JP2013245258A - Composition containing polyamide resin and glass fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition showing a smaller dimensional change, friction coefficient and wear amount in an actual use compared to polyamide 66 that is generally used and includes 25 to 35 mass% of glass fiber.SOLUTION: A composition containing a polyamide resin and glass is provided for a sliding component, wherein the polyamide resin contains a polyamide resin produced from an oxalic acid compound as a raw material. Alternatively, a composition is provided which contains a polyamide resin and glass fiber, wherein the polyamide resin contains a polyamide resin produced from an oxalic acid compound as a raw material and the fiber diameter of the glass is 3 μm or more and 13 μm or less.

Description

  The present invention relates to a composition comprising a polyamide resin and glass fibers.

  Polyamide resins exhibit excellent properties as engineering plastics, and are therefore widely used in automobile parts, machine parts, and electric / electronic parts. Polyamide resins are particularly useful as molding materials for sliding parts such as gears, cams, and bearings because they are particularly excellent in mechanical properties and frictional wear resistance.

  Among them, polyamide 66 reinforced with glass fiber is excellent in mechanical properties and frictional wear resistance properties as disclosed in Patent Document 1, so that molding of sliding parts such as gears, cams and bearings is performed. A polyamide 66 which is used as a material and generally contains 25 to 35% by mass of glass fiber is used.

WO06 / 054774 WO2008-072754

However, generally used polyamide 66 including glass fiber has a large dimensional change, friction coefficient, and wear amount during actual use, and may not be sufficient for use in sliding parts. In particular, gears used in electric power steering require a device for adjusting the backlash (gap) when the dimensional change during actual use is large. In the case of polyamide 66 containing 25-35% by weight of commonly used glass fibers, the equipment is usually required.
The actual use refers to a state of being placed in an atmosphere of a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50% ± 10% for 500 hours or more.

  The problem to be solved by the present invention is to provide a composition having smaller dimensional change, coefficient of friction and wear amount in actual use than polyamide 66 containing 25 to 35% by mass of commonly used glass fiber. That is.

  The present inventors have found that a composition containing a polyamide resin and glass fiber using a specific raw material can achieve the above-mentioned problem.

That is, the present invention is a composition comprising a polyamide resin and glass,
The said polyamide resin is a composition for sliding components characterized by including the polyamide resin which uses an oxalic acid compound as a raw material.

  It is an object of the present invention to provide a composition having a smaller dimensional change, friction coefficient, and wear amount during actual use than polyamide 66 containing 25 to 35% by mass of glass fiber.

A test piece for obtaining dimensional stability is shown.

  The composition of this invention is a composition containing the polyamide resin and glass fiber which used the specific raw material.

[Polyamide resin]
The polyamide resin used for this invention contains the polyamide resin which uses an oxalic acid compound as a raw material. From the viewpoint of dimensional change during actual use of the composition, the amount of wear, and the reduction of the friction coefficient, the polyamide resin made from oxalic acid compound is preferably 10% by mass or more, more preferably 50% by mass or more, based on the total amount of the polyamide resin. 99 mass% or more is more preferable.

(1) Polyamide resin using oxalic acid compound as raw material The oxalic acid compound is a compound that provides a unit derived from oxalic acid, and is a compound derived from oxalic acid such as oxalic acid and / or oxalic acid diester. The oxalic acid compound only needs to have reactivity with an amino group. When producing a polyamide resin at a high polymerization temperature, if oxalic acid itself is used as a raw material, oxalic acid may be thermally decomposed. Derived compounds are preferred.

  As the compound derived from oxalic acid, oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction.

  Succinic acid diesters include oxalic acid diesters of aliphatic monohydric alcohols, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols.

  Examples of oxalic acid diesters of aliphatic monohydric alcohols include dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) butyl oxalate, and the number of carbon atoms is More than 3 aliphatic monohydric alcohol oxalate diesters are preferred, di-n-butyl oxalate, di-i-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is even more preferred.

  Examples of oxalic acid diesters of alicyclic alcohols include dicyclohexyl oxalate.

  Examples of oxalic acid diesters of aromatic alcohols include diphenyl oxalate.

  The oxalic acid diester is preferably at least one selected from the group consisting of an oxalic acid diester of an aliphatic monohydric alcohol having more than 3 carbon atoms, an oxalic acid diester of an alicyclic alcohol, and an oxalic acid diester of an aromatic alcohol. n-Butyl, di-i-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.

  These oxalic acid compounds can be added alone or in combination of two or more at the time of producing a polyamide resin using the oxalic acid compound as a raw material.

  Moreover, dicarboxylic acid compounds other than the oxalic acid compound can be used as the raw material for the polyamide resin using the oxalic acid compound as a raw material.

  Examples of dicarboxylic acid compounds other than oxalic acid compounds include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and compounds derived therefrom.

  Aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid. Examples include acids, azelaic acid, sebacic acid, and suberic acid.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid.

  Aromatic dicarboxylic acids include 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, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid Can be mentioned.

  These dicarboxylic acid compounds other than these oxalic acid compounds can be added alone or in combination of two or more when the polyamide resin is produced.

  Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible regardless of the presence or absence of dicarboxylic acids other than oxalic acid compounds.

  The content of units derived from dicarboxylic acid and / or polyvalent carboxylic acid other than oxalic acid compound contained in polyamide resin using oxalic acid compound as raw material is the total dicarboxylic acid and total polyvalent content contained in polyamide resin using oxalic acid compound as raw material. The total amount of carboxylic acid-derived units is preferably less than 50 mol%, more preferably 20 mol% or less, further preferably 10 mol% or less, further preferably 5 mol% or less, and further preferably 1 mol% or less. preferable.

  The diamine used in the polyamide resin using the oxalic acid compound as a raw material is not particularly limited, but ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentane. Diamine, 3-methyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 5-methyl-1, Aliphatic diamines such as 9-nonanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, cyclohexanediamine, methyl Cycloaliphatic diamine, isophorone diamine and other alicyclic diamines, p-phenylene diamine, m- And aromatic diamines such as enylenediamine, p-xylenediamine, m-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. Alternatively, two or more kinds can be added during production.

  Among these, from the relationship between the melting point of the obtained polyamide resin and the thermal decomposition temperature, it is composed of 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,10-decanediamine. At least one selected from the group is preferred, and 1,9-nonanediamine and 2-methyl-1,8-octanediamine are more preferred.

  The molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferably 1:99 to 99: 1 from the viewpoint of increasing the molecular weight of the polyamide resin using a succinic acid compound as a raw material, It is more preferable that it is 5: 95-95: 5. Furthermore, from the viewpoint of the melting point of the obtained polyamide resin, the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 5:95 to 40:60 or 60:40 to 95: 5. It is preferably 5:95 to 30:70 or more preferably 70:30 to 90:10.

  The content of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferably 50 mol% or more, more preferably in units derived from all diamines of the polyamide resin using oxalic acid compound as a raw material. Is 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and more preferably 99 mol% or more.

  Specific examples of polyamide resins made from oxalic acid compounds include homopolymers such as polyamide 92, polyamide 102, polyamide 122, and polyamide 62, and polyamide 92/62, polyamide 102/62, and polyamide 122/62. A copolymer is mentioned. These can use 1 type (s) or 2 or more types. Among these, at least one selected from the group consisting of polyamide 92, polyamide 102, polyamide 92/62, and polyamide 102/62 is preferable.

  Polyamide resin using an oxalic acid compound as a raw material has a relative viscosity of 2.3 or more and 6.0 in 96 mass% sulfuric acid in a polyamide resin concentration of 1 mass% and a temperature of 25 ° C. in accordance with JIS K-6920. The following is preferable from the viewpoint of fluidity during molding and toughness of the molded product, more preferably 2.5 or more and 5.0 or less, and further preferably 2.7 or more and 4.0 or less.

(2) Manufacture of polyamide resin using oxalic acid compound as raw material The polyamide resin using oxalic acid compound used as a raw material for the present invention can be manufactured using any method known as a method for manufacturing polyamide resin. However, from the viewpoint of increasing the molecular weight and productivity, it is preferable to carry out a batch-wise or continuous polycondensation reaction of a dicarboxylic compound containing a diamine and an oxalic acid compound, more preferably a diamine and an oxalic acid compound. Is produced by a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step or a pressure polymerization method described in WO2008-072754.

  The two-stage polymerization method and the pressure polymerization method are specifically shown by the following operations.

(2-1) Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then a diamine and a dicarboxylic compound containing an oxalic acid compound are mixed. In the case of mixing, a solvent in which both a diamine and a dicarboxylic compound containing an oxalic acid compound are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, 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.

  The charging ratio of the dicarboxylic compound containing diamine and oxalic acid compound is 0.8 to 1.5 (molar ratio), in terms of high molecular weight, in terms of the molar amount of dicarboxylic acid (a) / molar amount of diamine (b). Preferably it is 0.91-1.1 (molar ratio), More preferably, it is 0.99-1.01 (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 ultimate temperature of the prepolycondensation step, that is, preferably from 80 to 150 ° C., is finally preferably from 150 ° C. to 350 ° C., more preferably from 180 ° C. to 330 ° C., still more preferably 200 ° C. A temperature range of 320 ° C. or lower is reached.

  It is preferable to carry out the reaction while keeping the temperature rising time preferably 1 to 8 hours, more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final pressure in the case of performing the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(2-2) Pressurized polymerization method First, diamine is placed in a pressure vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, the dicarboxylic compound containing the oxalic acid compound is injected into the pressure vessel while maintaining the sealed pressure state at the reaction temperature, and the polycondensation reaction is started. The reaction temperature is not particularly limited as long as the polyamide resin produced by the reaction of the dicarboxylic compound containing diamine and oxalic acid compound can maintain a slurry or solution state and does not thermally decompose. The charging ratio of the dicarboxylic compound containing the diamine and the oxalic acid compound is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1, in terms of the molar amount of the dicarboxylic compound containing the oxalic acid compound / the molar amount of the diamine. (Molar ratio), more preferably 0.99 to 1.01 (molar ratio).

  Next, while maintaining the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of Component a, since the melting point is 245 to 300 ° C., the temperature is raised to 250 to 350 ° C., preferably 255 to 340 ° C., more preferably 260 to 335 ° C. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. The preferable final pressure in the case of performing the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(3) Polyamide resin other than polyamide resin using oxalic acid compound as raw material Polyamide resin other than polyamide resin using oxalic acid compound as raw material includes, for example, polycaprolactam (polyamide 6), polyundecanoic acid lactam (polyamide 11), and polylauryl. Lactam (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene Azelamide (polyamide 49), polytetramethylene sebamide (polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutata Amide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexa Methylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene diaminoadipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610) ), Polyhexamethylene dodecamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebamide (polyamide 910), poly Namethylene Dodecamide (Polyamide 912), Poly Decamethylene Adipamide (Polyamide 106), Poly Decamethylene Azelamide (Polyamide 109), Poly Decamethylene Decamide (Polyamide 1010), Poly Decamethylene Dodecamide (Polyamide 1012), Polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), caprolactam / hexamethylenediaminoadipic acid Copolymer (polyamide 6/66), caprolactam / hexamethylene diamino azelaic acid copolymer (polyamide 6/69), caprolactam / hexamethylene diamino sebacic acid copolymer (polymer) Amide 6/610), caprolactam / hexamethylenediaminoundecanoic acid copolymer (polyamide 6/611), caprolactam / hexamethylenediaminododecanoic acid copolymer (polyamide 6/612), caprolactam / aminoundecanoic acid copolymer (polyamide) 6/11), caprolactam / lauryl lactam copolymer (polyamide 6/12), caprolactam / hexamethylenediaminoadipic acid / lauryllactam (polyamide 6/66/12), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminosebacin Acid (polyamide 6/66/610) and caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedicarboxylic acid (polyamide 6/66/612). These can use 1 type (s) or 2 or more types.

[Glass fiber]
Although the glass fiber used for this invention is not specifically limited, From a viewpoint of improving the adhesiveness of glass fiber and resin, it is preferable that it is converged with the convergence material.

  The converging material is not particularly limited, but is preferably a urethane resin and / or an acrylic resin from the viewpoint of compatibility with the polyamide resin. In the case of other convergent materials, the compatibility with the polyamide resin is not sufficient, and the physical properties and the like may decrease.

  The glass fiber used in the present invention is not particularly limited, but when the average fiber diameter is 3 μm or more and 13 μm or less and outside the range of 3 μm or more and 13 μm or less, the dimensional stability and mechanical properties of the molded article of the present invention are deteriorated. . From the viewpoint of further improving the dimensional stability, mechanical properties, and sliding properties of the molded article of the present invention, 5 μm or more and 12 μm or less is preferable, and 6 μm or more and 11 μm or less is more preferable.

  The average fiber diameter of the glass fiber can be measured according to JIS R3420.

  The glass fiber is preferably surface-treated with a surface treatment agent from the viewpoint of adhesiveness with the polyamide resin. Examples of the surface treatment agent include silane compounds, chromium compounds, titanium compounds, and the like, and surface treatment agents of silane compounds and / or titanium compounds are preferable.

  As the surface treatment agent for the silane compound, an aminosilane coupling agent excellent in adhesion to the sizing agent is preferable, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ. -Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminodithiopropyltrihydroxysilane, γ- (polyethyleneamino) propyltrimethoxysilane, N-β- (aminopropyl) -γ-aminopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) -ethylenediamine, γ-dibutylaminopropyltrimethoxysilane, etc. It is done. These can use 1 type (s) or 2 or more types.

  As surface treatment agents for titanium-based compounds, isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl titanate, tetra Butyl titanate, tetraoctyl bis (ditridecyl phosphite) titanate, isopropyl trioctanoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl dimethacrylisostearoyl titanate , Tetra (2,2-diallyloxymethyl-1-butyl Bis (ditridecylphosphite) titanate, isopropyl tricumylphenyl titanate, bis (dioctyl pyrophosphate) oxy acetate titanate, and isopropyl isostearoyl diacryl titanate. These can use 1 type (s) or 2 or more types.

  Among these, at least selected from the group consisting of N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane and γ-aminopropyltriethoxysilane. One is preferred.

[Composition]
The composition of this invention contains the polyamide resin which uses an oxalic acid compound as a raw material, and a specific glass fiber.

  From the viewpoint of improving mechanical properties and slidability with respect to the total amount of the composition, the composition of the present invention includes 10% by mass or more and 80% by mass or less of glass fiber, and from the viewpoint of further improving physical properties and slidability, The glass fiber is preferably contained in an amount of 15% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less.

  The composition of the present invention preferably contains 20% by mass to 90% by mass of the polyamide resin with respect to the total amount of the composition. From the viewpoint of mechanical properties and slidability, the polyamide resin is 40% by mass to 85% by mass. % Or less, more preferably 50% by mass or more and 80% by mass or less.

  Furthermore, the composition of the present invention preferably contains cuprous iodide, potassium iodide and melamine, and the total amount of cuprous iodide, potassium iodide and melamine is 0.1% by mass or more. The content is preferably 2.0% by mass or less, more preferably 0.2% by mass or more and 1.0% by mass or less, and further preferably 0.25% by mass or more and 0.38% by mass or less. The mass ratio of cuprous iodide, potassium iodide and melamine (cuprous iodide: potassium iodide: melamine) is preferably 2 to 4:40 to 60: 1 to 2. It is more preferable that it is 5-3.5: 45-55: 1.5-2.5.

  The composition of the present invention preferably contains a fatty acid metal from the viewpoint of moldability, and preferably contains 100 ppm or more and 300 ppm or less of the fatty acid metal with respect to the total amount of the composition.

  Examples of the fatty acid metal include zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, lithium stearate, calcium laurate, zinc linoleate, calcium ricinoleate, and zinc 2-ethylhexoate. From the viewpoint of properties, at least one selected from the group consisting of lithium stearate, calcium stearate and sodium stearate is preferred.

  In the composition of the present invention, various additives, modifiers, reinforcing materials such as heat stabilizers, antioxidants, UV absorption, etc., which are usually blended within the range that does not impair the properties of the composition of the present invention. Agents, weathering agents, fillers, plasticizers, foaming agents, antiblocking agents, tackifiers, sealability improvers, anti-clouding agents, mold release agents, crosslinking agents, foaming agents, flame retardants, colorants (pigments, dyes Etc.), inorganic reinforcing materials such as coupling agents and glass fibers.

  The composition of the present invention can contain a thermoplastic resin other than the polyamide resin within a range not impairing the properties of the composition of the present invention. As the thermoplastic resin other than the polyamide resin, a high-density polyethylene (HDPE) can be used. ), Medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), ethylene / propylene copolymer (EPR), ethylene / Polyolefin resins such as butene copolymer (EBR), acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1 , 2-Dicarboxylic acid, Endobicyclo- [2.2.1] -5-heptene- Carboxyl groups such as 1,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5 With compounds containing functional groups such as epoxy groups such as acid anhydride groups such as heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl itaconate Modified polyolefin resins, polyether resins such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polymethacrylonitrile, acrylonitrile / styrene copolymer Combined (AS), methacrylate Nitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS).

  There is no restriction | limiting in particular in the manufacturing method of the composition of this invention, Usually, the following manufacturing methods can be mentioned. A method using a mixer such as a cylindrical mixer, a method using a twin screw extruder, a single screw extruder, a multi screw extruder, a Banbury mixer, a roll mixer, a kneader or the like, a combination of a mixer and an extruder The manufacturing method etc. can be mention | raise | lifted.

  The composition of the present invention is preferably used for slidable parts because of its low dimensional stability, coefficient of friction, and wear during actual use.

[Molding]
Examples of the method for forming the composition of the present invention into a molded product include injection molding and extrusion molding. Among these, the method by injection molding is preferable.

  As a molded product formed by molding the polyamide resin composition of the present invention, an injection molded product is preferable. Among the injection molded products, sliding parts are preferable, and among the sliding parts, one type selected from the group consisting of gears, pulleys, cams and bearings is preferable.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Various evaluation methods and materials used are shown below.

(1) Dimensional stability Using a SE100D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece of 200 mm × 40 mm × 3 mmt in FIG. 1 was prepared, and the test piece was subjected to conditions of 23 ° C. and humidity 50% RH. The weight change due to water absorption was measured at intervals of about 400 hours, and the time when equilibrium was reached was defined as the saturated water absorption. The distance between the marking lines in the test piece was measured with an OLYMPUS microscope, and the dimensional stability was calculated by the following equation. MD indicates dimensional stability in the A direction (flow direction) in FIG. 1, and TD indicates dimensional stability in the B direction (vertical direction) in FIG.
Dimensional stability = (Distance between mold marking lines-Distance between marking lines in test specimen) / Distance between mold marking lines x 100

(2) Limit PV value Using a SE100D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., creating a test piece of 100 mm × 30 mm × 3 mm and placing it under conditions of 23 ° C. and humidity 50% RH for 500 hours or more In accordance with the JIS K7218A method, a Suzuki friction friction tester was used, using a ring with an outer diameter of 25.6 mm, an inner diameter of 20 mm, and a height of 15 mm, which is S45C carbon steel described in JIS standard G4051. The limit PV value of the specimen is a ring-on-plate method, the test speed is 500 mm / s, the test load is multiplied by 20 kgf (196 N) at the start of the test, and the load is increased by 20 kgf (196 N) every 10 minutes. And measured. The load immediately before the load at which the test piece was melted was defined as the limit PV value.

(3) Coefficient of dynamic friction Using the above-mentioned limit PV value measuring device, the sliding speed is applied by applying a constant load of 500 mm / s and 20 kgf (196 N) by the ring-on-plate method in the same manner as the measurement of the limit PV value. Was measured under conditions of 3 km and 5 km. The dynamic friction coefficient was calculated from the following equation.
Coefficient of dynamic friction = (friction resistance) / (load applied to specimen)

(4) Amount of wear Using the above-mentioned limit PV value measuring device, measurement is performed under the same conditions as the measurement of the dynamic friction coefficient. Was calculated.
Abrasion amount = (weight of specimen before measurement) − (weight of specimen after measurement)

[material]
(1) Polyamide resin made from oxalic acid compound (polyamide 92)
Into a pressure vessel with an internal volume of about 150 L equipped with a raw material inlet, a nitrogen gas inlet, a pressure outlet, a stirrer, a thermometer, a torque meter, a pressure gauge, a pressure regulator, and a polymer outlet directly connected to a pump, a diamine ( b) 1,9-nonanediamine 20.1 kg (127 mol) and 2-methyl-1,8-octanediamine 3.5 kg (22 mol) were charged, and the pressure vessel was pressurized to 0.5 MPaG with nitrogen gas. Then, after repeating the operation of releasing nitrogen gas to normal pressure and replacing with nitrogen, the system was heated while stirring under a sealing pressure. After the internal temperature was raised to 150 ° C. over about 1 hour, 30.2 kg (149 mol) of dibutyl oxalate dicarboxylic acid (a) was supplied into the reaction vessel at a flow rate of 1.49 L / min by a pump and the temperature was raised at the same time. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPaG by butanol produced by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. Meanwhile, the internal pressure was adjusted to 1.0 MPaG while extracting the generated butanol from the pressure release port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure relief port, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was adjusted to 260 ° C., and the reaction was continued at 260 ° C. until the torque value reached a constant value. Thereafter, the stirring is stopped and the inside of the system is pressurized to 1 MPaG with nitrogen and allowed to stand, and then released to an internal pressure of 0.5 MPaG. Polyamide 92 (hereinafter sometimes referred to as PA92) is drawn from the lower outlet of the pressure vessel. Extracted into a shape. The string-like PA92 was immediately cooled with water and pelletized by a pelletizer. The relative viscosity was 3.13. In the obtained PA92, the content of units derived from the succinic acid compound is 100 mol% in the total amount of units derived from all dicarboxylic acids contained in PA92, and 1 in the total amount of units derived from all diamine (b), The total content of units derived from 9-nonanediamine and 2-methyl-1,8-octanediamine is 100 mol%, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 83: 17-86: 14.
(2) Polyamide resins other than polyamide resins made from oxalic acid compounds (polyamide 66)
Polyamide 66 (PA66-1) (hereinafter sometimes referred to as (PA66-1))
Polyamide 66 having a relative viscosity of 2.6 to 2.8 measured in 96 mass% sulfuric acid in a polyamide concentration of 1 mass% and a temperature of 25 ° C. according to JIS K-6920.
Polyamide 66 (PA66-2) (hereinafter sometimes referred to as (PA66-2))
A polyamide 66 having a relative viscosity of 3.2 to 3.4 measured in 96 mass% sulfuric acid under the conditions of a polyamide resin concentration of 1 mass% and a temperature of 25 ° C in accordance with JIS K-6920.

(3) Glass fiber / glass fiber (GF-1) (hereinafter sometimes referred to as (GF-1))
ECS03T-251DE manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 6.5 μm was used.
Glass fiber (GF-2) (hereinafter sometimes referred to as (GF-2))
ECS03T-251H manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 10.5 μm, was used.
Glass fiber (GF-3) (hereinafter sometimes referred to as (GF-3))
ECS03T-289DE manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 6.5 μm, was used.
Glass fiber (GF-4) (hereinafter sometimes referred to as (GF-4))
ECS03T-289 manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 13.0 μm, was used.

[Examples 1 and 2, Comparative Examples 1 and 2]
The polyamide resin and glass fiber described in Table 1 are kneaded at a ratio described in Table 1 with a 44 mmφ vented twin-screw extruder set at a barrel temperature of 260 ° C., pelletized with a pelletizer, and pellets of the composition are obtained. Obtained.
Next, the pellets of the obtained composition were dried at 110 ° C. and 10 Torr (1330 Pa) for 24 hours, and then injection molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. to obtain various test pieces. The obtained test piece was evaluated by the above evaluation method. The results are shown in Table 1.

  From the results shown in Table 1, it is clear that a composition containing a polyamide resin and glass fiber made from an oxalic acid compound is excellent in dimensional stability and wear resistance.

  The composition of the present invention can be suitably used as various sliding members such as automobiles, electric / electronics, industrial materials, industrial materials, daily necessities, and household items.

Claims (6)

A composition comprising a polyamide resin and glass fibers;
The composition for a sliding part, wherein the polyamide resin includes a polyamide resin made of an oxalic acid compound as a raw material. A composition comprising a polyamide resin and glass fibers;
The polyamide resin includes a polyamide resin using a oxalic acid compound as a raw material,
The composition whose fiber diameter of the said glass fiber is 3 micrometers or more and 13 micrometers or less.   The fiber diameter of the said glass fiber is 3 micrometers or more and 13 micrometers or less, The composition of Claim 1 characterized by the above-mentioned.   The composition according to any one of claims 1 to 3, comprising 10% by mass or more and 80% by mass or less of glass fiber with respect to the total amount of the composition.   The sliding component which consists of a composition of any one of Claims 1-4.   The sliding component according to claim 5, wherein the sliding component is a gear.

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