controls its dimensions, and a take-up machine.
  • a resin composition containing PA11 of the present invention in the hopper of the innermost layer (layer 4) extruder A resin composition containing PA12 in the hopper of the inner layer (layer 3) extruder
  • the resin composition of the present invention is applied to the hopper of the intermediate layer (layer 1) extruder.
  • a multilayer tube can be produced by introducing another resin composition into the hopper of the outer layer extruder.
  • fuel pipe parts such as tubes for automobile fuel pipe systems are preferably mentioned.
  • the fuel pipe joint of the present invention can be produced by any of the injection molding methods and other known methods for producing resin joints of the present invention. Also good.
  • a fuel pipe quick connector More preferably, the quick connector for fuel pipes obtained by molding the polyamide resin composition for fuel pipe parts of the present invention in the cylindrical main body portion of the quick connector for fuel pipes may be mentioned.
  • FIG. 3 shows a cross section of a typical quick connector 1.
  • the end of the steel tube 2 and the end of the plastic tube 3 are connected to each other.
  • the flange-shaped portion 4 located away from the end of the steel tube 2 is detachably engaged by the retainer 5 of the connector 1, and the fuel is sealed by the row of O-rings 6.
  • the connector end portion forms an elongated nipple 7 having a plurality of jaw portions 8 protruding in the radial direction.
  • the end portion of the plastic tube 3 is closely fitted to the outer surface of the nipple 7 and the fuel is sealed by mechanical joining with the jaw portion 8 and an O-ring 9 provided between the tube and the nipple.
  • each part such as a cylindrical main body, a retainer and an O-ring is formed by injection molding and then assembled and assembled at a predetermined place.
  • the quick connector is assembled into an assembly that is engaged with a tube, preferably a tube formed from a resin composition containing a resin (hereinafter also referred to as a resin tube), and used as a fuel piping component.
  • a tube preferably a tube formed from a resin composition containing a resin (hereinafter also referred to as a resin tube), and used as a fuel piping component.
  • 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. Thereby, airtightness can be improved.
  • airtightness can be improved by using a thick resin tube, heat-shrinkable tube, clip or the like that can apply a sufficient tightening force to the overlapping part.
  • the resin tube may have a corrugated area 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 accordion shape, a corrugated shape, or the like.
  • the resin tube preferably includes a layer made of a polyamide resin composition including a polyamide resin such as nylon 11 or nylon 12, and preferably has a multilayer structure including a barrier layer.
  • a polyamide resin such as nylon 11 or nylon 12
  • a barrier layer preferably has a multilayer structure including a barrier layer.
  • PBT, PBN, fluorine resin, PA92 Nylon in which clay is nano-dispersed, EVOH, or the like can be used as a resin for forming the barrier layer.
  • a configuration in which a conductive layer is included in the innermost layer is preferable for preventing damage due to static electricity.
  • the protective member may be a sponge-like porous body by a known method.
  • a protective part that is lightweight and excellent in heat insulation can be formed. Moreover, material cost can also be reduced. Alternatively, the strength may be improved by adding glass fiber or the like.
  • the shape of a protection member is not specifically limited, Usually, it is a block-shaped member which has a recessed part which receives a cylindrical member or a multilayer tube. In the case of a cylindrical member, a multilayer tube can be inserted later into a cylindrical member prepared in advance, or the cylindrical member can be coated and extruded on 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 integrated with each other. Forming a structure.
  • the quick connector according to the present invention when combined with an airtightness improving technique such as O-ring or welding, has a small amount of wall permeation of fuel / gasoline mixed fuel and the like, and has excellent characteristics such as creep deformation resistance. . Therefore, the quick connector according to the present invention is useful as an excellent fuel line system capable of flexibly responding to strict fuel emission regulations in combination with a resin tube excellent in fuel barrier properties, preferably a fuel tube according to the present invention.
  • SMT surface mounting technology
  • SMD surface mounted component
  • the polyamide resin composition for SMD of the present invention (hereinafter also referred to as a resin composition) is a good moldable temperature range, heat resistance, and the like for improving the productivity at the time of molding SMD. From the viewpoint of ensuring melt moldability (hereinafter also referred to as thermal characteristics), ensuring stable heat resistance at high temperatures of SMD, and stable chemical resistance to various chemicals,
  • the content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, still more preferably 60 to 100% by mass, and still more preferably 70 to 90% by mass. It is.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, and still more preferably with respect to 100 parts by weight of component A. Is 0 to 30 parts by mass.
  • the resin composition of the present invention preferably contains component C7 that is inorganic particles, Considering that SMD is used as a component of a printed wiring board, inorganic particles such as metal oxides and inorganic compounds having no conductivity are more preferable. More preferred are metal oxides such as iron oxide and zinc oxide, and sulfides such as molybdenum sulfide.
  • inorganic particles having a density of 5 g / cm 3 or more can be preferably used.
  • magnetic particles such as ferrites such as barium ferrite and strontium ferrite, rare earth magnetic materials such as samarium-cobalt and neodymium-iron-boron are used. It can be preferably used.
  • 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 coupling agent, surface treatment with a silane surface treatment agent, and the like.
  • a titanate coupling agent for example, a known method described in the above-mentioned JP-A-2-255760
  • a known method described in the above-mentioned JP-A-10-158507 can be employed.
  • the mass ratio of component A and component C7 is such that the weight ratio of component A and component C7 (component A / component C7) is from the viewpoint of efficiently adding properties such as higher specific gravity and magnetism.
  • the ratio is preferably 50/50 to 5/95, more preferably 20/80 to 5/95.
  • the resin composition of the present invention preferably contains a reinforcing fiber from the viewpoint of ensuring the resistance to deformation load received under high temperature, and has conductivity when considering that SMD is used as a component of a printed wiring board. Preferably not.
  • reinforcing fibers examples include inorganic fibers such as glass fibers and mineral fibers, and organic fibers such as aramid fibers that are tougher than polyamide resins. Glass fibers are preferred from the viewpoint of availability. By blending the reinforcing fiber, physical properties such as strength and creep resistance of the composition are improved.
  • the fiber diameter is preferably 0.01 to 50 ⁇ m, more preferably 0.03 to 30 ⁇ m
  • the fiber length is preferably 1 to 50 mm, more preferably 1 to 30 mm, still more preferably 1 to 20 mm, Are preferably used.
  • the fiber diameter of the inorganic fiber is 0.01 to 50 ⁇ m, preferably 0.03 to 30 ⁇ m
  • the fiber length of the inorganic fiber may be about 0.5 to 10 mm, preferably about 0.7 to 5 mm.
  • the blending ratio of the glass fiber ensures the effect of improving the rigidity and creep resistance of the molded body by the resin composition of the present invention stably, and stably secures the fluidity of the resin composition of the present invention to suppress short shots.
  • the amount is preferably 2 to 40 parts by weight, more preferably 2 to 38 parts by weight, and still more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the total resin of the resin composition of the present invention. Part.
  • Component A has excellent mechanical strength, chemical resistance, low water absorption, hydrolysis resistance, etc., has a wide moldable temperature range, and excellent melt moldability. In addition, it is basically maintained as it is, and certain characteristics such as mechanical strength and heat resistance are improved by the addition of the reinforcing fiber.
  • the SMD of the present invention is obtained by, for example, injection molding, extrusion molding, blow molding, (press, roll) compression molding, hollow molding, foaming, vacuum / compressed air, It can be produced by molding by combining stretch foaming, stretching and the like.
  • the reinforcing fibers and inorganic particles It is also possible to add the reinforcing fibers into the resin that is blended in advance with the resin and the reinforcing fibers blended in the resin composition of the present invention, such as component A, or melted and kneaded in the middle of the molding machine.
  • a flexible wiring board, a harness / cable, an SMT connector and the like are preferable, and an SMT connector is more preferable.
  • the polyamide resin composition for an electrophotographic apparatus component (hereinafter also referred to as a resin composition) of the present invention can be molded well to improve productivity during molding of the electrophotographic apparatus component. From the viewpoint of ensuring the temperature range, heat resistance, melt moldability, and ensuring that the electrophotographic apparatus parts stably maintain conductivity, surface smoothness and mechanical properties at high temperatures,
  • the content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, and still more preferably 60 to 100% by mass.
  • Conductivity means, for example, an electrical characteristic such that static electricity does not accumulate in an insulator such as a resin when an electrophotographic apparatus component operates in the electronic apparatus. Thereby, it is possible to dissipate static electricity generated when the electrophotographic apparatus component operates in the electronic apparatus.
  • the blending amount of the conductivity imparting agent varies depending on the type of the conductivity imparting agent to be used, it cannot be specified unconditionally, but from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc.
  • the amount is preferably 2 to 40 parts by mass with respect to 100 parts by mass of the entire resin including the polyamide resin.
  • the amount is more preferably 2 to 30 parts by weight, still more preferably 2 to 15 parts by weight.
  • the amount is more preferably 3 to 40 parts by mass, still more preferably 5 to 35 parts by mass, and still more preferably 7 to 35 parts by mass.
  • the conductivity required for the material for an electrophotographic apparatus component of the present invention may vary depending on the application, but considering that the surface resistance of the polyamide resin is about 10 15 ⁇ , the conductivity of the resin composition of the present invention is By adding a property-imparting agent, it is preferably about 10 1 to 10 12 ⁇ , more preferably about 10 3 to 10 10 ⁇ .
  • the resin composition of the present invention can produce an electrophotographic apparatus component that is excellent only in components A and B6 and has excellent conductivity, surface smoothness, and mechanical properties at high temperatures.
  • the addition of layered silicate can improve the rigidity and mechanical properties of the electrophotographic apparatus parts produced from the resin composition of the present invention.
  • the amount of the above-mentioned layered silicate ensures the viewpoint of improving the rigidity, weather resistance and / or heat resistance of the parts of the electrophotographic apparatus, and the barrier property against liquid or vapor, and the molding processability and impact resistance of the resin composition. From the viewpoint, with respect to 100 parts by mass of component A, The amount is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.05 to 5 parts by mass.
  • polystyrene resin elastomer other than Component A
  • component A elastomer
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, and still more preferably with respect to 100 parts by weight of component A. Is 0 to 30 parts by mass.
  • the resin composition of this invention may mix
  • the blending ratio of the glass fiber ensures the effect of improving the rigidity and creep resistance of the molded body by the resin composition of the present invention stably, and ensures the fluidity of the resin composition of the present invention to suppress short shots.
  • the amount is preferably 2 to 40 parts by weight, more preferably 2 to 38 parts by weight, and still more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the total resin of the resin composition of the present invention. Part.
  • Component A has excellent mechanical strength, chemical resistance, low water absorption, hydrolysis resistance, etc., has a wide moldable temperature range, and excellent melt moldability. In addition, it is basically maintained as it is, and certain characteristics such as mechanical strength and heat resistance are improved by the addition of the reinforcing fiber.
  • Electrophotographic apparatus component The electrophotographic apparatus component of the present invention is obtained by, for example, injection molding, extrusion molding, blow molding, (press, roll) compression molding, hollow molding, foaming, vacuum- It can be produced by molding by combining compressed air, stretched foaming, stretching and the like.
  • Ingredients such as component A and the resin to be blended with the resin composition of the present invention and component B6, if necessary, component C8 are blended in advance, or component B is necessary in the resin melt-kneaded in the middle of the molding machine.
  • reinforcing fibers can be introduced.
  • the electrophotographic component can be produced by molding the electrophotographic apparatus component of the present invention by, for example, injection molding, extrusion molding, blow molding, compression molding or the like.
  • the electrophotographic apparatus component of the present invention is preferably obtained by inflation extrusion from the viewpoint of productivity.
  • a molded product having a cylindrical shape having an arbitrary diameter and a thickness of 30 to 1000 ⁇ m, more preferably 30 to 500 ⁇ m, still more preferably 30 to 300 ⁇ m is obtained.
  • the parts of the electrophotographic apparatus formed in this way have no seams, and the electrophotographic apparatus such as an electrophotographic copying machine, an intermediate transfer belt used for a printer, a fax machine, a transfer conveying belt, etc. It is useful as a belt for photographic devices.
  • a conductive roll for an electrophotographic apparatus can be obtained by coating an electrophotographic apparatus part formed into a cylindrical shape on a conductive support, and heating and fusing it. Or it can also be set as an electroconductive roll by carrying out melt coating of the electroconductive polyamide composition continuously on an electroconductive support body with an extruder.
  • the conductive roll is useful as, for example, a cleaning roll, a charging roll, a developing roll, or a transfer roll.
  • the electrophotographic apparatus component of the present invention formed into a cylindrical shape with the above-described thickness has an average surface roughness Ra of 1 ⁇ m or less, and the ratio between the maximum value and the minimum value of the surface resistivity in the same plane is 10. It is desirable to be less than double.
  • Ra is 1 ⁇ m or less, the sharpness of the generated image is remarkably improved.
  • the parts of the electrophotographic apparatus of the present invention have a uniform attractive force for attracting toner and paper, and the intermediate transfer belt, transfer conveyance It can be used more suitably as an electrophotographic apparatus component such as a belt, a cleaning roll, a charging roll, a developing roll, and a transfer roll.
  • an electrophotographic apparatus component such as a belt, a cleaning roll, a charging roll, a developing roll, and a transfer roll.
  • the Ra of the electrophotographic apparatus component it is effective to set the temperature of the annular die at the time of molding slightly higher.
  • the aggregate size of the conductivity imparting agent in order to suppress the ratio of the maximum value and the minimum value of the volume resistivity in the same plane of the electrophotographic apparatus component to 10 times or less, it is effective to suppress the aggregate size of the conductivity imparting agent to be small. Specifically, a method of forming the aggregate so that the average diameter thereof is 3 ⁇ m or less, more preferably 2 ⁇ m or less is effective.
  • the polyamide resin composition for IC tray of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range and heat resistance for improving the productivity at the time of molding an IC tray. From the viewpoint of ensuring the heat resistance and melt moldability (hereinafter, also referred to as thermal characteristics), and ensuring stable heat resistance at high temperatures of SDM and chemical resistance to various chemicals,
  • the content of component A in the resin composition is preferably 50 to 99% by mass, more preferably 55 to 99% by mass, and still more preferably 60 to 98% by mass.
  • the polyamide resin composition of the present invention has the above-mentioned conductivity from the viewpoint that the IC tray can dissipate static electricity generated when the integrated circuit component is transported or packaged, and the integrated circuit component can be prevented from being damaged.
  • An imparting agent (component B6) is blended.
  • Conductivity means, for example, an electrical characteristic such that static electricity does not accumulate in an insulator such as a resin when an IC tray transports or packages an integrated circuit component. As a result, it is possible to dissipate static electricity generated when the IC tray carries or packages integrated circuit components.
  • the blending amount of the conductivity imparting agent varies depending on the type of the conductivity imparting agent to be used, it cannot be specified unconditionally, but from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc.
  • the amount is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and further preferably 5 to 40 parts by mass with respect to 100 parts by mass of the entire resin including the polyamide resin.
  • carbon black from the viewpoint of the balance between conductivity and fluidity, with respect to 100 parts by mass of the entire resin including the polyamide resin, The amount is more preferably 2 to 30 parts by weight, still more preferably 2 to 15 parts by weight.
  • the amount is more preferably 3 to 40 parts by mass, still more preferably 5 to 35 parts by mass, and still more preferably 7 to 35 parts by mass.
  • the conductivity required for the IC tray material of the present invention may vary depending on the application, but considering that the surface resistance of the polyamide resin is about 10 15 ⁇ , imparting conductivity to the resin composition of the present invention.
  • the agent it is preferably about 10 0 to 10 12 ⁇ , more preferably about 10 0 to 10 10 ⁇ .
  • polymers other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, and still more preferably with respect to 100 parts by weight of component A. Is 0 to 30 parts by mass.
  • the resin composition of this invention may mix
  • the blending ratio of the glass fiber ensures the effect of improving the rigidity and creep resistance of the molded body by the resin composition of the present invention stably, and stably secures the fluidity of the resin composition of the present invention to suppress short shots.
  • the amount is preferably 2 to 40 parts by weight, more preferably 2 to 38 parts by weight, and still more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the total resin of the resin composition of the present invention. Part.
  • Component A has excellent mechanical strength, chemical resistance, low water absorption, hydrolysis resistance, etc., has a wide moldable temperature range, and excellent melt moldability. In addition, it is basically maintained as it is, and certain characteristics such as mechanical strength and heat resistance are improved by the addition of the reinforcing fiber.
  • IC tray of the present invention is obtained by subjecting the resin composition of the present invention to, for example, injection molding, extrusion molding, blow molding, (press, roll) compression molding, hollow molding, foaming, vacuum / pressure air, stretched foaming. It can be produced by molding by combining stretching and the like.
  • component A and the resin to be blended with the resin composition of the present invention and component B, and if necessary, component B in the resin that is pre-blended with reinforcing fibers or melt-kneaded in the middle of the molding machine For example, reinforcing fibers can be introduced.
  • Preferred IC trays obtained by molding the resin composition of the present invention include IC transport trays, IC storage trays, trays for heat treatment processes such as baking treatment, IC substrate cleaning trays, and the like.
  • the polyamide resin composition for industrial tubes of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range, heat resistance, and the like for improving productivity during molding. From the viewpoint of ensuring melt formability (hereinafter also referred to as thermal characteristics), environmental resistance such as low temperature impact resistance of industrial tube products, chemical resistance and impermeability of liquid, vapor and / or gas,
  • the content of component A in the resin composition is Preferably, it is 50 to 100% by mass, more preferably 55 to 100% by mass, and still more preferably 60 to 100% by mass.
  • polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer, Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.
  • polyamides other than component A such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers
  • An elastomer can be included.
  • the polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but with respect to 100 parts by mass of Component A,
  • the amount is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and still more preferably 0 to 30 parts by mass.
  • the resin composition of the present invention can produce an industrial tube excellent in environmental resistance such as low-temperature impact resistance, chemical resistance and liquid, vapor and / or gas impermeability only with Component A. Furthermore, in the use for which highly accurate dimensional stability is calculated
  • the amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but the rigidity, weather resistance and / or heat resistance of the industrial tube, and liquid or vapor are not limited. From the viewpoint of improving the barrier properties against and from the viewpoint of securing the molding processability and impact resistance of the resin composition, the amount is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.05 to 5 parts by mass.
  • plasticizer (component C) From the viewpoint of improving impact resistance at low temperatures, the above-mentioned plasticizer (component C) is preferably blended with the polyamide resin composition of the present invention.
  • the compounding amount of the plasticizer is based on 100 parts by mass of the resin component in the polyamide resin composition of the present invention.
  • the amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 15 parts by mass.
  • the polyamide resin composition of the present invention preferably contains the above-described conductivity-imparting agent (component B6), As the conductivity imparting agent, conductive carbon black is preferable.
  • the blending amount of the conductivity imparting agent is based on the polyamide resin composition of the present invention.
  • the amount is preferably 1 to 40 parts by mass, more preferably 3 to 35 parts by mass, and still more preferably 3 to 20 parts by mass.
  • Examples of the conductive carbon black include acetylene black and ketjen black. Among them, those having a good chain structure and a high aggregation density are preferable.
  • the industrial tube of the present invention is obtained by molding the polyamide resin of the present invention, and is preferably a layer comprising the industrial tube polyamide resin composition of the present invention (hereinafter also referred to as layer 1). It is preferable to have.
  • a hose is a hollow tube made of a soft material such as resin and used to send fluids such as liquids and gases. It is a slightly thick tube that can be bent at any time and used. It is called a tube.
  • the industrial tube of the present invention may be a single-layer tube composed of only the layer 1, but is preferably used as a multilayer tube in which one or more layers other than the layer 1 and the layer 1 are laminated. In practical industrial tubes, multilayer tubes are often used.
  • the thickness of the layer 1 is ensured from the viewpoint of stably ensuring the impermeability of liquid, vapor and / or gas, and simultaneously satisfying many required characteristics required for an industrial tube.
  • the thickness is preferably 20 to 80% of the wall thickness of the tube, and more preferably 30 to 70%.
  • the outer diameter of the industrial tube can be designed taking into account the flow rates of various liquids, vapors and / or gases, and the wall thickness does not increase the permeability of various liquids, vapors and / or gases, and is normal It can be designed with a thickness that can maintain the breaking pressure of the tube, and a thickness that can maintain flexibility with a satisfactory degree of ease of assembly work and vibration resistance during use.
  • the outer diameter is preferably 4 to 15 mm, more preferably 5 to 15 mm
  • the wall thickness is preferably 0.5 to 2 mm, more preferably 0.5 to 1.8 mm.
  • At least one resin selected from the group consisting of fluororesin, high-density polyethylene resin, PA11 resin and PA12 More preferably, it consists of a resin composition containing at least one resin selected from the group consisting of PA11 resin and PA12 and a plasticizer (preferably, the above-mentioned suitable plasticizer).
  • the content of the plasticizer is relative to 100 parts by mass of the resin component of the layer other than the layer 1. The amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 15 parts by mass.
  • a conductivity-imparting agent (the above-mentioned suitable conductivity-imparting agent) may be blended in the above-mentioned suitable blending amount. preferable.
  • fluororesin examples include polytetrafluoroethylene (PTEF), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). Further, it may be a resin partially containing chlorine, such as polychlorofluoroethylene (PCTFE), or a copolymer with ethylene or the like.
  • PTEF polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • PCTFE polychlorofluoroethylene
  • the high density polyethylene resin those having an average molecular weight of about 200,000 to 300,000 are preferable in consideration of mechanical properties.
  • the high-density polyethylene resin has a low-temperature embrittlement temperature of ⁇ 80 ° C. or lower and excellent low-temperature impact resistance.
  • layers other than the layer 1 may be provided via an adhesive layer when the adhesiveness to the composition layer is poor.
  • extrusion molding is preferably used, and as a method for producing a multilayer industrial tube, for example, from the number of extruders corresponding to the number of constituent layers or the number of materials.
  • a multilayer tube such as a multilayer fuel tube
  • the molten resin extruded from a number of extruders corresponding to the number of constituent layers or the number of materials is introduced into one multilayer tube die, Bond each layer in the die or immediately after exiting the die, After that, the method of manufacturing in the same way as normal tube molding, Once the single layer tube is formed, Examples include a method of coating another layer on the outside of the tube.
  • the shape of the tube may be a straight tube or may be processed into a bellows shape.
  • a protective layer may be provided on the outside,
  • the forming material include rubbers such as chloroprene rubber, ethylene propylene diene terpolymer, epichlorohydrin rubber, chlorinated polyethylene, acrylic rubber, chlorosulfonated polyethylene, and silicon rubber.
  • multilayer tubes can be formed with a Plabor (Plastics Engineering Laboratory Co., Ltd.) 2-layer hose molding machine and a 3-layer tube molding machine.
  • an innermost layer extruder, an inner layer extruder, an intermediate layer extruder and an outer layer extruder are provided, and the resin discharged from these four extruders is collected by an adapter into a tube shape.
  • an apparatus comprising a die to be formed, a sizing die that cools the tube and controls its dimensions, and a take-up machine.
  • a resin composition containing PA11 of the present invention in the hopper of the innermost layer (layer 4) extruder A resin composition containing PA12 in the hopper of the inner layer (layer 3) extruder
  • the resin composition of the present invention is applied to the hopper of the intermediate layer (layer 1) extruder.
  • a multilayer tube can be produced by introducing another resin composition into the hopper of the outer layer extruder.
  • Industrial tubes are preferably pneumatic tubes, hydraulic tubes, paint spray tubes, tubes for automobile piping (intake systems, cooling systems, fuel systems, etc.), and medical tubes such as catheters.
  • Production Example 1 (Component A: PX6-1) In a pressure vessel with an internal volume of about 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with a diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator and polymer outlet.
  • the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port.
  • butanol was extracted from the pressure relief port over about 20 minutes, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was brought to 310 ° C. over about 1 hour, and the reaction was carried out at 310 ° C. for 1.5 hours. . Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes.
  • the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
  • the string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
  • the temperature was raised to 275 ° C. over 1.5 hours. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 270 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was changed to 290 ° C. over about 1 hour, and the reaction was carried out at 290 ° C. for 2 hours. Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes.
  • the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
  • the string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
  • the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
  • the string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
  • Comparative resin 1 (polyamide resin: PX6-6, comparative production example 1)
  • Pre-polycondensation step The inside of a 1 L separable flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a raw material inlet is replaced with nitrogen gas having a purity of 99.9999%. 500 ml of dehydrated toluene, 1,6-Hexanediamine 58.7209 g (0.5053 mol) was charged. After this separable flask was placed in an oil bath and heated to 50 ° C, Dibutyl oxalate (102.1956 g, 0.5053 mol) was charged.
  • the temperature of the salt bath was set to 340 ° C. over 1 hour, the pressure in the container was reduced to about 66.5 Pa, and the reaction was further continued for 2 hours. Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin.
  • Compound B1 release agent
  • Compound p terminal modified product of polypropylene glycol (PPGA)
  • Compound q Tris (tridecyl phosphite)
  • Compound r Myristyl myristyl
  • Compound s Zinc stearate
  • Compound t Ethylene bisstearyl amide
  • Compound u Low molecular weight PE
  • Compound v Talc (magnesium silicate)
  • Compound w 1,3,2,4-dibenzylidenesorbitol
  • Compound x 3,9-bis [2- (3- (t-butyl-4-hydroxy-5-methylphenyl) propoxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5,5) Undecane
  • Compound y Triethylene glycol-bis [3- (3t-butyl-5methyl-4-hydroxyphenyl) propionate]
  • B4-1 Glass fiber (ECST-289 manufactured by Nippon Electric Glass (fiber diameter 13 ⁇ m)
  • B4-2 Carbon fiber (Toho Tenax Co., Ltd.
  • Besphite HTA-C6NR (fiber diameter 7 ⁇ m)
  • B4-3 Brass fiber (fiber diameter 80 ⁇ m)
  • B4-4 Strontium ferrite powder with an average particle diameter of 10 ⁇ m surface-treated with an aminosilane coupling agent
  • B4-5 Tungsten powder with an average particle diameter of 10 ⁇ m surface-treated with an aminosilane coupling agent (component B5 (layered silicate))
  • B6-1 Carbon black (Evonik Degussa Japan Co., Ltd.
  • B6-2 Carbon fiber (Toho Tenax Co., Ltd. Besphite HTA-C6NR (fiber diameter 7 ⁇ m) B6-3: Brass fiber (fiber diameter 80 ⁇ m), Ketjen black (EC600JD made by Ketjen Black International)
  • FIG. 1 is a cross-sectional view showing an outline of an injection molding machine for measuring a mold release force.
  • the fixed mold 3 and the movable mold 6 are processed so as to form a box having a width of 80 mm, a length of 100 mm, a depth of 30 mm, a wall thickness of 2.3 mm, and a cross rib inside.
  • the polyamide resin composition of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, is excellent in chemical resistance and hydrolysis resistance, and has mechanical properties under wet conditions.
  • Excellent polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component has a wider moldable temperature range, better melt moldability, higher molecular weight, and better heat resistance It turns out that a heat-resistant molded object can be manufactured. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Examples 1 to 7 and Comparative Examples 2 to 3 For the resin compositions containing the polyamide resins of Production Examples 1 to 5 and Comparative Resin Examples 2 (PA6) and 3 (PA66) and heat-resistant agents (compounds a and b), the compositions shown in Table 1 In a twin-screw kneader PCM-45 manufactured by Ikekai Tekko Co., Ltd., set the cylinder temperature to 340 ° C when PA6-1-2 and 6 are included as polyamide resin.
  • the heat-resistant molded article of the present invention was obtained by injection molding at a mold temperature of 80 ° C.
  • the polyamide resin composition of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, is excellent in chemical resistance and hydrolysis resistance, and has mechanical properties under wet conditions.
  • Excellent polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component has a wider moldable temperature range, better melt moldability, higher molecular weight, and better heat resistance It turns out that a heat-resistant molded object can be manufactured. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • the polyamide resin used in the present invention has low water absorption compared to nylon 6 and nylon 66, excellent chemical resistance, hydrolysis resistance, excellent mechanical properties under wet conditions, and It can be seen that it is possible to produce a tough molded body having a wider moldable temperature range and better melt moldability than the polyamide resin using 1,6-hexanediamine alone as the diamine component, and capable of increasing the molecular weight.
  • the polyamide resin composition of the present invention includes an impact modifier (component B) in addition to the polyamide resin (component A).
  • the polyamide resin composition basically includes a polyamide resin (component A). ) Characteristics.
  • Example 1 100 parts by weight of PX6-1 pellets, 40 parts by weight of Mitsui DuPont Himiran 1706 pellets (Ionomer) (B3-1) were blended in advance, and the resulting mixed pellets were fed to a Japanese-made TEX44 twin screw extruder for melt kneading. The strand was cooled and solidified in a cooling water tank, and then a pellet-like sample was obtained with a pelletizer. The pellet was dried under reduced pressure, and the pellet was subjected to evaluation.
  • Example 2 Except for following the formulation in Table 4, pellets were prepared in the same manner as in Example 1, and the pellets were subjected to evaluation.
  • Example 3 The impact improving material (B) was made by Mitsui DuPont, made by HiMilan 1855 pellets (ionomer) (B3-2), and the pellets were prepared in the same manner as in Example 1 except that the formulation shown in Table 4 was followed. The pellets were evaluated. It was used for.
  • Example 4 Except for the impact modifier (B), Exxelor VA1801 (maleic acid-modified ethylene-propylene resin) (B3-3), manufactured by Exxon Chemicals, the pellets were prepared in the same manner as in Example 1 except that the formulation shown in Table 4 was followed. The pellet was subjected to evaluation.
  • B impact modifier
  • Exxelor VA1801 maleic acid-modified ethylene-propylene resin
  • B3-3 manufactured by Exxon Chemicals
  • Example 5 Except for following the formulation in Table 4, pellets were prepared in the same manner as in Example 4, and the pellets were subjected to evaluation.
  • Example 6 The impact modifier (B) was Tafmer MH5020 (maleic acid-modified ethylene-butene resin) (B3-4) manufactured by Mitsui Chemicals, and pellets were prepared in the same manner as in Example 1 except that the formulation shown in Table 4 was followed. The pellet was subjected to evaluation.
  • Example 7 A pellet was prepared in the same manner as in Example 6 except that the impact modifier (B) was Tafuma-MH7020 (maleic acid-modified ethylene-butene resin) (B3-5) manufactured by Mitsui Chemicals and the formulation shown in Table 4 was followed. The pellet was used for evaluation.
  • the impact modifier (B) was manufactured by Asahi Kasei Corporation, Tuftec M1943 (epoxy-modified styrene block copolymer resin) (B3-6), and pellets were produced in the same manner as in Example 1 except that the formulation shown in Table 4 was followed. The pellet was subjected to evaluation.
  • Example 1 A pellet was prepared in the same manner as in Example 1 except that 100 parts by mass of Ube Industries 1015B pellet (nylon 6) and 18 parts by mass of B3-3 were used, and the pellet was subjected to evaluation.
  • Example 2 A pellet was prepared in the same manner as in Example 1 except that 100 parts by mass of Ube Industries 2020B pellet (nylon 66) and 25 parts by mass of B3-4 were used, and the pellet was subjected to evaluation. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Tables 5 to 8 (Examples 1 to 22 and Comparative Examples 1 to 4) (Test Example 1) Production Examples 1-5, Polyamides PX6-1 to PX6-6 produced in Comparative Production Example 1, nylon 6 (Ube Industries, UBE nylon 1015B: PA6) and nylon 66 (Ube Industries, UBE nylon 2020B: PA66) The relative viscosity, melting point, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, and mechanical properties in dry and wet conditions were measured. The results are shown in Table 5.
  • Examples 1 to 12, Comparative Examples 1 and 2 Polyamides PX6-1 to PX6-5 produced in Production Examples 1 to 5, nylon 6 (Ube Industries, UBE nylon 1015B) and nylon 66 (Ube Industries, UBE nylon 2020B), and glass fiber (manufactured by Nippon Electric Glass) Using ECST-289 (fiber diameter 13 ⁇ m), carbon fiber (Toho Tenax Co., Ltd., Besphite HTA-C6NR (fiber diameter 7 ⁇ m), brass fiber (fiber diameter 80 ⁇ m), a mixture having the ratio shown in Table 6 was prepared. .
  • the mixture was used in a biaxial kneader having a cylinder diameter of 40 mm, using resin temperatures of 300 ° C. (Examples 5 to 9), 340 ° C. (Examples 1 to 4 and Examples 10 to 12), and nylon 6.
  • the mixture was melt-kneaded at 260 ° C. and nylon 266 at 290 ° C., extruded into a strand, cooled in a water tank, and then pelletized using a pelletizer.
  • a predetermined test piece was prepared by injection molding using the obtained pellet.
  • Examples 13 to 22, Comparative Examples 3 to 4 Polyamides PX6-1 to PX6-5 produced in Production Examples 1 to 5 and Nylon 6 (manufactured by Ube Industries, UBE nylon 1015B), strontium ferrite having an average particle diameter of 10 ⁇ m and an aminosilane coupling treated with an aminosilane coupling agent Mixtures having the ratios shown in Tables 7 and 8 were prepared using tungsten powder having an average particle size of 10 ⁇ m and surface-treated with an agent.
  • these mixtures were mixed using a biaxial kneader having a cylinder diameter of 40 mm, and the resin temperature was 300 ° C. (Examples 14, 19, 21), 340 ° C. (Examples 13, 15, 16, 17, 18, 20, 22).
  • nylon 6 was melt-kneaded at 260 ° C., extruded into a strand shape, cooled in a water tank, and then pelletized using a pelletizer.
  • a predetermined test piece was prepared by injection molding using the obtained pellet. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Test Example 2 Using the resin composition and test piece obtained above, tensile strength, tensile strength after oxidation-resistant gasoline treatment, saturated water absorption, and calcium chloride resistance were evaluated. The evaluation results are shown in Table 6.
  • Tables 9 to 11 (Examples 1 to 14 and Comparative Examples 1 to 4) (Test Example 1) Polyamides PX6-1 to PX6-6 produced in Production Examples 1 to 5 and Comparative Production Example 1, nylon 6 (Ube Industries, UBE nylon 1015B: PA6) and nylon 66 (Ube Industries, UBE nylon 2020B: PA66) The relative viscosity, melting point, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, and mechanical properties in dry and wet conditions were measured. The results are shown in Table 9.
  • Example 1 To 100 parts by mass of PX6-1 produced in Production Example 1, 0.5 parts by mass of organic montmorillonite (Nanocor, Nanomer 30TC) was added, and melt-kneaded using a twin-screw kneader at 340 ° C. A composite material of the present invention in the form of pellets was obtained.
  • organic montmorillonite Nanocor, Nanomer 30TC
  • Examples 2 to 7 A composite material of the present invention in the form of a pellet was obtained in the same manner as in Example 1 except that the composition in Table 10 was followed.
  • the kneading temperature of Examples 5 to 7 was 300 ° C.
  • the kneading temperature of Examples 2 to 4 was 340 ° C.
  • Example 1 A composite material was obtained in the same manner as in Example 1 using PA6 (manufactured by Ube Industries, UBE nylon 1015B) instead of the polyamide resin.
  • the kneading temperature was 260 ° C.
  • Test Example 2 The composite materials of Examples 1 to 7 and Comparative Example 1 were measured for dry and wet mechanical properties, calcium chloride resistance, and ethanol vapor permeability coefficient. The results are shown in Table 10. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Example 8 To 100 parts by mass of PX6-1 produced in Production Example 1, 1.5 parts by mass of organic montmorillonite (Nanocor, Nanomer 30TC) was added, and melt-kneaded at 340 ° C. using a biaxial kneader. A composite material of the present invention in the form of pellets was obtained.
  • organic montmorillonite Nanocor, Nanomer 30TC
  • Example 9 to 14 A composite material of the present invention in the form of a pellet was obtained in the same manner as in Example 8 except that the composition in Table 11 was followed.
  • the kneading temperature of Examples 12 to 14 was 300 ° C.
  • the kneading temperature of Examples 9 to 11 was 340 ° C.
  • Example 3 A composite material was obtained in the same manner as in Example 8 using PA6 (manufactured by Ube Industries, UBE nylon 1030B) instead of the polyamide resin.
  • the kneading temperature was 260 ° C.
  • Table 11 shows the measurement results of Examples 8 to 14 and Comparative Examples 3 to 4.
  • Tables 12 to 14 (Examples 1 to 20 and Comparative Examples 1 to 3) Production Examples 1-5, Polyamides PX6-1 to PX6-6 produced in Comparative Production Example 1, nylon 6 (Ube Industries, UBE nylon 1015B: PA6) and nylon 66 (Ube Industries, UBE nylon 2020B: PA66) The relative viscosity, melting point, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, and mechanical properties in dry and wet conditions were measured. The results are shown in Table 12.
  • these mixtures were mixed using a twin-screw kneader having a cylinder diameter of 40 mm, the cylinder set temperature was 340 ° C. in Examples 1 to 9 and 14 to 15, and 300 ° C. in Examples 10 to 13 (260 when nylon 6 was used).
  • the cylinder set temperature was 340 ° C. in Examples 1 to 9 and 14 to 15, and 300 ° C. in Examples 10 to 13 (260 when nylon 6 was used).
  • a temperature of 290 ° C. for PA66 extruded into a strand, cooled in a water bath, and then pelletized using a pelletizer to obtain a polyamide resin composition.
  • the polyamide resin composition using PX6-6 could not be melt kneaded and molded because Td-Tm was small.
  • Various test pieces were prepared from the obtained pellets by injection molding.
  • Example 16 to 20 Comparative Example 3
  • a cylinder set temperature of 340 ° C. in Examples 16 to 17 and 300 ° C. in Examples 18 to 20 (260 ° C. in PA6)
  • the resin temperature was 340 ° C. in Examples 16 to 17, the resin temperature was 300 ° C. in Examples 18 to 20 (260 ° C. in PA6), and the mold temperature was 80 ° C.
  • the evaluation shown in Table 14 was performed by the method described above.
  • U-BOND Z488 used as an impact modifier is acid-modified polyethylene manufactured by Ube Maruzen Polyethylene
  • Tuffmer MC1307 is a polyolefin elastomer manufactured by Mitsui Chemicals
  • Tuffmer MH5010 is an acid manufactured by Mitsui Chemicals. It is a modified ethylene / butadiene copolymer.
  • Examples 2-1-1 to 3 and Examples 2-2 to 5 The metal coating material and metal-coated article of the present invention were produced.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Example 1-1: Comparative Resin 1 (PX6-6) Comparative Example 1-2: Comparative Resin 2 (PA6) Comparative Example 1-3: Comparative Resin 4 (PA12)
  • Examples 2-1-1 to 3, Examples 2-2 to 5, and Comparative Examples 2-3-1 to 2 The polyamide resin produced in Examples 1-1 to 5 and PA12, As an epoxidized styrenic thermoplastic elastomer, Daicel Chemical Epofriend A1010 is used, In the composition shown in Table 16, in a biaxial kneader PCM-45 manufactured by Ikekai Tekko Co., Ltd., the cylinder set temperature is 340 ° C. when PA 6-1 to 2 and 6 are included as the polyamide resin.
  • a metal coating material was prepared by melt-kneading at a rotational speed of 150 rpm.
  • a metal-coated article was produced by sandwiching the melt-kneaded metal-coated polyamide resin composition between metal substrates (galvanized steel sheet and aluminum plate). Moreover, the saturation water absorption rate and chemical resistance were evaluated by the methods described later using films formed under the conditions of (5) above from the melt-kneaded samples.
  • the polyamide resin composition for metal coating of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. It has excellent mechanical properties, has a wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component, has excellent melt moldability, and can have a higher molecular weight. It turns out that it can shape
  • Examples 1 to 8 and Comparative Examples 1 to 4 Examples 1 to 7, Comparative Examples 1 to 4
  • the polyamide resin composition for injection molding of the present invention was produced.
  • Examples 1 to 5 are polyamide resin compositions for injection molding composed of Component A
  • Examples 6 and 7 are polyamide resin compositions for injection molding composed of Component A and glass fibers.
  • Example 1 Production Examples 1 to 5 (PX6-1 to 5) Comparative Example 1: Comparative Resin 1 (PX6-6) Comparative Example 2: Comparative resin 2 (PA6) Comparative Example 3: Comparative Resin 3 (PA66) Comparative Example 4: PX6-5 of Example 7 was replaced with PA6, and pellets that were polyamide resin compositions for injection molding containing glass fibers were prepared under the same conditions as in Example 7.
  • Example 6 and 7 100 parts by mass of PX6-1 and PX6-5 pellets were kneaded in a twin screw extruder with a 44 mm ⁇ vent set to a barrel temperature of 340 and 300 ° C., respectively.
  • glass fiber fiber diameter 11 ⁇ m, fiber cut length 3 mm
  • Pellets that were polyamide resin compositions for molding were prepared.
  • Example 8 Intake manifolds and fuel injections were produced by injection molding using the resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4.
  • the polyamide resin compositions for injection molding of Examples 1 to 7 had moldability equal to or higher than that of PA6 and PA66.
  • the polyamide resin composition for injection molding of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, is excellent in chemical resistance and hydrolysis resistance, and is a machine under wet conditions. Excellent physical properties, wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine as a diamine component, excellent melt moldability, and higher molecular weight. It can be seen that a tough injection-molded product with reduced warpage can be produced even when glass fiber, which is said to have a large warpage and low dimensional stability, is added. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Examples 1-1 to 5 The polyamide resin composition for extrusion molding of the present invention was produced.
  • Examples 2-1 to 5 A filament (monofilament) using the polyamide resin composition for extrusion molding of the present invention was produced.
  • Examples 3-1 to 5 A single-layer tube using the polyamide resin composition for extrusion molding of the present invention was produced.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Example 1-1: Comparative Resin 1 (PX6-6) Comparative Example 1-2: Comparative Resin 2 (PA6)
  • Example 2-1 to 5 and Comparative Example 2-2 Each of the polyamide resin compositions of Examples 1-1 to 5 and Comparative Example 1-2 was Using an extruder with a screw diameter of 30 mm, the cylinder set temperature was 280 to 310 ° C. in Examples 2-3 to 5 and Comparative Example 2-2. In the case of Examples 2-1 and 340 ° C.
  • Examples 3-1 to 5 and Comparative Example 3-2 For the polyamide resin and PA6 produced in Examples 1 to 5, using an extruder with a screw diameter of 30 mm (cylinder temperature 250 to 340 ° C.) manufactured by Nippon Steel Co., Ltd., the outer diameter is 1/2 inch and the thickness is 1 mm. Single layer tubes were produced.
  • Example 19 (Examples 1-1 to 5, 2-1 to 6, and 3-1 to 5, Comparative Examples 1-1 to 3, 2-2, 2-4, and 3-2 to 3) (Examples 1-1 to 5) A polyamide resin composition for molding vehicle parts of the present invention comprising Component A was produced. (Examples 2-1 to 6) A polyamide resin composition for molding vehicle parts according to the present invention comprising component A and glass fiber was produced. (Examples 3-1 to 5) A polyamide resin composition for molding vehicle parts of the present invention comprising Component A, an ultraviolet absorber and a light stabilizer was produced. (Example 4) Vehicle interior parts were produced using the polyamide resin composition for molding vehicle parts of the present invention. (Example 5) A vehicle exterior part using the polyamide resin composition for molding vehicle parts of the present invention was produced.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Example 1-1: Comparative Resin 1 (PX6-6) Comparative Example 1-2: Comparative Resin 2 (PA6) Comparative Example 1-3: Comparative Resin 3 (PA66)
  • Examples 2-1 to 6 and Comparative Examples 2-2 and 4 For the polyamide resin compositions of Examples 2-1 to 6 and Comparative Examples 2-2 and 4, the barrel temperature is 340 ° C. when PA 6-1 to 2 and 6 are included as the polyamide resin. 300 ° C when PA 6-3 to 5 is included as a polyamide resin, 260 ° C when PA6 is included as the polyamide resin, Were kneaded with a 44 mm ⁇ vented twin screw extruder set to When kneading into this polyamide resin, glass fiber (average diameter 11 ⁇ m, average fiber length 3 mm) is supplied from the middle of the extruder to 43 parts by mass with respect to 100 parts by mass of the polyamide resin. Pellets of polyamide resin compositions for molding vehicle parts of 2-1 to 6 and Comparative Examples 2-2 and 4 were prepared.
  • Examples 3-1 to 5 and Comparative Examples 3-2 to 3 Into the polyamide resin composition pellets produced in Examples 1-1 to 5 and Comparative Examples 1-2 to 3, Tinuvin 327 as an ultraviolet absorber and Tinuvin 123 as a light stabilizer were added to 100 parts by mass of the polyamide resin.
  • Example 4 Production of vehicle interior parts
  • Examples 1-1 to 5 sun visor brackets and instruments by injection molding using the polyamide resin compositions of Examples 3-1 to 5 and Comparative Examples 3-2 to 3 containing an ultraviolet absorber and a light stabilizer A mental panel was manufactured.
  • Examples 1-1 to 5 and 3-1 to 5 had a moldability equal to or higher than that of Comparative Examples 3-2 to 3 including PA6 or PA66.
  • Example 5 Manufacture of vehicle exterior parts
  • front grills and mudguards were manufactured by injection molding.
  • the polyamide resins of Examples 1-1 to 5 had a moldability equal to or higher than that of Comparative Examples 1-2 to 3 including PA6 or PA66.
  • the molded product obtained by molding the resin composition of the present invention and the resin composition of the present invention has low water absorption compared to materials such as nylon 6, nylon 66 and nylon 12, and has chemical resistance.
  • the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Tables 21 to 23 (Examples 1-1 to 5, 2-1 to 4, 3-1 to 2, 3-5, 4-1 to 4, 5-1 to 5, and 6-1 to 7, Comparative Examples 1-1 to 4, 2-4, 3-3 to 4, 4-4, 5-2 and 5-4) Examples 1-1 to 5, Examples 2-1 to 4, Examples 3-1, 2, and 5, Examples 4-1 to 4,
  • the polyamide resin composition for fuel pipe parts of the present invention was produced in the intermediate layer and outer layer of Examples 6-1 to 6 and the outer layer of Example 6-7.
  • a joint for a fuel pipe part which is a fuel pipe part of the present invention was manufactured.
  • Examples 5-1 to 5 a single-layer fuel tube that is a fuel piping component of the present invention was manufactured, In Examples 6-1 to 5, a three-layer fuel tube that is a fuel piping component of the present invention was manufactured, In Example 7, a gasoline tank and a fuel tube, which are fuel piping parts of the present invention, were manufactured.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Example 1-1: Comparative Resin 1 (PX6-6) Comparative Example 1-2: Comparative Resin 2 (PA6) Comparative Example 1-3: Comparative Resin 3 (PA66) Comparative Example 1-4: Comparative resin 4 (PA12)
  • Example 2-1 to 4 and Comparative Examples 4 to 4 PX6-1 produced in Example 1-1 with the composition shown in Table 21
  • Glass fiber (CS-3J-265S manufactured by Nitto Boseki Co., Ltd.) and / or carbon fiber (K223SE manufactured by Mitsubishi Chemical) was kneaded in a TEX44 twin screw extruder manufactured by Nippon Steel, The strand was cooled and solidified in a cooling water tank, and then a pellet of Example 2-1 was obtained with a pelletizer.
  • glass fiber was described as GF and carbon fiber as CF.
  • a pellet of Example 2-4 was obtained under the same conditions as in Example 2-1, except that PX6-1 was replaced with PX6-4 produced in Example 1-4.
  • Example 1-2 30% by mass of glass fiber (CS-3J-265S manufactured by Nitto Boseki Co., Ltd.) was kneaded in a TEX44 twin-screw extruder manufactured by Nippon Steel, The strand was cooled and solidified in a cooling water tank, and then a pellet of Example 2-2 was obtained with a pelletizer.
  • Examples 2-2 Examples 2-3 to 4 and Comparative Example 2-4 were performed under the same conditions except that PX6-2 was replaced with PX6-3 and 4 prepared in Examples 1-3 and 4, respectively, and PA12. Pellets were obtained.
  • a 30 mm screw extruder (Cylinder temperature: 250 to 340 ° C.) manufactured by Nippon Steel Co., Ltd., a plastic joint for fuel piping having an outer diameter of 8 mm, a wall thickness of 2 mm, and a length of 100 mm was manufactured.
  • Examples 5-1 to 5 and Comparative Examples 2 and 4 For the polyamide resins PA6 and PA66 produced in Examples 1-1 to 5, using an extruder with a screw diameter of 30 mm (cylinder temperature 250 to 340 ° C.) manufactured by Nippon Steel Co., Ltd., an outer diameter of 1/2 inch. A single-layer tube having a thickness of 1 mm was manufactured.
  • Multi-layer tube forming equipment includes an inner layer extruder, an intermediate layer extruder and an outer layer extruder. Resin discharged from these three extruders is collected by an adapter and molded into a tube, and the tube is cooled.
  • a three-layer tube having an inner diameter of 6 mm and an outer diameter of 8 mm was prepared using an apparatus (product name: Platform, manufactured by Plastic Engineering Laboratory Co., Ltd.) consisting of a sizing die and a take-up machine for controlling the size.
  • Table 3 shows the composition and thickness of the resin composition of the inner layer, intermediate layer, and outer layer of the tube. In addition, the following was used as a raw material.
  • Resin r1 Vinylidene fluoride resin (cefal soft, manufactured by Central Glass)
  • Resin r2 High density polyethylene resin (8600A, manufactured by Tosoh Corporation)
  • Plasticizer Benzenesulfonic acid butyramide (BBSA, manufactured by Proviron) (In Table 23, it is described as BSBA)
  • Adhesive Maleic acid-modified polyethylene (U Bond F1100, manufactured by Ube Industries)
  • Example 7 Using PX6-1 to PX6-5, PA6, PA66, and PA12 manufactured in Examples 1 to 5, a fuel tank for transporting a gasoline tank and gasoline fuel, which are fuel pipe components, was manufactured by injection molding. Injection molding conditions are When using PX6-1-3 as polyamide resin, When using PX6-4-6 as polyamide resin, When PA6 is used as a polyamide resin, 290 ° C when PA66 is used as the polyamide resin 23 ° C when PA12 is used as polyamide resin A test plate was obtained by molding with an electrophotographic apparatus part having a mold temperature of 80 ° C. The injection molding conditions were: injection pressure: primary pressure 650 kg / cm 2 , injection time: 11 seconds, cooling time: 20 seconds. The gasoline tank and the fuel tube, which are fuel piping parts of the present invention, had a formability equal to or higher than that of PA6, PA66, and PA12.
  • Example 3-1, 2 and 5 Comparative Examples 3-3 to 4, Examples 4-1 to 4 and Comparative Example 4-4, the fuel barrier properties of the joint for fuel piping which is a fuel piping component of the present invention (Measure fuel permeation (total permeation and HC permeation)
  • Examples 5-1 to 5 and Comparative Examples 5-2 and 4 the vapor barrier properties (moisture permeability) of the single-layer fuel tubes were measured. The results are shown in Table 22.
  • the polyamide resin composition for fuel pipe parts of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. It has excellent mechanical properties, and has a wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component, and it has excellent melt moldability and can have a higher molecular weight. It can be seen that a fuel piping component having excellent environmental resistance such as low temperature impact resistance, chemical resistance, and fuel impermeability can be produced by molding it. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Examples 1-1 to 5 2-1-1 to 2, 2-2 to 3, 2-4-1 to 2, and 2-5, the polyamide resin composition for a printed circuit board surface mount component of the present invention is manufactured. did.
  • it is a polyamide resin composition for printed circuit board surface-mount components comprising component A
  • Examples 2-1-1 to 2, 2-2 to 3, 2-2-4-1 to 2, and 2-5 printed circuit board surface-mount components comprising component A and glass fibers (inorganic particles) It is a polyamide resin composition.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Example 1-1: Comparative Resin 1 (PX6-6) Comparative Example 1-2: Comparative Resin 2 (PA6) Comparative Example 1-3: Comparative Resin 2 (PA66) Comparative Example 1-4: Comparative resin 2 (PA12)
  • Examples 2-1-1 to 2, 2-2 to 3, 2-4-1 to 2, 2-5 and Comparative Examples 2-3-1 to 2 The polyamide resin and PA66 produced in Examples 1-1 to 5 and Comparative Example 1-1; Using glass fiber (ECST-289 manufactured by Nippon Electric Glass (fiber diameter 13 ⁇ m)) A mixture having the ratio shown in Table 2 was prepared.
  • each of these mixtures was used using a biaxial kneader with a cylinder diameter of 40 mm, 340 ° C when PA 6-1 to 2 and 6 are included as polyamide resin, 300 ° C when PA 6-3 to 5 is included as a polyamide resin,
  • PA66 is included as a polyamide resin
  • the mixture was melt kneaded and extruded into a strand shape, cooled in a water tank, and then pelleted using a pelletizer.
  • the polyamide resin composition for a printed circuit board surface mount component of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. It has excellent mechanical properties, and has a wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component, and it has excellent melt moldability and can have a higher molecular weight. It can be seen that a printed circuit board surface mount component having excellent heat resistance under high temperature and chemical resistance against various chemicals can be produced. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Resin Example 1-1: Comparative Resin 1 (PX6-6) Comparative Resin Example 1-2: Comparative Resin 2 (PA6) Comparative Resin Example 1-3: Comparative Resin 3 (PA66)
  • Examples 1-1 to 4, 2-1, 3-1 to 5, Comparative Examples 1-1 and 2-1, Examples 4-1 to 4, 5-1, 6-1 to 5, and Comparative Example 4 -1 and 5-1) (I) Polyamide resins produced in Examples 1-1 to 5, PA6 and PA66, conductive fillers and layered silicates, Carbon black (EC600JD made by Ketjen Black International), Carbon fiber (Besfight HTA-C6NR manufactured by Toho Tenax Co., Ltd. (fiber diameter 7 ⁇ m), Organized montmorillonite (Nanocor, Nanomer 30TC) Were used to make a mixture of the proportions shown in Table 26 (carbon black is labeled CB).
  • each of these mixtures was used using a twin-screw kneader with a cylinder diameter of 40 mm (Tex44 twin-screw extruder manufactured by Nippon Steel).
  • PX6-1 to 3 As the polyamide resin
  • PA6 290 ° C when PA66 is used as the polyamide resin
  • the mixture was melt kneaded and extruded into strands, cooled in a water tank, and then pelletized as a resin composition of the present invention using a pelletizer.
  • a seamless belt-like film having a thickness of 200 ⁇ m was prepared by an inflation extrusion molding method.
  • the inflation extrusion molding method uses an extruder with a screw diameter of 30 mm (cylinder temperature 250 to 340 ° C.) manufactured by Nippon Steel, Ltd., with a take-off speed of 40 m / min, a die lip width of 2 mm, and a blow ratio of 1.2.
  • a seamless belt-like film of 150 mm was produced.
  • the polyamide resin composition for electrophotographic apparatus parts of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and wet conditions. Excellent mechanical properties at lower temperatures, wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as diamine component, and excellent melt moldability, and higher molecular weight Thus, it can be seen that it is possible to produce an electrophotographic apparatus component that is excellent in electrical conductivity, surface smoothness, and mechanical property stability at high temperatures. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Tables 27 to 28 (Examples 1-1 to 4, 2-1, 3-1 to 5, 4-1 to 3, 5-1 to 4, 6-1, 7-1 to 5, 8- 1-3 Comparative Examples 1-1 and 2-1) In Production Examples 1-1 to 5, component A was produced. In Examples 1-1 to 4, 2-1, 3-1 to 5, and 4-1 to 3, the polyamide resin composition for IC tray of the present invention was produced. In Examples 5-1 to 4, 6-1, 7-1 to 5 and 8-1 to 3, IC trays of the present invention were produced.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Production Example 1-1: Comparative Resin 1 (PX6-6) Comparative Resin Example 1-2: Comparative Resin 2 (PA6) Comparative Resin Example 1-3: Comparative Resin 2 (PA66)
  • Example 1-1 to 4, 2-1, 3-1 to 5, and 4-1 to 3 and Comparative Examples 1-1 and 2-1 Polyamide resins produced in Examples 1-1 to 5, PA6 and PA66, and conductive fillers, Carbon black (EC600JD made by Ketjen Black International), Carbon fiber (Toho Tenax Co., Ltd. Besfight HTA-C6NR (fiber diameter 7 ⁇ m), Brass fiber (fiber diameter 80 ⁇ m) Were used to make a mixture of the proportions shown in Table 28 (carbon black is labeled CB). Furthermore, each of these mixtures was used using a twin-screw kneader with a cylinder diameter of 40 mm (Tex44 twin-screw extruder manufactured by Nippon Steel).
  • Examples 5-1 to 4, 6-1, 7-1 to 5, and 8-1 to 3 and Comparative Examples 1-1 and 2-1 Using the pellets produced in Examples 1-1 to 2, 2-1, 3-1 to 5, and 4-1 to 3 and Comparative Examples 1-1 and 2-1, the IC tray of the present invention is shown in FIG. Was obtained by injection molding under the following injection conditions. ⁇ Injection molding machine: IS-80 manufactured by Toshiba Machine Co., Ltd.
  • Cylinder set temperature When PX6-1 and PX6-2 are included as polyamide resins C1 310 ° C; C2 340 ° C; C3 340 ° C; C4 340 ° C; Nozzle heater 340 ° C When PX6-3 to 5 are included as polyamide resin C1 280 ° C; C2 300 ° C; C3 300 ° C; C4 300 ° C; Nozzle heater 300 ° C When PA6 is included as a polyamide resin C1 210 ° C; C2 260 ° C; C3 260 ° C; C4 260 ° C; Nozzle heater 260 ° C When PA66 is included as a polyamide resin C1 240 ° C; C2 290 ° C; C3 290 ° C; C4 290 ° C; Nozzle heater 290 ° C Injection pressure: Primary pressure 650 kg / cm 2 -Mold temperature: Moving mold 40 ° C; Fixed mold 40 ° C ⁇ Injection time: 11 seconds
  • the polyamide resin composition for IC trays of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. It has excellent mechanical properties, has a wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component, has excellent melt moldability, and can have a higher molecular weight. It can be seen that an IC tray having a smooth surface and stable mechanical properties and conductivity even at high temperatures can be produced. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Tables 29 to 30 (Examples 1-1 to 5, 2-1 to 5 and 3-1 to 7, Comparative Examples 1-1 to 3, 2-2 and 3-2 to 3) Examples 1-1 to 5, Examples 2-1 to 5, Inner layer, intermediate layer and outer layer of Examples 3-1 to 5,
  • the polyamide resin composition for industrial tubes of the present invention was produced in the intermediate layer of Example 3-6 and the outer layers of Examples 3-6 and 7. In Examples 2-1 to 5 and Examples 3-1 to 7, industrial tubes of the present invention were produced.
  • Examples 1-1 to 5 Production examples 1 to 5 (PX6-1 to 5) Comparative Example 1-1: Comparative Resin 1 (PX6-6) Comparative Example 1-2: Comparative Resin 2 (PA6) Comparative Example 1-3: Comparative Resin 4 (PA12)
  • Examples 2-1 to 5 and Comparative Example 1-2 For the polyamide resin and PA6 produced in Examples 1 to 5, using an extruder with a screw diameter of 30 mm (cylinder temperature 250 to 340 ° C.) manufactured by Nippon Steel Co., Ltd., the outer diameter is 1/2 inch and the thickness is 1 mm. Single layer tubes were produced.
  • Multi-layer tube forming equipment includes an inner layer extruder, an intermediate layer extruder and an outer layer extruder. Resin discharged from these three extruders is collected by an adapter and molded into a tube, and the tube is cooled.
  • a multilayer tube having an inner diameter of 6 mm and an outer diameter of 8 mm was prepared using an apparatus (Plabor (manufactured by Plastic Engineering Laboratory Co., Ltd.)) consisting of a sizing die and a take-up machine for controlling the size.
  • the composition and thickness of the resin composition of the inner layer, intermediate layer and outer layer of the tube are shown in Table 2. In addition, the following was used as a raw material.
  • Resin r1 Vinylidene fluoride resin (cefural soft (manufactured by Central Glass))
  • Resin r2 High density polyethylene resin (8600A, manufactured by Tosoh Corporation)
  • Plasticizer Benzenesulfonic acid butyramide (BBSA (Proviron)
  • Adhesive Maleic acid-modified polyethylene (U Bond F1100, manufactured by Ube Industries)
  • the polyamide resin composition for industrial tubes of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. It has excellent mechanical properties, and has a wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component, and it has excellent melt moldability and can have a higher molecular weight. It can be seen that an industrial tube excellent in environmental resistance such as low-temperature impact resistance, chemical resistance and liquid, vapor and / or gas impermeability can be produced by molding it. Note that the polyamide resin composition using PX6-6 could not be melt kneaded nor molded because of its small Td-Tm.
  • Relative viscosity ⁇ r of polyamide resin ⁇ r was measured at 25 ° C. using an Ostwald viscometer using a 96% sulfuric acid solution (concentration: 1.0 g / dl) of each polyamide resin of Production Examples 1 to 5 and Comparative Resins 1 and 2.
  • melt viscosity of polyamide resin The melt viscosity of each polyamide resin of Production Examples 1 to 5 and Comparative Resins 1 and 2 is a 25 mm cone plate in a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan. In the nitrogen, 340 ° C when PA 6-1 to 2 and 6 are included as polyamide resin, 300 ° C when PA 6-3 to 5 is included as a polyamide resin, 260 ° C when PA6 is included as the polyamide resin, The measurement was performed under the condition of a shear rate of 0.1 s-1.
  • Tm Melting point of polyamide resin (Tm) Tm of each polyamide resin of Production Examples 1 to 5, Specific Resin 1 and Comparative Resins 1 to 4 was measured under a nitrogen atmosphere using PYRIS Diamond DSC manufactured by PerkinELmer.
  • Tm when PA 6-1 to 2 and 6 are included as the polyamide resin is The temperature is raised from 30 ° C. to 350 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), After holding at 350 ° C for 3 minutes, Decrease the temperature to -100 ° C at a rate of 10 ° C / min (referred to as the first temperature drop) Next, the temperature was raised to 350 ° C.
  • Tm when PA6-3-5, PA6, PA66 and PA12 are included as the polyamide resin is The temperature is increased from 30 ° C. to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature rising first run), After holding at 310 ° C for 3 minutes, Decrease the temperature to -100 ° C at a rate of 10 ° C / min (referred to as the first temperature drop) Next, the temperature was raised to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature rise second run). The endothermic peak temperature of the elevated temperature second run was defined as Tm.
  • Test film and plate molding conditions (5-1) Saturated water absorption rate, chemical resistance, hydrolysis resistance, water absorption rate and calcium chloride resistance test film Vacuum press machine TMB-10 manufactured by Toho Machinery Co., Ltd. was used to obtain films for testing the saturated water absorption, chemical resistance, hydrolysis resistance and water absorption of each polyamide resin of Production Examples 1 to 5 and Comparative Resins 1 to 4.
  • Zinc chloride resistance (cycle) (Table 7, Table 8) An ASTM No. 1 test piece was used and immersed in water at 80 ° C. for 8 hours as a pretreatment. Next, after conditioning for 1 hour in an 80 ° C. and 85% RH constant temperature and humidity chamber, a saturated zinc chloride aqueous solution was applied to the test piece and heat treated in a 100 ° C. oven for 1 hour. The humidity control and heat treatment were repeated as one cycle up to 30 cycles, and the number of cycles in which the test piece cracked was used as an index.
  • Ethanol vapor transmission coefficient (Table 10) 50 ml of ethanol was put into a stainless steel container, and the film formed under the condition (5) was covered with a PTFE gasket and covered with a screw pressure. The cup was placed in a constant temperature bath at 60 ° C., and nitrogen was allowed to flow at 50 ml / min in the bath. The change in weight over time was measured, and when the rate of change in weight per hour was stabilized, the fuel permeability coefficient was calculated from the following equation. The transmission area of the sample is 78.5 cm 2 .
  • Ethanol permeability coefficient [permeation weight (g) ⁇ film thickness (mm)] / [permeation area (mm 2 ) ⁇ days (day) ⁇ pressure (atom)]
  • Adhesive strength of metal-coated articles (Table 16) A test film (dimensions: 150 mm ⁇ 100 mm, thickness 0.1 mm) which is a metal coating material, Scissors between galvanized steel sheet (JIS G3302 SPGC Z22, dimensions: 150 mm x 150 mm, thickness 0.5 mm) and aluminum plate (JIS No. 1100, dimensions: 150 mm x 150 mm, thickness 0.5 mm), Using the Toyo Machinery vacuum press TMB-10, In a reduced pressure atmosphere of 500 to 700 Pa, when PA 6-1 to 2 and 6 are included as a polyamide resin, 340 ° C.
  • Warpage (warping of inward tilt) (%) (B length ⁇ A length) / B length ⁇ 100
  • Oxygen permeability coefficient of polyamide resin (Table 18) Test piece cut out from test film (thickness 30 ⁇ m) is measured based on “ASTM D3985” using MOCON tester OX-TRAN 2 / 20-MH at a temperature of 23 ° C. and a humidity of 97% RH. did. (12) Tensile strength, tensile elongation, and tensile modulus of monofilament The tensile strength, tensile elongation, and tensile modulus of the monofilament were measured according to JIS L1070 and L1073.
  • Ethanol vapor permeability coefficient of polyamide resin (Table 21) 50 ml of ethanol was put in a stainless steel container, and a test film was used to cover the container covered with a PTFE gasket and tightened with screw pressure. The cup was placed in a constant temperature bath at 60 ° C., and nitrogen was allowed to flow at 50 ml / min in the bath. The change in weight with time was measured, and when the weight change rate per hour was stabilized, the ethanol vapor transmission coefficient was calculated from the following equation. The transmission area of the sample is 78.5 cm2.
  • Ethanol vapor transmission coefficient [Permeation weight (g) x film thickness (mm)] / [Permeation area (mm 2 ) ⁇ days (day) ⁇ pressure (atom)]
  • E10 fuel permeability coefficient of polyamide resin (Table 21)
  • an E10 fuel permeation test was performed at a measurement ambient temperature of 60 ° C. using a test piece of ⁇ 75 mm and thickness 1 mm molded by injection molding.
  • 10% ethanol was mixed with Fuel C in which isooctane and toluene were mixed at a volume ratio of 1: 1.
  • the fuel permeation measurement sample surface was placed with the permeation surface facing downward so that the fuel always contacted.
  • PX6-1 to 3 Permeation weight (g) x film thickness (mm)] / [Permeation area (mm 2 ) ⁇ days (day) ⁇ pressure (atom)]
  • PA6 is used as a polyamide resin
  • 290 ° C when PA66 is used as the polyamide resin 230 ° C when PA12 is used as the polyamide resin A test plate was obtained by molding with an electrophotographic apparatus part having a mold temperature of 80 ° C.
  • the injection molding conditions were: injection pressure: primary pressure 650 kg / cm 2 , injection time: 11 seconds, cooling time: 20 seconds.
  • Test pieces (Type I test pieces described in ASTM D638) were prepared by the following method. That is, a metal piece made into a half of a mold for producing a Type I test piece is inserted, and polyethylene which has been modified with maleic anhydride is injected and filled into a portion where the metal piece is not inserted. Next, after the injection-filled maleic anhydride-modified polyethylene is sufficiently cooled, the metal piece in the mold is removed, and the resin to be evaluated is injected into the mold part from which the metal piece has been removed. Fill.
  • a test piece having the following interface is obtained. Injection molding conditions are When using PX6-1-3 as polyamide resin, When using PX6-4-6 as polyamide resin, When PA6 is used as a polyamide resin, 290 ° C when PA66 is used as the polyamide resin 23 ° C when PA12 is used as polyamide resin 20 ° C when polyethylene modified with maleic anhydride is used A test plate was obtained by molding with an electrophotographic apparatus part having a mold temperature of 80 ° C.
  • the injection molding conditions were: injection pressure: primary pressure 650 kg / cm 2 , injection time: 11 seconds, cooling time: 20 seconds.
  • the resin to be evaluated peels off from the boundary surface between polyethylene modified with maleic anhydride at a tensile speed of 50 mm / min and a metal piece or breaks at a portion other than the boundary surface (base material breakdown) ) was measured as the initial adhesive strength.
  • Adhesive strength after immersion of polyamide resin in fuel (Table 21) A test piece molded in the same procedure as the evaluation of the initial adhesive strength was put in an autoclave, and Fuel C + 10% ethanol mixed fuel was sealed until the test piece was completely immersed. The autoclave was left in a 60 ° C. hot water tank for 350 hours. Thereafter, the maximum tensile strength of the test piece taken out was measured in the same manner as described above, and was taken as the adhesive strength after immersion in fuel.
  • Ethanol permeability (Table 29) The following operations were performed on the tubes manufactured in Examples 2-1 to 5, Comparative Example 2-2, Examples 3-1 to 7 and Comparative Examples 3-2 to 3 in Table 29. One end of the tube cut to 30 cm was sealed, ethanol was put inside, the other end was also sealed, the whole weight was measured, and then the test tube was placed in an oven at 60 ° C. to change the weight (g / 24 Time) was measured and ethanol permeability was evaluated.
  • Tube low temperature impact resistance (Table 30) The tubes produced in Examples 3-1 to 7 and Comparative Examples 3-2 to 3 in Table 30 were measured for low temperature impact resistance according to SAE J844.

Abstract

La présente invention concerne : une composition de résine polyamide comprenant une résine polyamide et divers additifs, la résine polyamide étant capable de présenter une résistance thermique, une aptitude au moulage à chaud et une réduction du nombre de cycles de moulage par rapport à celles des résines polyoxamide conventionnelles et pouvant être moulée à l'intérieur d'un article moulé ayant d'excellentes propriétés de résistance chimique, de résistance à l'hydrolyse et d'imperméabilité aux carburants sans détériorer la faible capacité d'absorption de l'eau ; et un article moulé produit en moulant la composition de résine polyamide. L'invention concerne plus particulièrement une composition de résine polyamide comprenant une résine polyamide (composant (A)) et comprenant de plus divers additifs, le composant (A) étant produit en liant une unité dérivée d'un acide dicarboxylique à une unité dérivée d'une diamine, l'acide dicarboxylique comprenant l'acide oxalique (composé (a)), la diamine comprenant la 1,6-hexanediamine (composé (b)) et la 2-méthyl-1,5-pentanediamine (composé (c)), et le rapport molaire du composé (b) sur le composé (c) étant situé dans la plage allant de 99 : 1 à 50 : 50 ; et un article moulé produit en moulant la composition de résine polyamide.
PCT/JP2012/065877 2011-10-28 2012-06-21 Composition de résine polyamide WO2013061650A1 (fr)

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JP2011-237642 2011-10-28
JP2011-237721 2011-10-28
JP2011237642A JP2013095789A (ja) 2011-10-28 2011-10-28 バイオディーゼル燃料と直接接触する成形体用ポリアミド樹脂組成物及びそれを成形して得た成形体
JP2011237361A JP2013095777A (ja) 2011-10-28 2011-10-28 プリント基板表面実装部品用ポリアミド樹脂組成物及びそれを成形して得たプリント基板表面実装部品
JP2011-237361 2011-10-28
JP2011237713A JP2013095790A (ja) 2011-10-28 2011-10-28 層状珪酸塩含有ポリアミド樹脂組成物
JP2011237901A JP2013095798A (ja) 2011-10-28 2011-10-28 金属被覆用ポリアミド樹脂組成物、その樹脂組成物を成形して得た金属被覆材及びその樹脂組成物で被覆された金属物品
JP2011-237386 2011-10-28
JP2011237374A JP2013095778A (ja) 2011-10-28 2011-10-28 ポリアミド樹脂組成物及びそれを成形して得た成形体
JP2011-237957 2011-10-28
JP2011237954A JP2013095801A (ja) 2011-10-28 2011-10-28 電子写真装置部品用ポリアミド樹脂組成物及びそれを成形して得た電子写真装置部品
JP2011237956A JP2013095803A (ja) 2011-10-28 2011-10-28 ポリアミド樹脂組成物及びそれを成形して得た耐熱性成形体
JP2011237957A JP2013095804A (ja) 2011-10-28 2011-10-28 押出成形用ポリアミド樹脂組成物及びそれを押出成形して得た押出成形体
JP2011-237916 2011-10-28
JP2011-237723 2011-10-28
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JP2011237916A JP2013095800A (ja) 2011-10-28 2011-10-28 燃料配管部品用ポリアミド樹脂組成物及びそれを成形して得た燃料配管部品
JP2011237722A JP2013095792A (ja) 2011-10-28 2011-10-28 充填材含有ポリアミド樹脂組成物
JP2011-237956 2011-10-28
JP2011-237901 2011-10-28
JP2011-237954 2011-10-28
JP2011-237722 2011-10-28
JP2011237721A JP2013095791A (ja) 2011-10-28 2011-10-28 導電性ポリアミド樹脂組成物及びその成形体
JP2011237386A JP2013095780A (ja) 2011-10-28 2011-10-28 射出成形用ポリアミド樹脂組成物及びそれを射出成形して得た射出成形体
JP2011-237713 2011-10-28
JP2011-237910 2011-10-28
JP2011237723A JP2013095793A (ja) 2011-10-28 2011-10-28 ポリアミド樹脂組成物
JP2011-237374 2011-10-28
JP2011237955A JP2013095802A (ja) 2011-10-28 2011-10-28 産業用チューブ用ポリアミド樹脂組成物及びそれを成形して得た産業用チューブ
JP2011237910A JP2013095799A (ja) 2011-10-28 2011-10-28 Ｉｃトレイ用ポリアミド樹脂組成物及びそれを成形して得たｉｃトレイ
JP2011237641A JP2013095788A (ja) 2011-10-28 2011-10-28 車両部品成形用ポリアミド樹脂組成物及びそれを成形して得た車両部品
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Cited By (7)

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FR3006318A1 (fr) * 2013-06-03 2014-12-05 Rhodia Operations Charges en tant qu'agent permettant de diminuer la deterioration de proprietes barrieres
JP2015034276A (ja) * 2013-07-08 2015-02-19 宇部興産株式会社 ポリアミド樹脂
JPWO2015093060A1 (ja) * 2013-12-20 2017-03-16 三井化学株式会社 半芳香族ポリアミド樹脂組成物およびその成型品
US9955562B2 (en) 2014-12-26 2018-04-24 Toyota Jidosha Kabushiki Kaisha Engine and method of production of engine
WO2018147315A1 (fr) * 2017-02-09 2018-08-16 東洋紡株式会社 Composition de résine polyamide conductrice
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
US10718299B2 (en) 2014-12-25 2020-07-21 Toyota Jidosha Kabushiki Kaisha Intake system of vehicle

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JP2006522208A (ja) * 2003-04-01 2006-09-28 ハーキュリーズ・インコーポレーテッド アミン末端ポリアミドからの高固形分樹脂の合成
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
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JP2006522208A (ja) * 2003-04-01 2006-09-28 ハーキュリーズ・インコーポレーテッド アミン末端ポリアミドからの高固形分樹脂の合成
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
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3006318A1 (fr) * 2013-06-03 2014-12-05 Rhodia Operations Charges en tant qu'agent permettant de diminuer la deterioration de proprietes barrieres
WO2014195328A1 (fr) * 2013-06-03 2014-12-11 Rhodia Operations Charges en tant qu'agent permettant de diminuer la deterioration de proprietes barrieres
JP2015034276A (ja) * 2013-07-08 2015-02-19 宇部興産株式会社 ポリアミド樹脂
JPWO2015093060A1 (ja) * 2013-12-20 2017-03-16 三井化学株式会社 半芳香族ポリアミド樹脂組成物およびその成型品
US10718299B2 (en) 2014-12-25 2020-07-21 Toyota Jidosha Kabushiki Kaisha Intake system of vehicle
US9955562B2 (en) 2014-12-26 2018-04-24 Toyota Jidosha Kabushiki Kaisha Engine and method of production of engine
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

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