Polyamide composition and molded articles made from the composition. (2023)

The present invention relates to a polyamide resin composition and to molded articles made from the composition.

Polyamide resins have excellent resistance to organic solvents such as gasoline, have high fluidity when melted, are excellent in moldability, and are also excellent in thermal and mechanical properties. Consequently, polyamide resins have been widely used as automotive exterior materials and engine room components.

Fuel parts that come into contact with fuel and with parts of the human body, such as fuel caps, present a risk of ignition due to electrostatic discharge, e.g. generated when the lid is opened or closed. Therefore, in order to suppress the occurrence of electric discharges, compositions containing, for example, conductive carbon black are used in fuel components.

On the other hand, printing is usually done on fuel parts, and fuel parts must be suitable for laser marking, which is great in terms of cost and productivity. In order to achieve excellent laser marking performance and excellent impact resistance, Japanese Unexamined Patent Publication No. 2011-32320 proposes a composition comprising carbon black, carbon fiber, aramid, and a carbon black masterbatch. metallic organic fiber. Furthermore, Japanese Patent No. 4889987 proposes a polyamide resin composition comprising an ethylene-α-olefin copolymer, a modified high-density polyethylene and carbon black.

Patent document 1: JP 2011-32320

Patent Document 2: Japanese Patent No. 4889987

However, the composition disclosed in Japanese Unexamined Patent Publication No. 2011-32320 requires an additional separate step to prepare a master batch. In addition, the polyamide resin composition described in Japanese Patent No. 4889987 cannot satisfactorily satisfy both electrical conductivity and laser marking properties.

An object of the present invention is to provide a polyamide resin composition having both excellent electrical conductivity and excellent laser marking properties.

The present inventors carried out extensive and intensive investigations. As a result, it was found that a polyamide resin composition containing specific amounts of PAN carbon fiber, carbon black and black dye in a polyamide resin exhibited excellent electrical conductivity and excellent laser marking performance.

Specifically, the present invention includes the following examples.

The first embodiment is a polyamide resin composition comprising polyamide resin, PAN carbon fiber, carbon black, and black dye, wherein the polyamide resin composition comprises 7.5 to 25% by weight of carbon fiber. BREAD carbon. The weight of the composition comprises 0.01 to 0.55% by weight of carbon black, based on the weight of the composition, and comprises 0.01 to 1.0% by weight of black dye, based on the weight of the composition. composition weight.

The second embodiment is a molded article made from the above polyamide resin composition.

According to the present invention, a polyamide resin composition with excellent electrical conductivity and excellent laser marking properties can be provided.

As shown in the picture. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing a visual evaluation method for laser marking properties.

As shown in the picture. Fig. 2 is a view showing measurement locations of molded articles for measuring the rate of dimensional change after immersion in fuel.

In this description, with respect to the amount of a component in a composition, when a plurality of substances corresponding to the component are present in the composition, the amount of the component in the composition refers to the total amount of substances present in the composition. . Composition unless otherwise stated.

The polyamide resin composition according to the present invention is a polyamide resin composition comprising polyamide resin, PAN carbon fiber, carbon black and black dye, wherein the polyamide resin composition contains 7.5-25 % carbon fiber PAN. The weight, based on the weight of the composition, contains from 0.01 to 0.55% by weight of carbon black, based on the weight of the composition, and contains from 0.01 to 1.0% by weight of black colorant, based on the weight of the composition. .

[polyamide resin]

Polyamide resin has an amide bond (-CONH-) in its main chain, for example it is formed by polymerization or copolymerization of lactam, aminocarboxylic acid or diamine and dicarboxylic acid or diamine and oxalic acid. By using diester acid as raw material, it is synthesized by known methods such as melt polymerization, solution polymerization and solid phase polymerization.

Exemplary lactams include e-caprolactam, ω-enantholactame, ω-undecalactame, ω-laurolactam, a-pyrrolidone and a-piperidone, and e-caprolactam and ω-laurolactam.

Examples of aminocarboxylic acids include aliphatic ω-aminocarboxylic acids such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, preferably 12-aminodecanoic acid -aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

Examples of diamines include aliphatic diamines such as ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptandiamine, octyldiamine, nonandiamine, decandiamine, undecadiamine, methyldiamine, dodecamethylenediamine, dimethylenemethylenedipentadiene, dimethylenemethylene, dipentadiene, dimethylenemethylene, dipentecylamine. hexadecylmethylenediamine, heptadecmethylenediamine amine, octadecamethylenediamine, nonadecyldiamine, eicosamethylenediamine, 2-methyl-1,8-octanediamine or 2,2,4/2,4,4-trimethylhexane-1,6-diamine; alicyclic diamines such as 1,3-/1,4-ciclohexyldiamina, bis(4-aminociclohexyl)methano, bis(4-aminociclohexyl)propano, bis(3-metil-4-aminociclohexyl)methano, (3-metil-4-aminociclohexilo )propano, 1,3-/ 1,4-bisaminometilciclohexano, 5-amino-2,2,4-trimetil-1-cyclopentanmethanamina, 5-amino-1,3,3-trimetilciclohexanomethanamina, bis(aminopropyl)piperazine, bis( aminoethyl)piperazine or norbornanemethyleneamine; m -/p-xylylenediamine and other aromatizing diamines, preferably hexamethylenediamine, nonamethylenediamine, 2-methyl-1,8-octanediamine.

Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, acid, tridecanedioic acid, dodecanedioic acid, , pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid and eicosanodic acid, 1,3-/1, alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid and norbornanoic acid. Aromatic dicarboxylic acids, such as isophthalic acid, terephthalic acid, 1,4-/1,8-/2,6-/2,7-naphthalenedicarboxylic acid, preferably oxalic acid and adipic acid.

Examples of oxalic acid diesters include oxalic acid diesters of aliphatic alcohols such as dimethyl oxalate, diethyl oxalate, di-n-(or iso)propyl oxalate and di-n-(iso- or tert-)butyl oxalate , dicyclohexyl oxalate and oxalic acid diesters of alicyclic alcohols such as oxalic acid esters and diesters of aromatic alcohols such as diphenyl oxalate. Di-n-butyl oxalate, diisobutyl oxalate and di-tert-butyl oxalate are more preferred, and di-n-butyl oxalate is most preferred.

Examples of polyamide resins include polyamide resins that are polymers of lactam and aminocarboxylic acid, or diamine and dicarboxylic acid, or diesters of diamine and oxalic acid, or polyamide resins that are copolymers of these monomers. wear. Polyamide resins can be used singly or in combination of two or more.

Examples of polyamid resins include polycaprolactam (polyamid 6), polyundecanolactam (polyamid 11), polylaurolactam (polyamid 12), polyethylenadipamid (polyamid 26), polyamid Butylenadipamid (polyamid 46), polyhexamethylenedipamid (polyamide 66-methylenedipamid (polyamid-6-methylene)), polihexametilenadipamid (polyamide) 610), polihexametilenenundecamid (polyamida 611), polihexametilenodecamid (polyamide 612), polihexametileneterephthalamida (polyamide 6T), polyhexamethylene polyisophthalamide (polyhexametilenodecamid (polyamide(61))methylene(polyamide) H)), 96), polinonamethylene adipamide Methylazamide (polyamide 99), polinonamethylene-sebacamide (polyamide 910), polinonamethyleneendodecamid (polyamide 912), polinonamethylene-p-phenylenediamine (polyamide 9T), politrimetil-phenmethylene-HT, politrimetil-hexamethylene-HT - p-phenylenediamine (polyamide 9T(H )), polinonametilennaphthalenediamida (polyamide 9N), polihexametilen-sebacamida (polyamida 106), polidecametilennonandiamina (poliamida 1) 09), polidecametileindecilamida (poliamida 1010), polyamide 1010, polyamide 1010, polyamide 1010, cametilenterephthalamida (polyamide 10T), polidecamethylene hexahidroterephtalamida (polyamide) 10T (H )), polidecametilennaphthalenediamina (polyamide 10N), polidodecametilennonandiamina (polyamide 126), polidodecametilennonandiamina (poliamide 129-polido12-dimetilen-polido129), (polyamide-129-methylene-polido12), cametilendodecamid (polyamide 1212), polidodecamethyleneterephthalamide (polyamide 12T), polidodecam ethylenehexahidroparaftalamida (polyamide 12T(H)), polidodecamethylenenaphthalenedicarboxamide (polyamide 12N), polihexamethyleneisophthalamida (polyamideMXthalamidD6) polyamide MXthalamid (polyamide MXthalamidD6) 8), polyisophthalyleno-nonandiamine (polyamide MX) D9), polyisophthaloyl sebacamide (polyamide MXD10), polyamide dipthalamide (polyamide MXD12) , polyamide malondimethylacetamfetamina (polyamide MXDT), polyamide dien dialyl Drosophila (polyamide MXDI) (polyamide MXDI MXDI) polyamide polihexamina IDE PACM-42, Phamamine IDE PACM12, polibis (4-aminociclohexyl) methane m-phenylenediamine (polyamide PACMI) , polibis (3 -metil-4-aminociclohexyl) methane dodecamid (polyamide dimethyl PACM12), polyisophoron adipamid (polyamide IPD6) and polyisophoron terephthalamide (polyamide IPDT).

Eksempler på copolymerer omfatter caprolactam/hexamethylendiaminoadipinosyre copolymer (polyamide 6/66), caprolactam/hexamethylendiamine azelainsyre copolymer (polyamide 6/69), caprolactam/hexamethylendiaminosebacinsyre copolymer (polyamide 6/610), caprolactam acid 6/610, caprolactam 6/610 copolymer /611), caprolactam/hexamethylendiaminedodecansyre copolymer-copolymer (polyamide 6/612), caprolactam/aminoundecansyre copolymer (polyamide 6/11), caprolactam/laurillactam copolymer (polyamide 6/12), caprolactam/hexamethylendiamid -6-/6 -/laulyenylamidactam-6/12), Caprolactam / Hexamethylendiaminoadipat / Hexamethylendiaminosebacinsyre (Polyamide 6/66/610), Caprolactam / Hexamethylendiaminoadipat / Hexansyre Diaminododecanedicandicarboxylsyre (Polyamide 6/66/612, Polyamide/220, Polyamide/22,612, polyamide/120, polyamide/62 og caprolactam/polyisophorone-adipamide-copolymer (polyamide 6/IPD 6-copolymer).

Among them, from the viewpoint of formability, at least one selected from polyamide 6, polyamide 66, polyamide 610, polyamide 1010, polyamide 6/66, polyamide 11, polyamide 12 and polyamide 6/12 is preferred. A polyamide and polyamide 6/66/12, more preferably selected from the group consisting of polyamide 6, polyamide 66, polyamide 6/66, polyamide 11, polyamide 12, polyamide 610, and polyamide 1010 At least one polyamide from the group, more preferably polyamide 6 and/or polyamide 66.

The polyamide resin preferably has a relative viscosity of 1.0 to 6.0 measured in 96% by weight sulfuric acid, at a 1% by weight polyamide concentration and at a temperature of 25°C according to JIS K- 6920. If the relative viscosity of the polyamide resin is within the above range, the viscosity of the composition at the time of melting is moderate, molding is easy, and the resulting molded article has excellent mechanical properties. From the same point of view, the relative viscosity of the polyamide resin is more preferably 1.5 to 5.0, even more preferably 1.7 to 4.5, especially preferably 2.2 to 3, 5.

From the point of view of adhesion during injection welding, the polyamide resin preferably contains terminal amino groups with a concentration of (10⁻⁵eq/g) is greater than the carboxyl terminal concentration (10⁻⁵equivalent/g). More preferably, all polyamide resins have a terminal amino group concentration of (10⁻⁵eq/g) is greater than the carboxyl terminal concentration (10⁻⁵equivalent/g). The ratio of the concentration of the terminal amino group to the concentration of the terminal carboxyl group is more preferably 1.1 or more, more preferably 1.5 to 40.0.

Terminal amino concentration (10⁻⁵eq/g) can be measured by dissolving a polyamide resin in a mixed phenol/methanol solution and titrating with 0.05 N hydrochloric acid. Terminal carboxyl concentration (10⁻⁵eq/g) can be measured by dissolving polyamide resin in benzyl alcohol and titrating the resulting solution with 0.05 N sodium hydroxide solution.

The end-modified polyamide is produced by polymerization or copolymerization by known methods, such as melt polymerization, solution polymerization, and solid phase polymerization in the presence of an amine. Alternatively, the end-modified polyamide is prepared by carrying out the polymerization in the presence of an amine and then melt-kneading the resulting polymer. Therefore, the amine can be added at any stage during polymerization or at any stage during the melt-kneading process after polymerization. However, it is preferred to add amines in stages during polymerization for reasons of adhesion at the time of injection welding.

Examples of amines include monoamines, diamines, triamines, and polyamines. In addition to the amine, a carboxylic acid such as monocarboxylic acid, dicarboxylic acid or tricarboxylic acid may be added, if necessary, in an amount meeting the aforementioned terminal group concentration requirement. The amine and carboxylic acid can be added simultaneously or separately. Furthermore, the following amines and carboxylic acids can be used alone or in combination.

Specific examples of the added monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, octylamine, octylamine, pentadecylamine, octylamine, octylamine, eicosylamine and behenylamine, cycloaliphatic monoamines such as cyclohexylamine and methylcyclohexylamine, aromatic monoamines such as benzylamine and β-benzylamine, N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, N, N-dihexylamine, N,N-dioctylamine and other symmetrical and mixed secondary amines such as N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine , N-ethyl-N-hexadecylamine, N-ethyl-N-octadecylamine, N-propyl-N-hexadecylamine and N-propyl-N-benzylamine. These can be used alone or in combination.

Specific examples of added diamines include aliphatic diamines such as 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8- octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,15-pentadecanediamine, 1,16-1,17-heptadecanediamine, 1,18-octadecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octyldiamine, 2,2, 4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine or 5-methyl-1,9-nonanediamine; alicyclic diamines such as 1,3-bis(aminometil)ciclohexano, 1,4-bis(aminometil)ciclohexano, bis(4-aminociclohexyl)methano, 2,2-bis(4-aminociclohexyl)propano, bis(3-metil)- 4-aminocyclohexyl)methano, 2,2-bis(3-methyl-4-aminocyclohexyl))propano, 5-amino-2,2,4-trimethyl-1-cyclopentanemethanamine, 5-amino-1,3,3-trimethylcyclohexanemethanamine . ) triciclodecano, aromatic diamines, such as m-xylylenediamine and p-xylylenediamine. These can be used alone or in combination.

Specific examples of triamines to be added include 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2,4-triaminobutane, 1,2,3,4-tetraaminobutane, 1, 3 , 5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,3,5-triaminocyclohexane Aminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2 , 4-triaminonaphthalene, 2,5,7-triaminonaphthalene and 2,4,6-triaminonaphthalene Aminopyridine. Specific examples of tetraamines include 1,2,4,5-tetraaminocyclohexane, 1,2,4,5-tetraaminobenzene, 1,2,7,8-tetraaminonaphthalene, and 1,4,5,8-tetraaminonaphthalene. These can be used alone or in combination.

The added polyamine can have several primary amino groups (-NH₂) and/or secondary amino group (-NH-), and examples of polyamines include polyalkyleneimines, polyalkylenepolyamines, polyvinylamines and polyallylamines. The amino groups with active hydrogen serve as reactive sites for the polyamines.

Polyalkyleneimines, for example by ionic polymerization of alkyleneimines such as ethyleneimine or propyleneimine, or by polymerization of alkyloxazolines and then subjecting the resulting polymer to partially or completely hydrolyzed hydrolysis. Examples of polyalkylenepolyamines include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and ethylenediamine reaction products and polyfunctional compounds. Polyvinylamine is obtained, for example, by polymerizing N-vinylformamide to form poly(N-vinylformamide) and then partially or completely hydrolyzing the resulting polymer with an acid such as hydrochloric acid. Polyallylamine is generally obtained by polymerizing the hydrochloride salt of the allylamine monomer and then removing the hydrochloric acid from the resulting polymer. These can be used alone or in combination. Among them, polyalkyleneimines are preferred.

Examples of polyalkyleneimines include homopolymers and copolymers obtained by polymerizing one or two or more kinds of alkyleneimines having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine or 1, 1-dimethylethylenimine, according to the general method. Among them, polyethyleneimine is more preferable. The polyalkyleneimine may be a branched polyalkyleneimine containing primary amine, secondary amine and tertiary amine obtained by ring-opening polymerization of alkyleneimine as a raw material, or a branched polyalkyleneimine containing only primary amine and secondary amine. Any linear polyalkyleneimine obtained by polymerization of an alkyloxazoline as raw material and a polyalkyleneimine with a three-dimensional crosslinked structure. Furthermore, polyalkyleneimines can be compounds containing, for example, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylene. Those of tetramine, dihexamethylenetriamine, aminopropylethylenediamine or bisaminopropylethylenediamine. Polyalkyleneimines generally have reactive tertiary amino groups derived from active hydrogen atoms on nitrogen atoms contained therein and primary and secondary amino groups (imino groups) each having one active hydrogen atom.

There is no particular limitation on the number of nitrogen atoms in the polyalkyleneimine. However, the number of nitrogen atoms in the polyalkyleneimine is preferably 4 to 3,000, more preferably 8 to 1,500, most preferably 11 to 500. Furthermore, the number average molecular weight of the polyalkyleneimine is preferably 100 to 20,000, more preferably from 200 to 10,000, and even more preferably from 500 to 8,000.

On the other hand, examples of the added carboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, caprylic acid, capric acid, nonanoic acid, undecanoic acid, lauryl acid, , tridecanoic acid, myristic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, cycloaliphatic monocarboxylic acids such as cyclohexylalkanecarboxylic acids and methylcyclohexanecarboxylic acids such as benzoaromaticcarboxylic acids such as benzoaromaticcarboxylic acids; acid, toluic acid, ethylbenzoic acid, phenylacetic acid, etc.; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanedic acid, hexadecanoic acid, hexadecanoic acid, octadecanoic acid, octadecanoic acid, eicosanodic acid, eicosanodic acid, docosanodic acid, diglycolic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethylalidipic acid, such as methylarboxyladipic acid3; -cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and norbornenedicarboxylic acid. Terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and other aromatic dicarboxylic acid family. and tricarboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, and trimesic acid. These can be used alone or in combination.

The amount of the amine used can be appropriately determined by a known method by taking into account the concentration of terminal amino groups, the concentration of terminal carboxyl groups, the relative viscosity and the like of the polyamide resin to be produced. Generally, the amount of amine to be added is preferably 0.5 to 20 meq/mol, more preferably 1.0 to 10 meq/mol per . The number of monomers or monomeric units that make up the repeating unit. (In terms of the equivalent (equivalent) of amino groups, 1 equivalent corresponds to the number of amino groups that react with carboxyl groups in a 1:1 ratio to form amido groups.)

For polyamide resins, among the above amines, it is preferred to add diamine and/or polyamine during polymerization, to meet the end group concentration requirement, and it is more preferred to add diamine and/or polyamine selected from aliphatic At least one selected from the group consisting of diamines, alicyclic diamines, and polyamines.

Examples of polyamide resin production equipment include known polyamide production equipment such as batch reaction tanks, single and multi-chamber continuous reaction equipment, tubular continuous reaction equipment, and kneading reaction extruders. Single screw kneading extruder and twin screw kneading extruder. As the polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used for polymerization, and the polymerization can be performed by repeating operations under normal pressure, reduced pressure, and increased pressure. These polymerization methods can be used alone or in a suitable combination.

[PAN Carbon Fiber] PAN carbon fiber is a carbon fiber obtained by carbonizing polyacrylonitrile fiber.

As for the length of the PAN carbon fiber, the PAN carbon fiber may be a short fiber or a continuous fiber with a length of up to 1,000 mm, depending on the use of the composition. However, from the point of view of productivity, for example, feeding the composition to a twin-screw kneader, the length of the PAN carbon fiber before kneading is preferably 0.1 to 20 mm, more preferably from 1 to 15mm.

There is no particular limitation on the fiber diameter of the PAN carbon fiber. However, PAN carbon fibers with smaller fiber diameter may exhibit strength in the resulting resin composition or molded article, but PAN carbon fibers with excessively small fiber diameter may suffer from carbon fiber fibrillation, for example, when they are introduced into a mixer. production efficiency during kneading. From the viewpoint of mechanical properties such as productivity and strength when using a kneader, PAN carbon fibers with a fiber diameter of 5 to 15 µm are preferable. A masterbatch or granulated carbon fibers preliminarily prepared by adding a high concentration of carbon fibers to the resin are less likely to fibrillate the carbon fibers during the manufacture of the polyamide resin composition, so it is preferable to use carbon fibers extremely fine.

[negro request]

The carbon black may be any of furnace black obtained by a furnace method, channel black obtained by a channel method, acetylene black obtained by an acetylene method, and thermal black obtained by a thermal method, but from a point from an electrical standpoint from an electrical standpoint In view of availability and cost, acetylene black is preferred and the conductivity and furnace type are preferred.

[Black dye]

Examples of the black dye include nigrosin and nigrosin, and any of them can be used to achieve similar effects, but nigrosin is preferable from cost and formability standpoints. Examples of commercially available nigrosin products include SPIRIT BLACK SB, SPIRIT BLACK AB, SPIRIT BLACK SA, SPIRIT BLACK SZ, Nigrosin EE, Nigrosin EX and Nigrosin manufactured by Orient Chemical Industries Co., Ltd. EX-BP.

[Fiberglass]

From the viewpoint of improving impact resistance, the polyamide resin composition preferably contains glass fibers.

The glass fibers are preferably glued with a bonding agent, taking into account the feeding properties of the composition to a kneading machine or the like.

The adhesive is preferably a polyurethane resin and/or an acrylic resin from the viewpoint of compatibility with the polyamide resin. From the viewpoint of further improving compatibility with polyamide resins, acrylic resins are more preferred.

From the viewpoint of improving the dispersibility and adhesiveness of the polyamide resin, it is preferable to treat the surface of the glass fiber with a surface treatment agent. Examples of the surface treatment agent include silane compounds, chromium compounds and titanium compounds, and a surface treatment agent containing a silane compound and/or a titanium compound is preferred.

As a surface treatment agent composed of a silane compound, an aminosilane coupling agent excellent in adhesion to a sizing agent, e.g. γ-aminopropyltrimethoxysilane, γ-thioaminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-y-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ- aminodithiopropyltrihydroxysilane, γ-(polyethyleneamino)propyltrimethoxysilane, N-β-(aminopropylmethyl)-γ-N-(trimethoxysilylpropyl))-ethylenediamine and γ-dibutylaminopropyltrimethoxy-based silane. These can be used alone or in combination.

Examples of surface treatment agents combined with titanium compounds include isopropyltriisoesteariltitanato, isopropyltris(N-aminoetil)titanato, isopropyltris(dioctilpirofosfato)titanioéster, tetraisopropylbis(dioctilphosphit)titanato, tetraisopropyltitanato, tetraisopropyl-tetrafiloctitanato, tetrabutritiloctilo éster de titanato de tetrabutiloctyl-(dioctylpirofosfato), isopropyltridodecylbenzenesulfonilitanato , isopropiltris (DioCtilfosfat) Titanato, Bis (Dioktilpirofosfato) Etilentitanato, IsopropildimetacriloilisoESTEARILTITANATO, 2- Arilltitanato, Tetrakis-Dibutiloximetil (2-dibutilsiloxi) éster) Titanato, isopropiltricumilfeniltitanato, bis (dioCtilpirofosfato) Oxiacetatitanato o Isopropilistearildiacrilatanato. These can be used alone or in combination.

Among them, they are preferably selected from N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-aminopropylmethyldimethoxysilane and γ-amino. At least one from the group consisting of propyltriethoxysilane.

As regards the glass fibers, there may be glass fibers with a circular section taken in a direction perpendicular to the longitudinal direction and/or glass fibers with a non-circular section taken in a direction perpendicular to the longitudinal direction. Used.

There is no particular limitation on the average fiber diameter of glass fibers with a circular cross section. However, from the viewpoint of dimensional stability and mechanical properties of the resulting molded product, the average diameter of the glass fibers of circular cross section is preferably 5 to 25 µm, more preferably 5 to 24 µm and even more preferably from 6 to 25 µm. µm. µm. 23 microns.

The average fiber diameter of glass fibers with a circular cross section can be measured in accordance with JIS R3420.

In glass fibers with a non-circular cross section perpendicular to the longitudinal direction, the ratio of the large diameter to the small diameter of the cross section perpendicular to the longitudinal direction is 1.2 to 10. In glass fiber with a non-circular cross section circular cross section, low torsion and From the point of view of mechanical properties, the ratio of the major axis to the minor axis in the cross section perpendicular to this direction is preferably 1.2 to 10 in the direction length of the fiber, more preferably from 1.5 to 6, and even more preferably from 1.7 to 4.5. The major diameter represents the maximum length of a straight line connecting two points on the cross section profile, and the minor diameter represents the minimum length of a straight line perpendicular to the major diameter and connecting two points on the section contour. cross.

The glass fiber of non-circular cross section preferably has a major axis of 2 to 100 µm and a minor axis of 1 to 20 µm.

Glass fibers with a non-circular cross section may be glass fibers with a predetermined ratio of major diameter to minor diameter and are generally shaped like a cocoon, ellipse, semicircle, circular arc, rectangle, or use a parallelogram or the like. In fact, glass fibers with a cocoon-shaped, elliptical or rectangular cross section are preferable from the point of view of fluidity, mechanical properties and low twist.

[Fluency Enhancer]

From the viewpoint of improving flowability, the polyamide resin composition preferably contains an agent for improving flowability.

Examples of flow improvers include dicarboxylic acids and polyols, and polyols are preferred from the viewpoint of reactivity with polyamide resins.

Examples of dicarboxylic acids include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and specific examples include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid and terephthalic acid, formic acid.

The polyols include not only polyols but also partial ester compounds of polyols and fatty acids and partial ester compounds of alkylene oxide addition products of polyols and fatty acids. Specific examples of polyols include ethylene glycol, propylene glycol, 1,3-/1,4-butanediol, 2-methyl-1,3-propanediol, 1,2-/1,3-/1,4-/1,5- pentanediol, neopentylglycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl- 1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, glycerin, diglycerol, triglycerol, tetraglycerol, polyoleglycerol, trimethylolpropane, Ditriol Methylpropane , Tris-(Trimethylolpropane), Trimethylolbutane, Erythritol, Pentaerythritol, Dipentaerythritol, Tripentaerythritol, Polypentaerythritol, 1,2,4-Butanetriol, 1,3,5-Pentanetriol, 1,3,5-H1ex,2,6,1 -H1ex , 2,6, 1,3,4-butanetritol, sorbitol, isosorbide, sorbitol, adonitol, arabitol, xylitol, mannitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, trehalose , raffinose, maltose, isoraffinose, gentisana and melecitose.

Among them, from the viewpoint of improving fluidity, at least one selected from the group consisting of pentaerythritol, polyglycerol, trimethylolethane, trimethylolpropane, dipentaerythritol, sorbitan and sorbitol is preferable. A polyol, more preferably at least one polyol selected from pentaerythritol, dipentaerythritol, polyglycerol, trimethylolethane and trimethylolpropane. From the viewpoint of suppression of dispersion of the composition during kneading or molding and excellent dispersibility, at least one polyhydric alcohol selected from pentaerythritol, polyglycerol, dipentaerythritol and trimethylolethane and at least one polyol are more preferred. An alcohol selected from pentaerythritol, dipentaerythritol and trimethylolethane.

[polyamide resin composition]

The polyamide resin composition contains 7.5-25% by weight of PAN carbon fiber, 0.01-0.55% by weight of carbon black and 0.01-1.0% by weight of black dye, based on weight. About the weight of the composition.

The polyamide resin composition contains 7.5 to 25% by weight of PAN carbon fiber based on the weight of the composition and from the viewpoint of electrical conductivity, preferably in an amount of 8 to 20% by weight. , more preferably in an amount of 8 to 20% by weight. 15% by weight

From the viewpoint of conductivity, the ratio of PAN carbon fiber to polyamide resin is preferably 10.0 to 40.0% by weight, more preferably 12.0 to 25.0% by weight.

Based on the weight of the composition, the polyamide resin composition contains 0.01 to 0.55% by weight of carbon black, and from the point of view of laser marking, it preferably contains 0.03 to 0 0.52% by weight of carbon black, more preferably from 0.05 to 0.5% by weight,% by weight

From the viewpoint of laser marking properties, the ratio of carbon black to polyamide resin is preferably 0.02 to 1.20% by weight, more preferably 0.05 to 1.00% by weight. weight. From the viewpoint of electrical conductivity and laser marking properties, the proportion of carbon black in the PAN carbon fiber is preferably 0.1 to 2.5% by weight, more preferably 0.6 to 3.5% by weight.

The polyamide resin composition contains 0.01 to 1.0% by weight of a black colorant based on the weight of the composition, and from the viewpoint of laser marking performance, formability and impact resistance , an amount of 0.01 0.5% by weight to 0.5% by weight is preferred. % An amount of 0.02 to 0.5% by weight is more preferred, an amount of 0.03 to 0.3% by weight is even more preferred, and an amount of 0.05 to 0.3 is particularly preferred. % in weigh.

The proportion of the black dye to the polyamide resin is preferably 0.02 to 2.00% by weight, more preferably 0.08 to 0.75% by weight, from the viewpoint of laser marking properties. , formability and impact resistance. From the viewpoint of laser marking properties, the ratio of black dye to carbon black is preferably 1.5 to 99.0% by weight, more preferably 10.0 to 90.0% by weight.

From the viewpoint of impact resistance, the content of glass fibers in the polyamide resin composition is preferably 15 to 60% by weight, more preferably 25 to 50% by weight, and even more preferably 30% by weight. 45% by weight. % by weight, based on the weight of the composition.

From the viewpoint of impact resistance, the ratio of glass fibers to polyamide resin is preferably 20 to 55% by weight, more preferably 35 to 50% by weight.

From the viewpoint of improving flowability, the content of the flowability-improving agent in the polyamide resin composition is preferably 0.01 to 5% by weight, more preferably 0.03 to 4% by weight, and even more preferably from 0.01 to 5% by weight. From 0.05 to 3% by weight, based on the weight of the composition.

From the viewpoint of the flowability improvement, the ratio of the flowability improving agent to the polyamide resin is preferably 0.02 to 10% by weight, more preferably 0.08 to 6.0% by weight. weight.

From the viewpoint of mechanical properties, the content of polyamide resin in the polyamide resin composition is preferably 20 to 100% by weight, more preferably 70 to 100% by weight, and even more preferably 90 to 100% by weight. 100% by weight. % by weight, based on the weight of the residue obtained by removing from the composition the PAN carbon fiber, carbon black, black dye, glass fiber and flotation improver.

Examples of the method for producing the polyamide resin composition include a dry mixing method using a drum or a mixer, a melt kneading method using a single screw or a twin screw extruder, and a masterbatch method in which the resin is previously kneaded. in a blender. The raw material is concentrated to a high concentration using a single or twin screw extruder and the resulting mixture is diluted before use. From the viewpoint of improving the dispersibility, the melt kneading method is preferable.

The polyamide resin composition may contain various commonly incorporated additives, modifiers or reinforcing agents, such as heat stabilizers, antioxidants, ultraviolet absorbers, weathering agents, fillers, plasticizers, foaming agents, antiblocking agents, additives, tackifiers , sealing agents, antifog agents, mold release agents, crosslinkers, foaming agents, dispersants, flame retardants, colorants (pigments, dyes, etc.), coupling agents or glass Inorganic compounds other than talc, such as talc, are used in amounts that do not sacrifice the properties of the composition.

Furthermore, thermoplastic resins other than polyamide resins can be used in the polyamide resin composition within the range that does not impair the properties of the composition.

Eksempler på other thermoplastiske harpikser end polyamide harpikser omfatter polyolefinharpikser såsom højdensitetspolyethylen (HDPE), mediumdensitetspolyethylen (MDPE), lavdensitetspolyethen (LDPE), lavdensitetspolyethylen (LDPE), linear lavdensitetspolyethylen (LLDPE), ultrahøjmolekylær - vægt polyethylene (UHMWPE), polypropylene (PP) ) , Polybutylene (PB), Polymethylpentene (TPX), Ethylene/Propylene Copolymer (EPR), Ethylene/Butylene Copolymer (EBR), Ethylene/Vinyl Acetate Copolymer (EVA), Ethylene/Acrylic Copolymer (EAA), Copolymer ethylene/methacrylic acid (EMAA), ethylene/methyl acrylate copolymer (EMA), ethylene/methacrylic acid methyl ester copolymer (EMMA) and ethylene/ethyl acrylate copolymer (EEA); polystyrenharpikser såsom polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate/styrene copolymer (MS), methyl methacrylate/styrene/butadiene copolymer (MBS), styrene/butadiene copolymer (SBR), styrene/butadiene copolymer isoprene (SIR), styrene/isoprene/butadiene copolymer (SIBR), styrene/butadiene/styrene copolymer (SBS), styrene/isoprene/styrene copolymer (SIS), benzene copolymer, ethylene/ethylene/butylene/styrene ( SEBS) and styrene/ethylene/propylene/styrene copolymer (SEPS) for horn polyolefin groups that contain functional groups, such as carboxyl groups or their sales, sireanhydride groups and epoxy groups and polystyrene groups. Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly(ethylene glycol ester/ethylene isophthalate) copolymer (PET/PEI), polytrimethylene terephthalate (PTT), methylene polycyclophthalate (PCT), polynaphthalene ethylene dicarboxylate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), crystalline flydende polyester (LCP), polymælkesyre (PLA), polyglycolsyre (PGA); polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO); polysulfone resins such as polysulfone (PSU), polyethersulfone (PESU) and polyphenylsulfone (PPSU); polysulphide, polyphenylene sulphur (PPS) and polysulphide sulfone (PTES) trap; Polyketonharpikser såsom polyketon (PK), polyetherketone (PEK), polyetherketone (PEEK), polyetherketone (PEKK), polyetheretherketone (PEEEK), polyetheretherketone (PEEKK), polyetherketoneketone (PEKKK) y polyetherketone etherketone (PEKEKK), polinitriloharpikser, såsom polyac rilnitrile (PAN ), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer (ABS) and acrylonitrile/butadiene copolymer (NBR); polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), assom polyvinyl chloride (PVC) polyethylene resins, vinyl chloride/chlorine copolymer vinylidene, vinylidene chloride/methyl acrylate copolymer; cellulose resins such as cellulose acetate and cellulose butyrate; fluorharpikser såsom polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorofluoroethylene (PCTFE), tetrafluoroethylene/ethylene copolymer (ETFE), ethylene/chlorotrifluoroethylene (PTFE) copolymer, tetrafluoroethylene/hexafluoropropylene copolymer ( FEP), tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride (THV) copolymer, tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride/perfluoro(alkyl vinyl ether) copolymer, tetrafluoroethylene/perfluoro-(tetrafluoroethylene/perfluoro-(copolymer) hexafluoropropylene/perfluoro) (alkyl vinyl ether) or chlorotrifluoroethylene vinyl fluoride/perfluoro(alkyl vinyl ether)/tetrafluoroethylene copolymer (CPT); polycarbonate and polycarbonate (PC) resins; polyimide and thermoplastisk polyimide (TPI) resins, polyetherimide, polyesterimide, polyamide- imide (PAD and polyesteramide-imide; thermoplastiske polyurethane resins, polyamide elastomers, polyurethane elastomers and polyester elastomers Said kan bruges alene eller i combinación.

The polyamide resin composition has excellent electrical conductivity and excellent laser marking performance, and therefore can be used advantageously for fuel parts that require laser marking.

[cast product]

The molded article made from the polyamide resin composition of the present invention is molded, for example, by injection molding, extrusion molding, blow molding, pressure molding, roller molding, foam molding, injection molding, etc. vacuum or pressure, or stretch molding, although from the point of view of productivity, injection molding is preferable. That is, the present invention includes the use of the above polyamide resin composition as a molded article and the use of the polyamide resin composition as an injection molded article.

The molded article made from the polyamide resin composition of the present invention can be used advantageously as injection welding parts and fuel parts requiring laser marking, and has excellent electrical conductivity and laser marking performance. excellent, so it can be used particularly advantageously as parts that require laser marking. Fuel components must be laser marked. That is, the present invention includes the use of the above polyamide resin composition as an injection welding part and the use of the polyamide resin composition as a fuel part.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, which are not to be construed as limiting the scope of the present invention.

[relative viscosity]

The relative viscosity is measured in accordance with JIS K-6920 in 96% sulfuric acid, 1% polymer concentration and a temperature of 25°C.

[Terminal amino group concentration]

Terminal amino concentration (10⁻⁵eq/g) is measured by dissolving a polyamide resin in a mixed phenol/methanol solution and titrating the resulting solution with 0.05 N hydrochloric acid.

[Terminal carboxyl group concentration]

Terminal carboxyl concentration (10⁻⁵eq/g) is measured by dissolving polyamide resin in benzyl alcohol and titrating the resulting solution with 0.05N sodium hydroxide solution.

[Laser Marking Features]

Each of the polyamide resin compositions of Examples and Comparative Examples were molded into a 100 x 70 x 3 mm molded product by an injection molding machine, and the molded product was printed using a laser marker manufactured by KEYENCE. , using YVO₄(yttrium vanadate) crystal laser with a printing speed of 1,000 mm/sec, an efficiency of 40% and a frequency of 20 kHz.

The surface of the molded article on which printing was performed by marking was observed under the above conditions, as shown in Fig. 10. 1. Evaluate according to the following criteria.

A: You can read letters.

B: The letters are hard to read.

[Volume resistivity (in absolute dry state)]

The polyamide resin compositions in the examples and comparative examples were respectively molded into 100 x 70 x 3mm molded products by an injection molding machine, and then Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Analytical Technology Co., Ltd. used to install at Hiresta UP The URS probe of MCP-HT450 is in contact with the center of the surface of the molded product, and a voltage of 10 V is applied to the molded product for 30 s. After 30 s, measure the resistance of the volume. This operation was repeated five times and the average value of five measured values ​​was obtained.

To suppress discharge, the acceptance criteria is a volume resistivity of 10⁷Ω·cm or less.

[Volume resistivity (EC10 60 ℃ × 1000 hours after treatment)]

Each of the polyamide resin compositions of Examples and Comparative Examples were molded into 100 x 70 x 3 mm molded articles by an injection molding machine. Place the synthetic gasoline prepared by adding 10% by volume of ethanol to fuel C with a 1:1 isooctane toluene ratio in a stainless steel autoclave and immerse the strained product in synthetic gasoline at 60°C for 1000 hours. Then, the molded product was taken out of the autoclave and left in an atmosphere of 23°C and 50% relative humidity for 24 hours, and Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Analytical Technology Co., Ltd.. it was used. , put the URS probe connected to the Hiresta UP MCP-HT450 in contact with the center of the surface of the molded product, apply a voltage of 10 V to the molded product for 30 seconds, and measure the resistance of the volume after 30 seconds. This operation was repeated five times and the average value of five measured values ​​was obtained.

To suppress discharge, the acceptance criteria is a volume resistivity of 10⁷Ω·cm or less.

[Rate of dimensional change after immersion in fuel]

The polyamide resin compositions of Examples and Comparative Examples were molded into molded products of 200 mm x 40 mm x 3 mm, respectively, as shown in Figure 1 using an injection molding machine. 2. After standing in an atmosphere of 23°C and 50% relative humidity for 48 hours, the distance between the scoring lines formed on the surface of the molded article is measured using a microscope manufactured by OLYMPUS CORPORATION. , to obtain dimensions before immersion in fuel. The units of the numbers are shown in the figure. 2 is etc.

Then, synthetic gasoline (CE10) was prepared by adding 10% by volume of ethanol to fuel C with a toluene to isooctane ratio of 1:1 (CE10), placed in a stainless steel autoclave, and the mold was immersed in the gasoline. synthetic at 60°C. After standing at °C for 1000 hours, the distance between the marking lines on the surface of the molded article was measured with a microscope manufactured by OLYMPUS CORPORATION, and the size after immersion in fuel was obtained.

Using the dimensions before the fuel immersion and the dimensions after the fuel immersion obtained above, the rate of dimensional change after the fuel immersion was determined according to the calculation formula shown below. The rate of dimensional change after immersion in fuel with respect to the longitudinal direction (MD direction) and the transverse direction (TD direction) was determined.
Dimensional change rate after oil immersion (%) = (dimension after oil immersion-dimension before oil immersion)/dimension before oil immersion × 100

[polyamide resin]

• • PA-1 Place 20 kg of ε-caprolactam as polymerizable monomer, 0.5 kg of water and m-xylylenediamine in a 70-liter autoclave so that the ratio of m-xylylenediamine to ε-caprolactam is 1/290 (equiv/ mol) of lactam), the autoclave was flushed with nitrogen, and then the mixture was heated to 100°C and stirred to homogenize the mixture in the autoclave. Then, polymerization was carried out in an autoclave at 260°C and 1.7 MPa to obtain polyamide 6 (hereinafter generally referred to as "PA-1").

The relative viscosity of the obtained PA-1, the amino terminal concentration and the carboxyl terminal concentration are, respectively, 2.47, 5.9 (10⁻⁵equivalent/g) and 4.6 (10⁻⁵equivalent/g).

• • PA-2 In a 70 liter autoclave, 20 kg of e-caprolactam as polymerizable monomer, 0.5 kg of water and m-xylylenediamine are loaded, and the ratio of m-xylylenediamine to e-caprolactam is 1/290 (equiv /mol lactam) The autoclave was flushed with nitrogen and then the mixture was heated to 100°C and stirred to homogenize the mixture in the autoclave. Next, polymerization was carried out in an autoclave at 260°C and 1.7 MPa to obtain polyamide 6 (hereinafter generally referred to as "PA-2").

The relative viscosity of the obtained PA-2, the amino terminal concentration, the carboxyl terminal concentration are 2.41, 9.6 respectively (10⁻⁵equivalent/g) and 2.6 (10⁻⁵equivalent/g).

• • PA-3 Polyamide 66 (hereinafter sometimes referred to as "PA-3"). The relative viscosity is measured in 96% by mass sulfuric acid, the polyamide concentration is 1% by mass and the temperature is 25°C. According to JIS K-6920, the concentration of the terminal amino group and the concentration of the terminal carboxyl group are 2.75 and 3.7 (10⁻⁵eq./g) y 6,3 (10⁻⁵equivalent/g).
  • PA-4 Polyamide 6/66 (hereinafter referred to as "PA-4"), its relative viscosity is measured in 96% by weight sulfuric acid, the polyamide concentration is 1% by weight and the temperature is 25 °C .°C. According to JIS K-6920 the concentration of the terminal amino group and the concentration of the terminal carboxyl group 3.04, 5.2 (10⁻⁵equivalent/g) and 4.5 (10⁻⁵equivalent/g).

【Carbon fiber bread】

• • CF-1 TRO6NL B6R made by Mitsubishi Rayon Co., Ltd., which is PAN carbon fiber (hereinafter generally referred to as "CF-1"), was used.

[negro request]

• • CB-1 HI BLACK 890B manufactured by Orion Engineered Carbons, which is a furnace black (hereinafter generally referred to as "CB-1"), was used.
  • CB-2 Ketjen black EC600JD with Ketjen black (hereinafter generally referred to as "CB-2") made by Lion Corporation.

[Black dye]

• • BA-1 SPIRIT BLACK manufactured by Orient Chemical Industries Co., Ltd., which is aniline black (generally referred to as "BA-1" hereinafter) was used.

[Fiberglass]

• • GF-1 T-249, manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having a circular cross section and a glass fiber diameter of 13 μm (hereinafter generally referred to as "GF- 1") was used.
  • GF-2 T-249H, manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having a circular cross section and a glass fiber diameter of 10.5 μm (hereinafter generally referred to as " GF-2") was used.
  • GF-3 CSO3TA FT692 manufactured by Owens Corning Japan Ltd., which is a glass fiber with a circular cross section and a glass fiber diameter of 23 µm (hereinafter generally referred to as "GF-3"), was used.
  • GF-4 CGS 3PA-820S, manufactured by Nitto Boseki Co., Ltd., is a glass fiber with an irregularly shaped cross section in which the distances between the long and short diameters of the cross section are taken in the vertical direction. and the longitudinal direction of the fiber is 28 µm and 7 µm, respectively µm, a major axis to minor axis ratio of 4.0 (hereinafter generally referred to as "GF-4") was used.

[Fluency Enhancer]

• • FA-1 Pentarit® manufactured by Koei Chemical Co., Ltd., which is pentaerythritol (hereinafter generally referred to as "FA-1"), was used.
  • FA-2-trimethylolethane (hereinafter referred to as "FA-2") manufactured by Mitsubishi Gas Chemical Co., Ltd. was used.

Polyamide resin shown in Table 1, PAN Carbon Fiber, Carbon Black, Black Dye, Fiberglass, Flow Improver is mixed with the formula shown in Table 1, use an extruder mix of double screw, granules with granulator. A pelletizing machine for obtaining pellets of the polyamide resin composition. Using the obtained pellets of the polyamide resin composition, measurements and evaluations were carried out according to the above method. The results are shown in Table 1.

The complete description of Japanese Patent Application No. 2014-218635 (filing date: October 27, 2014) and Japanese Patent Application No. 2014-223413 (filing date: October 31, 2014) is incorporated by reference into this manual. All references, patent applications and technical standards described in this specification are incorporated into this specification by each being cited by the same reference as is the case with each of the respective references, patent applications and technical standards, specifically and shown separately. included in this specification.