JP5572923B2 - Cable housing - Google Patents

Description

  The present invention relates to a cable housing that supports cables such as a power supply cable, a signal cable, and an optical cable, and in particular, has excellent slidability, mechanical strength, and electrical conductivity for precision machine manufacturing devices, as well as low water absorption, moldability, It relates to cable housings with excellent chemical resistance.

  Various assembly apparatuses and the like are configured to perform a predetermined work on the work unit while moving the work unit in an arbitrary direction. Various elements such as a motor, a solenoid, a camera, and a light source are assembled in the work unit, and cables such as a power supply cable, a signal cable, and an optical cable are connected to these elements. These cables are long, and the cables are held in the cable housing so that the movement of the work unit can be freely followed (see, for example, Patent Document 1).

  As the cable housing material, since sliding property and rigidity are required, a resin composition in which a filler such as glass fiber or carbon fiber is blended with a polyamide resin has been conventionally used (for example, Patent Document 2). To 3).

  However, in a precision machine manufacturing apparatus such as a semiconductor factory, there is a problem of dust adhesion due to static electricity. For this reason, a cable housing having high slidability and conductivity is required.

  As a material having conductivity, for example, a resin composition in which carbon black is blended with a polyamide resin has been proposed (see, for example, Patent Document 4).

  Although this material has improved conductivity, it has a defect that rigidity and impact resistance are deteriorated, and a cable housing excellent in slidability and rigidity and excellent in conductivity is desired.

  In addition, this polyamide material has problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, and deterioration in hot water, and there is also a demand for a polyamide having superior dimensional stability and chemical resistance.

  On the other hand, 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 5). It is expected to be used in fields where the use of conventional polyamide, where the change in physical properties due to water absorption has been a problem, is difficult.

  So far, polyoxamide resins using various aliphatic linear diamines as diamine components have been proposed. However, for example, a polyoxamide resin using 1,6-hexanediamine as a diamine component has a melting point (about 320 ° C.) higher than the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.) (non-patent document). 1) Melt polymerization and melt molding were difficult and could not withstand practical use.

  For a polyoxamide resin whose diamine component is 1,9-nonanediamine (hereinafter abbreviated as PA92), L. Franco et al. Discloses a production method and its crystal structure when diethyl oxalate is used as the oxalic acid source ( Non-patent document 2). The PA 92 obtained here is a polymer having an intrinsic viscosity of 0.97 dL / g and a melting point of 246 ° C., but only a low molecular weight substance that cannot form a tough molded article is obtained. It is also shown that PA92 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. was produced when dibutyl oxalate was used as the dicarboxylic acid ester (Patent Document 6). In this case as well, there is a problem that only a low molecular weight body that cannot be formed into a tough molded body is obtained.

  In prior literature, there is no specific disclosure of a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio.

  Therefore, there is a demand for a cable housing that is excellent in slidability, mechanical strength, and conductivity, and that is excellent in low water absorption, molding processability, chemical resistance, and the like.

JP 2002-112442 A Japanese Unexamined Patent Publication No. 1-110558 JP-A-3-265646 Japanese Patent Publication No. 1-35181 JP 2006-57033 A Japanese National Patent Publication No. 5-506466 S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988)

  An object of the present invention is to solve the above-mentioned problems and to provide a cable housing that is excellent in slidability, mechanical strength, and conductivity, and that is excellent in low water absorption, molding processability, chemical resistance, and the like. .

  As a result of intensive studies to solve this problem, the present inventors have found that, by blending an acid-modified ethylene copolymer, carbon fiber, and carbon black with a polyamide resin, it has excellent slidability and rigidity and is electrically conductive. The present inventors have found that a cable housing having excellent properties can be obtained, and have reached the present invention.

  That is, the present invention comprises a polyamide resin composition containing a polyamide resin (A), a conductivity imparting material (B), and an impact modifier (C), wherein the polyamide resin comprises oxalic acid as a dicarboxylic acid component, The diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 1:99 to 99: 1. It is related with the conductive cable housing characterized by including the polyamide resin which is.

  In the conductive cable housing of the present invention, the conductivity-imparting material (B) is carbon fiber and / or carbon black, and the impact modifier (C) is an LLDPE having a density of 0.89 to 0.94 g / cc. An acid-modified ethylene copolymer obtained by modification with an anhydride is preferable.

  Further, the preferred polyamide resin composition of the conductive cable housing of the present invention is polyamide resin (A) 65 to 75 wt%, carbon fiber 3 to 15 wt% and carbon black 2 to 10 wt% as conductivity imparting material (B), The impact modifier (C) is 10 to 20% by weight.

  The cable housing of the present invention is excellent in slidability, rigidity, and conductivity, and is suitably used for precision machine manufacturing apparatuses such as semiconductor factories.

The present invention is described in detail below.
(1) Constituent Component of Polyamide Resin The polyamide resin used in the present invention has a dicarboxylic acid component composed of oxalic acid, a diamine component composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, This is a polyamide resin (PA92C) having a molar ratio of 9-nonanediamine to 2-methyl-1,8-octanediamine of 1:99 to 99: 1.

  As the oxalic acid source used for the production of the polyamide PA92C used in the present invention, oxalic acid diester is used, and there is no particular limitation as long as it has reactivity with an amino group. Dimethyl oxalate, diethyl oxalate, di-oxalic acid -(Or i-) propyl, oxalic acid diester of aliphatic monohydric alcohol such as di-n- (or i-, or t-) butyl oxalate, oxalic acid diester of alicyclic alcohol such as dicyclohexyl oxalate, aromatic such as diphenyl oxalate And oxalic acid diesters of aliphatic alcohols.

  Among the above 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 preferred, and among them, dibutyl oxalate and diphenyl oxalate are particularly preferred.

  As the diamine component, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is used. Furthermore, it is 1:99 to 99: 1, preferably 5:95 to 95: 5, more preferably 5:95 to 40:60 or 60:40 to 95: 5, especially 5:95 to 30:70 or 70:30 to 90:10 mol%. By copolymerizing 1,9-nonanediamine and 2-methyl-1,8-octanediamine as described above, the amount of fuel passing through the wall surface is low, the rigidity and barrier properties at high temperature are excellent, and the melting point and thermal decomposition A polyamide having a wider moldable temperature range estimated from the temperature difference, excellent melt moldability, low water absorption, hydrolysis resistance, and the like can be obtained.

(2) Production of Polyamide Resin PA92C The novel polyamide resin PA92C used in the present invention can be produced using any method known as a method for producing polyamide. According to the study by the present inventors, it can be obtained by subjecting diamine and oxalic acid diester to a polycondensation reaction in a batch or continuous manner. Specifically, it is preferable to carry out in the order of (i) pre-polycondensation step and (ii) post-polycondensation step as shown by the following operations.

  (I) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then diamine (diamine component) and oxalic acid diester (oxalic acid source) are mixed. When mixing, a solvent in which both the diamine and the oxalic acid diester are soluble may be used. The solvent in which both the diamine component and the oxalic acid source are soluble is not particularly limited, but toluene, xylene, trichlorobenzene, phenol, trifluoroethanol, and the like can be used, and particularly, toluene can be preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this. At this time, the charging ratio of the oxalic acid diester and the diamine is oxalic acid diester / the diamine, 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), more preferably 0. .99 to 1.01 (molar ratio).

  The temperature in 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. In the temperature rising process, the final temperature of the prepolycondensation step, that is, from 80 to 150 ° C, is finally 220 ° C to 300 ° C, preferably 230 ° C to 280 ° C, more preferably 240 ° C to 270 ° C. Let reach the range. It is preferable to carry out the reaction for 1 to 8 hours including the temperature raising time, preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final ultimate pressure in the case of performing the vacuum polymerization is less than 0.1 MPa to 13.3 Pa.

The specific example of the manufacturing method of the polyamide resin used for this invention is demonstrated.
First, the raw oxalic acid diester is charged into the container. The container is not particularly limited as long as it can withstand the temperature and pressure of the polycondensation reaction to be performed later. Thereafter, the container is heated to a temperature at which it is mixed with the raw material diamine, and then the diamine is injected to start the polycondensation reaction. The temperature at which the raw materials are mixed is not particularly limited as long as it is a temperature that is not lower than the melting point and lower than the boiling point of the oxalic acid diester and diamine, and the polyoxamide generated by the polycondensation reaction of the oxalic acid diester and diamine is not thermally decomposed. For example, it consists of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 1:99 to 99: In the case of a polyoxamide resin using diamine 1 and dibutyl oxalate as raw materials, the mixing temperature is preferably 15 ° C to 240 ° C. Further, the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 90:10, which is liquid at room temperature or liquefied only by heating to about 40 ° C., so that it is easy to handle. Therefore, it is more preferable. When the mixing temperature is equal to or higher than the boiling point of the alcohol produced by the condensation reaction, it is desirable to use a container equipped with a device for distilling and condensing the alcohol. In addition, when pressure polymerization is performed in the presence of an alcohol generated by a condensation reaction, a pressure vessel is used. The charging ratio of oxalic acid diester and diamine is oxalic acid diester / diamine as described above, 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio), more preferably 0.98. -1.02 (molar ratio).

  Next, the inside of the container is heated to a temperature not lower than the melting point of the polyoxamide resin and not higher than the temperature at which it does not decompose. For example, a diamine and shu comprising 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 85:15. In the case of a polyoxamide resin using dibutyl acid as a raw material, the melting point is 235 ° C., so it is preferable to raise the temperature from 240 ° C. to 280 ° C. (pressure is 2 MPa to 4 MPa). While distilling off the produced alcohol, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. When the raw materials are mixed in a pressure vessel and subjected to pressure polymerization in the presence of an alcohol produced by a condensation reaction, the pressure is first released while the produced alcohol is distilled off. Thereafter, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 760 to 0.1 Torr. The temperature is preferably 240 to 280 ° C. The alcohol is cooled and liquefied by a water-cooled condenser and recovered.

(3) Properties and Physical Properties of Polyamide Resin There is no particular restriction on the molecular weight of the polyamide resin PA92C used in the present invention, but a 96% concentrated sulfuric acid solution having a polyamide resin concentration of 1.0 g / dl using 96% concentrated sulfuric acid as a solvent. The relative viscosity ηr measured at 25 ° C. is in the range of 1.8 to 6.0. Preferably it is 2.0-5.5, and 2.5-4.5 is especially preferable. If ηr is lower than 1.8, the molded product becomes brittle and the physical properties deteriorate. On the other hand, if ηr is higher than 6.0, the melt viscosity becomes high, and the molding processability deteriorates.

  The polyamide resin PA92C used in the present invention uses oxalic acid as the carboxylic acid component and copolymerizes 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component, whereby oxalic acid and 1,9-nonanediamine are copolymerized. The relative viscosity can be increased, that is, the molecular weight can be increased as compared with the polyamide made of The moldable temperature range represented by the difference (Td−Tm) between the 1% weight loss temperature (hereinafter abbreviated as Td) and the melting point (hereinafter abbreviated as Tm), which is a substantial thermal decomposition index, is oxalic acid. And a polyamide composed of 1,9-nonanediamine, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further 90 ° C. or higher. The polyamide resin used in the present invention has a Td of preferably 280 ° C. or higher, more preferably 300 ° C. or higher, still more preferably 320 ° C. or higher, and has high heat resistance.

(4) Components that can be blended in the polyamide resin The polyamide resin PA92C used in the present invention can be mixed with other dicarboxylic acid components as long as the effects of the present invention are not impaired. Examples of dicarboxylic acid components other than succinic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3, Aliphatic dicarboxylic acids such as 3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and terephthalic acid , Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, dibenzoic acid Acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenyls Hong-4,4'-dicarboxylic acid, 4,4'-biphenyl and the like alone aromatic dicarboxylic acids such as dicarboxylic acids, or may be added to any mixture thereof during the polycondensation reaction. Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible. The amount of the dicarboxylic acid component other than oxalic acid is preferably 5 mol% or less based on the total dicarboxylic acid component.

  In addition, other diamine components can be mixed with the polyamide resin PA92C used in the present invention within a range not impairing the effects of the present invention. Examples of diamine components other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, and 1,8-octanediamine. 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1 , 6-hexanediamine, aliphatic diamines such as 5-methyl-1,9-nonanediamine, alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine, p-phenylenediamine, m-phenylenediamine, p -Xylenediamine, m-xylenediamine, 4,4'-di Mino diphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-and aromatic diamines, such as diaminodiphenyl ether by itself, or may be added to any mixture thereof during the polycondensation reaction. The amount of the diamine component other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferably 5 mol% or less based on the total diamine component.

  Further, the polyamide PA92C used for the cable housing in the present invention may be a homopolymer of polyamide PA92C, or may be a mixture with other polyamide resins or other thermoplastic resins.

  Other polyamide resins include polyethylene adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene azepamide (nylon 69), poly Hexamethylene sebamide (nylon 610), polyhexamethylene undecanamide (nylon 611), polyhexamethylene dodecane (nylon 612), polycaproamide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (Nylon 12), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene dodecamide (nylon 912), polydodecamethylene dodecamide (nylon 1212), polymeta Silylene adipamide (nylon MXD6), polytrimethylhexamethylene terephthalamide (TMHT), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide ( Mention may be made of nylon dimethyl PACM 12), polyundecamethylene terephthalamide (nylon 11T) and the like, or copolymers thereof.

  In particular, nylon 6, nylon 11, nylon 12, nylon 610, nylon 612 or a copolymer thereof is preferably used for improving moldability and adhesion.

  The polyamide resin PA92C constituting the cable housing of the present invention may be a single resin or a polyamide resin partially substituted with another polyamide resin and / or another thermoplastic resin, but the resin replacing the polyamide resin PA92C Is preferably 50% by mass or less of the entire resin. If the polyamide resin PA92C is less than 50% by mass, the desired effect of the present invention may not be obtained.

  Examples of other polymers include polypropylene, ABS resin, polyphenylene oxide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polyphenylene sulfide.

  The blending ratio of the polyamide resin used in the present invention is preferably 65 to 75% by weight with respect to the entire resin composition. When the blending ratio of the polyamide resin is less than 65% by weight, it is not preferable because the toughness is lowered and deformation or breakage occurs. On the other hand, if it exceeds 75% by weight, impact resistance and slidability are lowered, which is not preferable.

(5) Conductivity-imparting material The polyamide resin composition of the present invention contains a conductivity-imparting material (B) for the purpose of preventing electrification.
The conductivity imparting material is not particularly limited as long as it can impart conductivity, and carbon fiber and carbon black are particularly preferably used.

  As the carbon fiber, pitch-based and PAN-based carbon fibers are used without limitation, but PAN-based carbon fibers are more preferable in view of properties such as physical properties and conductivity. The carbon fiber preferably has a fiber length of 0.1 to 12 mm before kneading, particularly preferably 1 to 8 mm. The fiber diameter of the carbon fiber is preferably 5 to 15 μm.

  The blending ratio of the carbon fiber is preferably 2 to 40% by weight, more preferably 3 to 35% by weight, and still more preferably 3 to 15% by weight with respect to the entire resin composition. When the blending ratio of the carbon fiber is less than 2% by weight, the electrical conductivity is lowered and it is easy to be charged with static electricity, and dust and dust are attached to cause a defect in a precision product. When the blending ratio exceeds 40% by weight, This is not preferable because it has high rigidity and inferior impact resistance, and the surface of the molded product is poor in smoothness and slidability is lowered.

  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 furnace black (Ketjen black) are particularly preferably used.

Carbon black is produced in various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, ash content and the like. Although there is no restriction | limiting in the characteristic of this carbon black, What has a favorable chain structure and a large aggregation density is preferable. A large amount of carbon black is not preferable in terms of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, more preferably 5 to 100 nm, more preferably from 10 to 70 nm, also the surface area (BET method) is preferably ^{10 m} 2 / g or more, more preferably 300 meters ² / g or more, to be 500 to 1500 ² / g Further, 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 is preferably 0.5% by weight or less, and more preferably 0.3% by weight or less. The DBP oil absorption here is a value measured by a method defined in ASTM D-2414. Carbon black preferably has a volatile content of less than 1.0% by weight.

  The blending ratio of carbon black is preferably 2 to 40% by weight, more preferably 2 to 30% by weight, and still more preferably 3 to 10% by weight with respect to the entire resin composition. When the blending ratio of the carbon black is less than 2% by weight, it is not preferable because sufficient conductivity cannot be obtained. When the blending ratio exceeds 40% by weight, the melt viscosity is high, the fluidity is lowered, and the molding processability is significantly impaired. Therefore, it is not preferable.

(6) Impact modifier The polyamide resin composition which comprises the cable housing of this invention contains an impact modifier (C).
Impact modifiers include (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) Examples thereof include a polymer, an ionomer polymer, and an aromatic vinyl compound / conjugated diene compound block copolymer, and these can be used alone or in combination.

  The above (ethylene and / or propylene) · α-olefin copolymer is a polymer obtained by copolymerizing ethylene and / or propylene and an α-olefin having 3 or more carbon atoms, and α- having 3 or more carbon atoms. Examples of olefins 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-eicocene, 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-1 Pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof.

  In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8- Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene- - norbornene, 2-ethylidene-3-isopropylidene-5-norbornene may be copolymerized non-conjugated diene polyene such as 2-propenyl-2,2-norbornadiene.

  The above (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer is ethylene and / or propylene and α, β-unsaturated carboxylic acid and A polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer. Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid, and α, β-unsaturated. Examples of 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.

  The ionomer polymer is obtained by ionizing at least part of the olefin and the carboxyl group of the α, β-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 α, β-unsaturated carboxylic acid, but are not limited to those exemplified here, The body may be copolymerized. In addition, 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. In the block copolymer, 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. In this case, aromatic vinyl compounds include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, 2,6-dimethyl styrene, vinyl naphthalene and vinyl. Anthracene, 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned. It may have a structural unit consisting of one or more of the monomers. In addition, 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 are 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. Here, the distribution in the polymer block mainly composed of the 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 the hydrogenated product thereof may be linear, branched, radial, or any combination thereof. Among them, in the present invention, as 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.

  Also, (ethylene and / or propylene) .alpha.-olefin copolymers used as impact modifiers, (ethylene and / or propylene). (. Alpha.,. Beta.-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) As the block copolymer of an aromatic copolymer, an ionomer polymer, an aromatic vinyl compound and a conjugated diene compound, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. 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 acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, Itaconic anhydride, no Citraconic acid, Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, acrylic Examples thereof include glycidyl acid, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid.

A preferred impact modifier in the present invention is an acid-modified ethylene copolymer.
The acid-modified ethylene copolymer is a graft of α, β-unsaturated carboxylic acid or a derivative thereof onto a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (hereinafter referred to as “unmodified ethylene copolymer”). It is obtained by polymerization.

  The unmodified ethylene copolymer is, for example, a Ziegler-Natta catalyst, particularly a vanadium compound such as vanadium oxytrichloride or vanadium tetrachloride and an organoaluminum compound, and usually 50 mol% or more, preferably 80 to It is obtained by copolymerizing 95 mol% of ethylene with an α-olefin having 3 or more carbon atoms, usually 50 mol% or less, preferably 20 to 5 mol%. Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, hexene-1, decene-1, 4-methylbutene-1, 4-methylpentene-1. In the present invention, LLDPE is preferably used.

  Examples of α, β-unsaturated carboxylic acids or derivatives thereof (hereinafter collectively referred to as “unsaturated carboxylic acids”) to be graft-polymerized to the above-mentioned unmodified ethylene copolymer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, Examples thereof include fumaric acid, anhydrides or esters of these acids. Of these, maleic anhydride is preferred.

  The graft amount of the unsaturated carboxylic acid is usually 0.05 to 1.5% by weight, preferably 0.1 to 1% by weight, based on the unmodified ethylene copolymer. When the amount of the unsaturated carboxylic acid is less than 0.05% by weight, the compatibility with the polyamide is deteriorated, so the effect of improving the slidability is reduced, and the amount of the unsaturated carboxylic acid is 1.5% by weight. In the case where it exceeds 1, the reaction with the terminal amino group of the polyamide is excessive, so that the melt viscosity becomes high or the gelling property is remarkably impaired, which is not preferable.

  Graft polymerization is performed by adding an unsaturated carboxylic acid to an unmodified ethylene copolymer according to a conventional method, and usually melt-kneading at 150 to 300 ° C. In the graft polymerization, an organic peroxide such as α, α'-bis-t-butylperoxy-p-diisopropylbenzene may be used for efficient polymerization. The amount of the organic peroxide used in this case is usually in the range of 0.001 to 0.05% by weight with respect to the unmodified ethylene copolymer.

  The density of the acid-modified ethylene copolymer used in the present invention is preferably 0.89 to 0.94 g / cc, particularly preferably 0.91 to 0.94 g / cc. When the density is less than 0.89 g / cc, the elastic modulus is lowered, so that the joint portion such as the meshing portion is easily deformed, and when the density is not more than 0.94 g / cc, the impact resistance is lowered. However, it is not preferable because the joint portion such as the meshing portion is broken.

  The blending ratio of the acid-modified ethylene copolymer used in the present invention is preferably 10 to 20% by weight with respect to the entire resin composition. When the blending ratio of the acid-modified ethylene copolymer is less than 10% by weight, the effect of improving the slidability is reduced, and dust due to friction is generated to cause a defect in precision products. On the other hand, if it exceeds 20% by weight, the elastic modulus is lowered, so that the joint part such as the meshing part is easily deformed, which is not preferable.

(7) Other components The polyamide resin composition used in the present invention may contain a reinforcing material such as glass fiber.
Moreover, a dispersing agent can be used for the purpose of dispersing the conductivity imparting material, the impact improving material, the reinforcing material, and the like.
In addition, the polyamide resin composition used in the present invention includes, as necessary, a heat resistance agent, a weather resistance agent, a mold agent, an antioxidant, a crystal nucleating agent, a crystallization accelerator, a lubricant, a pigment, a plasticizer, a crosslinking agent, Various additives such as a flame retardant, a flame retardant aid, and a dye may be added, and these are added when the resin composition is melt-kneaded or melt-molded.

(8) Manufacturing of cable housing The manufacturing method of the polyamide resin composition used in the present invention is not limited to a specific method, but as a specific and efficient example, a mixture of raw materials is used as a single-screw or twin-screw extruder, Banbury. Examples of the method include a method of supplying to a generally known melt mixer such as a mixer, a kneader, and mixin gall and kneading. In addition, there is no particular limitation on 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.

  Moreover, there is no restriction | limiting in particular about the method of shape | molding a cable housing from a polyamide resin composition, A polyamide resin composition can be injection-molded using an injection molding machine, or can be press-molded using a press molding machine.

  In the present invention, the polyamide resin (PA92C) (A) is blended with a conductivity imparting material (B) such as carbon fiber and / or carbon black, and an impact modifier (C) such as an acid-modified ethylene copolymer. By using such a polyamide resin composition, a cable housing having excellent slidability, mechanical strength, and electrical conductivity, as well as low water absorption, molding processability, chemical resistance, and the like can be obtained.

The volume resistivity of the polyamide resin composition in the present invention is desirably 1 × 10 ⁴ (Ωcm) or less. The volume resistivity of the polyamide resin composition is measured by the method of ASTM D257.

  The flexural modulus of the polyamide resin composition is preferably 6.0 GPa or more, and more preferably 6.4 GPa or more.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In addition, the used material and the measuring method of a physical property are shown below.

[Polyamide resin]:
PA92C-1 to PA92C-6, PA92 produced in the following production examples
・ Nylon 6 (Ube Industries, UBE nylon 1015B)
・ Nylon 66 (Ube Industries, UBE nylon 2020B)
・ Nylon 12 (Ube Industries, UBESTA3020U)
[Impact modifier (acid-modified ethylene copolymer)]:
-U-BOND Z488 manufactured by Ube Industries, Ltd .: Density 0.92 g / cc
・ Tafmer MC1307 manufactured by Mitsui Chemicals, Inc .: Density 0.89 g / cc
・ Tafmer MH5010 manufactured by Mitsui Chemicals, Inc .: Density 0.86 g / cc
[Carbon black]: Ketjen Black (EC600JD manufactured by Ketjen Black International Co., Ltd.)
[Carbon fiber]: Fortafil F243 manufactured by Akzo Nobel
[Dispersant]: Clariant Co., Ltd. Rico Wax-OP

(1) Relative viscosity (ηr):
ηr was measured at 25 ° C. using an Ostwald viscometer using a 96% polyamide sulfuric acid solution (concentration: 1.0 g / dl).

(2) Melting point (Tm) and crystallization temperature (Tc):
Tm and Tc were measured under a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer. The temperature was raised from 30 ° C. to 270 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 270 ° C. for 3 minutes, and then lowered to −100 ° C. at a rate of 10 ° C./min (temperature fall first). Then, the temperature was raised to 270 ° C. at a rate of 10 ° C./min (called a temperature raised second run). From the obtained DSC chart, the exothermic peak temperature of the temperature decrease first run was Tc, and the endothermic peak temperature of the temperature increase second run was Tm.

(3) 1% weight loss temperature (Td):
Td was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation. The temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min under a nitrogen stream of 20 ml / min, and Td was measured.

(4) Melt viscosity:
The melt viscosity was measured under the conditions of 250 ° C. in nitrogen and a shear rate of 0.1 s ⁻¹ by attaching a cone plate to a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan.

(5) Film molding:
Film forming was performed using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. After being melted by heating at 260 ° C. in a reduced pressure atmosphere of 500 to 700 Pa (290 ° C. when nylon 66 is used, 230 ° C. when nylon 12 is used) for 5 minutes, the film was formed by pressing at 5 MPa for 1 minute. Next, the reduced-pressure atmosphere was returned to normal pressure, and then cooled and crystallized at room temperature of 5 MPa for 1 minute to obtain a film.

(6) Water absorption rate (saturated water absorption rate, equilibrium water absorption rate):
A film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; weight about 0.05 g) obtained by molding the polyamide resin under the conditions of (5) is immersed in ion exchange water at 23 ° C., and the film is taken out every predetermined time. The weight of the film was measured. When the rate of increase in the film weight lasts 3 times within a range of 0.2% or less, it is determined that the absorption of water into the polyamide resin film has reached saturation, and the weight of the film before being immersed in water (Xg) From the weight (Yg) of the film when reaching saturation, the saturated water absorption (%) was calculated by the formula (1).
Saturated water absorption (%) = 100 (Y−X) / X (1)
The water absorption rate (equilibrium water absorption rate) calculated by the formula (1) from the weight (Yg) immediately after forming the film and the weight (Yg) when the film reached equilibrium at a humidity of 65% and a temperature of 23 ° C. ) As the wet water absorption.

(7) Chemical resistance:
After the polyamide hot press film obtained according to the present invention was immersed in the chemicals listed below for 7 days, the weight residual ratio (%) and changes in the appearance of the film were observed. In each of concentrated hydrochloric acid, 64% sulfuric acid, and glacial acetic acid solutions, tests were performed on samples immersed at 23 ° C.

(8) Hydrolysis resistance:
The polyamide hot press film obtained by the present invention was put in an autoclave, and each was 121 in water (pH = 7), 0.5 mol / l sulfuric acid (pH = 1), and 1 mol / l sodium hydroxide aqueous solution (pH = 14). The residual weight ratio (%) and the appearance change after the treatment at 60 ° C. for 60 minutes were examined.

(9) Mechanical properties:
In the following measurements [1] to [4], the following test pieces were measured at a resin temperature of 260 ° C. (290 ° C. when nylon 66 was used, 230 ° C. when nylon 12 was used), and a mold temperature of 80 ° C. This was molded by injection molding using this. The ones evaluated at 23 ° C. without conditioning immediately after molding are shown in the table as dry, and the ones evaluated at 23 ° C. after conditioning at a humidity of 65% and a temperature of 23 ° C. after molding are shown in the table.
[1] Tensile test (tensile yield point strength): Measured in accordance with ASTM D638 using a Type I test piece described in ASTM D638.
[2] Bending test (flexural modulus): Measured at 23 ° C. in accordance with ASTM D790 using a test piece having dimensions of 127 mm × 12.7 mm × 3.2 mm.
[3] Izod impact strength: Measured at 23 ° C. in accordance with ASTM D256 using a test piece having dimensions of 127 mm × 12.7 mm × 3.2 mm.
[4] Deflection temperature under load: Measured at a load of 1.82 MPa in accordance with ASTM D648 using a test piece having a test piece size of 127 mm × 12.7 mm × 3.2 mm.

(10) Volume resistivity:
It was measured by the method of ASTM D257.
(11) Amount of wear:
Using the Orientec Co., Ltd. friction and wear tester EFM-III-EN, the ring-on-plate method (plate size: width 30mm, thickness 3mm, length 100mm, plate material: S45C, ring is the same material as the plate) Evaluation was performed under the conditions of
Load: 0.5 MPa, peripheral speed: 50 cm / sec, time: 8 hr

[Resin Production Example 1: Production of PA92C-1]
Oxalic acid in a pressure vessel with a volume of 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with a diaphragm pump, nitrogen gas inlet, pressure relief port, pressure regulator and polymer outlet The operation of charging 28.40 kg (140.4 mol) of dibutyl, pressurizing the inside of the pressure vessel to 0.5 MPa with nitrogen gas having a purity of 99.9999%, and then releasing nitrogen gas to normal pressure is performed 5 After repeated nitrogen substitution, the system was heated while stirring under a sealing pressure. After adjusting the temperature of dibutyl oxalate to 100 ° C. over about 30 minutes, 18.89 kg (119.3 mol) of 1,9-nonanediamine and 3.34 kg (21.1 mol) of 2-methyl-1,8-octanediamine were obtained. ) (Molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 85:15) into a reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. The temperature was raised simultaneously with the supply. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. over 1 hour. 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 235 ° 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 brought to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. for 4.5 hours. . Thereafter, stirring was stopped, the inside of the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes, then released to an internal pressure of 0.5 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 obtained polyamide was a white tough polymer, and ηr = 3.20.

[Resin Production Example 2: Production of PA92C-2]
A mixture of 17.62 kg (111.3 mol) of 1,9-nonanediamine and 4.45 kg (28.1 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 80:20). The obtained polyamide was a white tough polymer and had ηr = 3.10.

[Resin Production Example 3: Production of PA92C-3]
A mixture of 11.11 kg (70.2 mol) of 1,9-nonanediamine and 11.11 kg (70.2 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 50:50). The obtained polymer was a white tough polymer, and ηr = 3.35.

[Resin Production Example 4: Production of PA92C-4]
1,9-nonanediamine 6.67 kg (42.1 mol), 2-methyl-1,8-octanediamine 15.56 kg (98.3 mol) in a mixture (1,9-nonanediamine and 2-methyl-1, A polyamide was obtained by reacting in the same manner as in Production Example 1 except that the molar ratio of 8-octanediamine was 30:70). The obtained polyamide was a white tough polymer, and ηr = 3.55.

[Resin Production Example 5: Production of PA92C-5]
A mixture of 1.33 kg (8.4 mol) of 1,9-nonanediamine and 20.88 kg (131.9 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 6:94). The obtained polymer was a white tough polymer, and ηr = 3.53.

[Resin Production Example 6: Production of PA92C-6]
A mixture of 1.33 kg (8.4 mol) of 1,9-nonanediamine and 20.88 kg (131.9 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -The octanediamine molar ratio was 6:94), and the reaction was carried out in the same manner as in Production Example 1 except that the internal pressure by extracting butanol was maintained at 0.25 MPa to obtain polyamide. The obtained polymer was a white tough polymer, and ηr = 4.00.

[Comparative Resin Production Example 1: Production of PA92]
Using only 22.25 kg (140.4 mol) of 1,9-nonanediamine as a diamine raw material, a reaction was carried out in the same manner as in Production Example 1 to obtain a polyamide. The obtained polymer was a yellowish white polymer, and ηr = 2.78.

  Polyamide resins PA92C-1 to PA92C-6, PA92 obtained in Resin Production Examples 1 to 6 and Comparative Resin Production Example 1, nylon 6 (Ube Industries, UBE nylon 1015B), nylon 66 (Ube Industries, UBE nylon) 2020B) and nylon 12 (Ube Industries, UBESTA3020U), relative viscosity, melting point, crystallization temperature, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, dry and wet machinery Characteristics were measured. The results are shown in Table 1.

実施例のポリアミド樹脂組成物を用いて所望の特性を有するケーブルハウジングを製造することができた。 [Examples 1-5, Comparative Examples 1-2]
Using the components shown in Table 2 in the proportions shown in Table 2, they were kneaded in a 44 mmφ vented twin-screw extruder set at a barrel temperature of 280 ° C. to produce the desired polyamide resin composition pellets.
Next, the obtained pellets were dried and injection molded to produce various test pieces. The physical properties shown in Table 2 (tensile elongation at break, dry and wet flexural modulus, Izod impact strength, volume resistivity, wear amount) ) Was evaluated. The obtained results are shown in Table 2.

A cable housing having desired characteristics could be manufactured using the polyamide resin composition of the example.

Claims (5)

It consists of a polyamide resin composition containing a polyamide resin (A), a conductivity imparting material (B), and an impact modifier (C). The polyamide resin is composed of oxalic acid as the dicarboxylic acid component and 1,9 as the diamine component. A polyamide resin comprising nonanediamine and 2-methyl-1,8-octanediamine, wherein the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 95: 5 A cable housing characterized by that.   The conductive cable housing according to claim 1, wherein the conductivity imparting material (B) is carbon fiber and / or carbon black.   The cable housing according to claim 2, wherein the carbon black is ketjen black.   The impact modifier (C) is an acid-modified ethylene copolymer obtained by modifying LLDPE having a density of 0.89 to 0.94 g / cc with an acid anhydride. Cable housing as described.   Polyamide containing 65 to 75% by weight of polyamide resin (A), 3 to 15% by weight of carbon fiber and 2 to 10% by weight of carbon black as conductivity imparting material (B), and 10 to 20% by weight of impact modifier (C) The cable housing according to claim 4, comprising a resin composition.