WO2013108344A1 - Composition de résine, et composition contenant une résine polyamide et des fibres de verre - Google Patents

Composition de résine, et composition contenant une résine polyamide et des fibres de verre Download PDF

Info

Publication number
WO2013108344A1
WO2013108344A1 PCT/JP2012/008164 JP2012008164W WO2013108344A1 WO 2013108344 A1 WO2013108344 A1 WO 2013108344A1 JP 2012008164 W JP2012008164 W JP 2012008164W WO 2013108344 A1 WO2013108344 A1 WO 2013108344A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
polyamide
acid
polyamide resin
oxalic acid
Prior art date
Application number
PCT/JP2012/008164
Other languages
English (en)
Japanese (ja)
Inventor
佳史 赤川
直靖 藪
亮輔 佐々木
斉 児玉
Original Assignee
宇部興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012118496A external-priority patent/JP2013245258A/ja
Priority claimed from JP2012268975A external-priority patent/JP2013166916A/ja
Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Publication of WO2013108344A1 publication Critical patent/WO2013108344A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a resin composition containing a polyamide resin and a polyphenylene ether resin.
  • the present invention relates to a composition comprising a polyamide resin and glass fibers.
  • polyamide resins typified by nylon 6 and nylon 66 have been widely used as textiles for clothing or industrial materials or general-purpose engineering plastics because of their excellent properties and ease of melt molding.
  • a polyamide resin using oxalic acid as a dicarboxylic acid component is called a polyoxamide resin, and is known to have a higher melting point and lower water absorption than other polyamide resins having the same amino group concentration (Patent Document 1).
  • polyphenylene ether is used in a wide range of applications because of its excellent mechanical properties and heat resistance and excellent dimensional stability.
  • polyamide resins are widely used in automobile parts, machine parts, and electric / electronic parts because they exhibit excellent properties as engineering plastics.
  • 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.
  • polyamide 66 reinforced with glass fiber is excellent in mechanical properties and frictional wear resistance properties as disclosed in Patent Document 2, so that it can form sliding parts such as gears, cams, and bearings.
  • a polyamide 66 containing 25 to 35% by mass of glass fiber is generally used.
  • polyphenylene ether Since polyphenylene ether has a high softening point, melt molding is difficult, and there are problems such as decomposition of the resin when the molding temperature is raised. For this reason, it has been attempted to improve melt molding by blending a styrene resin, but the heat resistance and chemical resistance of the resulting molded product are lowered, and the original properties of the polyphenylene ether resin itself are impaired. There is a drawback that it is easy.
  • the first problem to be solved by the present invention is to provide a resin composition having low water absorption and excellent heat resistance and electrical characteristics.
  • polyamide 66 including glass fiber has a large dimensional change, friction coefficient, and wear amount in actual use, and may not be sufficient for use in sliding parts.
  • gears used in electric power steering require a device for adjusting the backlash (gap) when the dimensional change during actual use is large.
  • 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 second problem to be solved by the present invention is 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. Is to provide.
  • the present invention is a resin composition comprising a polyamide resin (A) and a polyphenylene ether resin
  • the polyamide resin (A) includes a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b),
  • the dicarboxylic acid (a) contains an oxalic acid compound
  • the diamine (b) includes two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine; It is a resin composition whose content of the said polyphenylene ether resin is less than 60 mass% with respect to the total amount of the said polyamide resin (A) and the said polyphenylene ether resin.
  • 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.
  • the resin composition of the first invention has low water absorption and is excellent in electrical characteristics and heat resistance.
  • a test piece for obtaining dimensional stability is shown.
  • the present invention is a resin composition comprising a polyamide resin (A) and a polyphenylene ether resin
  • the polyamide resin (A) includes a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b),
  • the dicarboxylic acid (a) contains an oxalic acid compound
  • the diamine (b) includes two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine; It is a resin composition whose content of the said polyphenylene ether resin is less than 60 mass% with respect to the total amount of the said polyamide resin (A) and the said polyphenylene ether resin.
  • the polyamide resin (A) used in the present invention contains a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b), the dicarboxylic acid (a) contains an oxalic acid compound, and the diamine (b) Two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine are included.
  • the dicarboxylic acid (a) used in the present invention is a dicarboxylic acid compound having reactivity with an amino group and providing a unit derived from a dicarboxylic acid as a constituent unit of the polyamide resin of the present invention.
  • a oxalic acid compound that provides a unit derived from oxalic acid, which is one type, is included.
  • the dicarboxylic acid compound include compounds derived from dicarboxylic acid, and examples of the compound derived from dicarboxylic acid include esters derived from dicarboxylic acid.
  • the oxalic acid compound used in the present invention 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.
  • succinic acid may be thermally decomposed when oxalic acid itself is used as a raw material. Therefore, the oxalic acid compound produced at a high polymerization temperature was derived from oxalic acid. Compounds are preferred.
  • oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction.
  • oxalic acid diesters examples include oxalic acid diesters of aliphatic monohydric alcohols, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols.
  • 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 oxalic acid diesters of aliphatic monohydric alcohols are preferred, di-n-butyl oxalate, di-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.
  • oxalic acid diesters of alicyclic alcohols examples include dicyclohexyl oxalate.
  • oxalic acid diesters of aromatic alcohols examples 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-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.
  • oxalic acid compounds can be added alone or in combination of two or more when the polyamide resin (A) is produced.
  • 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-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic 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.
  • dicarboxylic acid compounds other than these oxalic acid compounds can be added singly or in combination of two or more when the polyamide resin (A) is produced.
  • polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within the range where 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 acids and / or polycarboxylic acids other than oxalic acid compounds contained in the polyamide resin (A) is the same as the units derived from all dicarboxylic acids and all polyvalent carboxylic acids contained in the polyamide resin (A).
  • the total amount 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.
  • the diamine (b) used in the present invention contains two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
  • the diamine (b) includes 1,9-nonanediamine and 2-methyl-1,8-octanediamine (also referred to as C9 diamine), which are diamines having 9 carbon atoms. It is preferable to contain.
  • the content of units derived from 1,9-nonanediamine and 2-methyl-1,8-octanediamine contained in the polyamide resin (A), that is, the content of units derived from C9 diamine is contained in the polyamide resin (A).
  • it is preferably 1 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and 60 mol% or more. Is more preferably 80 mol% or more, and more preferably 90 mol% or more.
  • the diamine (b) preferably contains 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the melting point and thermal decomposition temperature (in nitrogen) of the polyamide resin (A). From the viewpoint of the balance between the 1% weight loss temperature of the polymer and other properties), 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8- contained in the polyamide resin (A)
  • the total content of octanediamine-derived units is preferably 10 mol% or more, more preferably 20 mol% or more, in the total amount of all diamine-derived units contained in the polyamide resin (A). , 40 mol% or more, more preferably 60 mol% or more, further preferably 80 mol% or more, 90 mol% More preferably a top.
  • the molar ratio of the sum of 1,9-nonanediamine and 2-methyl-1,8-octanediamine to 1,6-hexanediamine ie, the molar ratio of C9 diamine to 1,6-hexanediamine is 1,9 -Maintaining the excellent properties of polyamide (hereinafter, sometimes referred to as polyamide 92) formed by polymerizing nonanediamine, 2-methyl-1,8-octanediamine and oxalic acid compound, and in particular, melt moldability and low water absorption. From the viewpoint of increasing the melting point of the polyamide resin (A) without impairing it, and particularly improving the mechanical properties, it is preferably 1:99 to 99: 1.
  • the molar ratio of C9 diamine to 1,6-hexanediamine is more preferably 5.1: 94.9 to 99: 1, still more preferably 10:90 to 99: 1, and the melting point of the polyamide resin (A) From the viewpoint of facilitating polymerization and molding process (melt moldability), more preferably 20:80 to 99: 1, still more preferably 30:70 to 98: 2, and polyamide resin ( From the viewpoint of making the melting point of A) 280 ° C. or less and facilitating melt moldability, it is more preferably 30:70 to 90:10, further preferably 30:70 to 70:30.
  • the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of C9 diamine, which is a diamine having 9 carbon atoms, is 1:99 to from the viewpoint of increasing the molecular weight of the polyamide resin (A).
  • 99: 1 is preferable, 5:95 to 95: 5 is more preferable, 5:95 to 40:60 or 60:40 to 95: 5 is further preferable, and 5:95 to 30 is preferable.
  • 70 or 70:30 to 90:10 is more preferable.
  • diamines can be contained as long as the effects of the present invention are not impaired. Specifically, as other diamines other than 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1, 8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4 -Aliphatic diamines such as trimethyl-1,6-hexanediamine and 5-methyl-1,9-nonanediamine, cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine, p-phenylenediamine and m-phenylenediamine , P-xylenediamine, m-xylenediamine, 4,4
  • the content of other diamine-derived units is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50 mol% in all diamine-derived units of the polyamide resin (A). More preferably, it is 20 mol% or less, More preferably, it is 10 mol% or less, More preferably, it is 5 mol% or less, More preferably, it is 1 mol% or less.
  • the polyamide resin (A) used in the present invention can be produced using any method known as a method for producing polyamide.
  • the diamine (b) and the dicarboxylic acid (a) are produced by polycondensation reaction batchwise or continuously, and more preferably, the diamine (b) and the dicarboxylic acid (a ) 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.
  • Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then the diamine (b) and the dicarboxylic acid (a) are mixed.
  • a solvent in which both the diamine (b) and the dicarboxylic acid (a) are soluble may be used.
  • 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.
  • oxalic acid diester is added with respect to this.
  • the charging ratio of the diamine (b) and the dicarboxylic acid (a) is 0.8 to 1.5 (molar ratio) in terms of high molecular weight in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). ), Preferably 0.91 to 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).
  • the temperature inside the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling.
  • the reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C.
  • the reaction time at the final temperature is preferably 3 to 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 raising process, the final reached temperature of the pre-polycondensation step, that is, preferably 80 to 150 ° C., is finally preferably 295 to 350 ° C., more preferably 298 to 345 ° C., and more preferably 298 ° C. A temperature range of 340 ° C. or lower is reached.
  • polymerization can be performed under reduced pressure as necessary.
  • the preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.
  • (3-2) Pressurized polymerization method First, the diamine (b) is placed in a pressure-resistant vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, while maintaining the sealed pressure state at the reaction temperature, the dicarboxylic acid (a) is injected into the pressure resistant vessel to start the polycondensation reaction.
  • the reaction temperature is not particularly limited as long as the polyamide produced by the reaction of diamine (b) and dicarboxylic acid (a) can maintain a slurry or solution state and does not thermally decompose.
  • the charge ratio of the diamine (b) and the dicarboxylic acid (a) is 0.8 to 1.5 (molar ratio), preferably 0.91 in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). To 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).
  • the temperature is raised to a temperature not lower than the melting point of the polyamide resin (A) and not thermally decomposing while keeping the inside of the pressure vessel in a sealed pressure state.
  • a 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.
  • the preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.
  • Polyphenylene ether resin Specific examples of the polyphenylene ether resin used in the present invention include poly-1,4-phenylene ether, poly-2,6-dimethyl-1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene.
  • poly-2,6-dipropyl-1,4-phenylene ether poly-2-methyl-6-allyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly -2-Methyl-6-ethyl-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2 , 3,6-trimethyl-1,4-phenylene ether, poly-2,3,5,6-tetrafluoro-1,4 phenylene ether, poly-2,3 Diphenyl-1,4-phenylene ether, poly-2,3-ditolyl-1,4-phenylene ether, copolymer of 2,6-dimethylphenol and other phenols and the like. Of these, poly-2,6-dimethyl-1,4-phenylene ether is preferred.
  • the polyphenylene ether resin used in the present invention may be a modified polyphenylene ether or a mixture of an unmodified polyphenylene ether and a modified polyphenylene ether. From the viewpoint of affinity with the polyamide resin (A), a modified polyphenylene ether is preferable.
  • the production method of polyphenylene ether may be any known method and is not particularly limited.
  • the modified polyphenylene ether resin has a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, a carboxylic acid imide group, and a carboxylic acid amide group from the viewpoint of affinity with the polyamide resin (A). And / or an epoxy group, and more preferably at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, and an epoxy group.
  • the intrinsic viscosity of the polyphenylene ether resin used in the present invention is not particularly limited, but the intrinsic viscosity measured in chloroform at 30 ° C. is preferably 0.01 to 5 dl / g, preferably 0.1 to 4.5 dl. / G is more preferable.
  • the content of the polyphenylene ether resin is less than 60% by mass, preferably 56% by mass, based on the total amount of the polyamide resin (A) and the polyphenylene ether resin, from the viewpoints of heat resistance and moldability. % Or less, and more preferably 51% by mass or less.
  • the total content of the polyamide resin (A) and the polyphenylene ether resin is preferably 50% by mass or more, and 70% by mass in the total amount of the resin composition from the viewpoint of maintaining the effects of the respective resins and the effects of the present invention. % Or more is more preferable, and 90 mass% or more is more preferable.
  • the resin composition of the present invention may contain other polymers as long as the effects of the present invention are not impaired.
  • other polymers include other polyamides such as polyoxamides other than polyamide resin (A), aromatic polyamides, aliphatic polyamides, alicyclic polyamides, and thermoplastic polymers other than polyamides and polyphenylene ethers.
  • the content of the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but in the resin composition of the present invention, the total is preferably less than 50% by mass, more preferably 30% by mass or less. Preferably, 10 mass% or less is more preferable.
  • the resin composition of the present invention, the polyamide resin (A) and polyphenylene ether used in the present invention can contain other additives as long as the effects of the present invention are not impaired.
  • additives for example, pigments, dyes, colorants, heat-resistant agents, antioxidants, weathering agents, ultraviolet absorbers, light stabilizers, compatibilizers, lubricants, crystal nucleating materials, crystallization accelerators, mold release agents.
  • examples thereof include an antistatic agent, a plasticizer, an antistatic agent, a flame retardant, glass fiber, a lubricant, a filler, and a reinforcing fiber.
  • These additives can be contained alone or in combination of two or more.
  • the content is not particularly limited as long as it does not impair the effects of the present invention, but in the resin composition of the present invention, the total content is preferably 50% by mass or less, more preferably 30% by mass or less. A mass% or less is more preferable.
  • a copper-containing compound is preferable, and among them, copper halides such as copper iodide and copper bromide are preferable.
  • the content of the copper-containing compound is preferably 10 to 1000 ppm in the resin composition of the present invention.
  • an alkyl halogen compound is further added as a secondary antioxidant.
  • antioxidants examples include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants, and one or more of them can be contained in the resin composition of the present invention.
  • phenolic antioxidants include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, N, N′-hexamethylenebis (3,5- Di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Til-4-hydroxybenzyl) benzene, 3,9-bis [2- ⁇ 3-
  • Examples of the phosphorus-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphine 6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [ d, f] [1,3,2] dioxaphosphine 6-yl] oxy] -ethyl] ethanamine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc.
  • Sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (dodecylthio) propionate] methane 1 type, or 2 or more types can be contained in the resin composition of the present invention.
  • Compatibilizers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, citric acid, fumaric 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 carboxylic acid metal salts thereof, monomethyl maleate, monomethyl itaconate, methyl acrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicar
  • the method for adding the other polymer and the additive is not particularly limited as long as each of them can be dispersed in the polyamide-based resin, and at any point that does not impair the effect, the polyamide resin ( A) can be added.
  • other polymers and additives can be added to the prepolymerization step and / or postpolymerization step of the polyamide resin (A), and can be added to the polyphenylene ether (B). It can also be added before, during and after production of the resin composition of the invention.
  • the production method of the resin composition of the present invention is not particularly limited as long as it contains the polyamide resin (A) and the polyphenylene ether resin.
  • Examples thereof include a production method by melt kneading such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder, and a kneader.
  • a production method by melt kneading is preferred, and among them, production using a twin screw extruder from the viewpoint of fluidity during kneading of the resin composition of the present invention. Is more preferable.
  • the resin composition of the present invention can be molded into various molded products by known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding, and press molding. It is particularly useful in the fields of injection molding and blow molding.
  • the resin composition of the present invention has a wide moldable temperature range and has a low dielectric constant and dielectric loss tangent, it is suitably used for, for example, antennas, ETCs, wireless LANs and mobile phones used in high frequency ranges. it can.
  • the resin composition of the present invention has excellent properties inherently possessed by the polyamide resin and polyphenylene ether in a well-balanced manner and has excellent heat resistance, it can be used for automobile parts, industrial materials, industrial materials, machinery. It can be usefully used for parts, office equipment parts, household goods, sheets, films, fibers and the like.
  • composition of this invention is a composition containing the polyamide resin and glass fiber which used the specific raw material.
  • 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.
  • 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.
  • oxalic acid may be thermally decomposed. Derived compounds are preferred.
  • oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction.
  • oxalic acid diesters examples include oxalic acid diesters of aliphatic monohydric alcohols, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols.
  • 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 oxalic acid diesters of aliphatic monohydric alcohols are preferred, di-n-butyl oxalate, di-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.
  • oxalic acid diesters of alicyclic alcohols examples include dicyclohexyl oxalate.
  • oxalic acid diesters of aromatic alcohols examples 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-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.
  • oxalic acid compounds can be added alone or in combination of two or more during the production of a polyamide resin using the oxalic acid compound as a raw material.
  • dicarboxylic acid compounds other than oxalic acid compounds can be used as raw materials for the polyamide resin using oxalic acid compounds as raw materials.
  • 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-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic 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.
  • dicarboxylic acid compounds other than these oxalic acid compounds can be added singly or in combination of two or more when the polyamide resin is produced.
  • polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within the range where 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 made from the oxalic acid compound 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 phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenylether.
  • the melting point and thermal decomposition temperature of the obtained polyamide resin 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 oxalic acid compound as a raw material, More preferably, it is 5:95 to 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 the units derived from all diamines of the polyamide resin starting from the oxalic acid compound. Is 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and more preferably 99 mol% or more.
  • 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 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 1 mass% of polyamide resin at a temperature of 25 ° C. according to 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.
  • 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 charging ratio of the dicarboxylic compound containing the diamine and the oxalic acid compound is 0.8 to 1.5 (molar ratio) in terms of the high molecular weight in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b).
  • the ratio is preferably 0.91 to 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).
  • the temperature inside the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling.
  • the reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C.
  • the reaction time at the final temperature reached is 3-6 hours.
  • (Ii) Post-polycondensation step In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature raising process, the final ultimate temperature of the pre-polycondensation step, that is, preferably 80 to 150 ° C., is finally preferably 150 to 350 ° C., more preferably 180 to 330 ° C., and further preferably 200 ° C. A temperature range of 320 ° C. or lower is reached.
  • polymerization can be performed under reduced pressure as necessary.
  • the preferable final pressure in the case of carrying out 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-resistant 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).
  • the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed.
  • a temperature not lower than the melting point of the polyamide resin 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.
  • the preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.
  • 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.
  • 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 ⁇ m or more and 13 ⁇ m or less and outside the range of 3 ⁇ m or more and 13 ⁇ m 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 ⁇ m or more and 12 ⁇ m or less is preferable, and 6 ⁇ m or more and 11 ⁇ m 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.
  • a surface treatment agent examples include silane compounds, chromium compounds, titanium compounds, and the like, and surface treatment agents of silane compounds and / or titanium compounds are preferable.
  • an aminosilane coupling agent excellent in adhesion to the sizing agent is preferable.
  • Surface treatment agents for titanium compounds include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl titanate, tetraisopropyl titanate, 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
  • composition of this invention contains the polyamide resin which uses an oxalic acid compound as a raw material, and a specific glass fiber.
  • 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.
  • 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.
  • 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 is preferably 2 to 4:40 to 60: 1 to 3. It is more preferably 5 to 3.5: 45 to 55: 1.5 to 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.
  • 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.
  • 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.
  • a thermoplastic resin other than the polyamide resin a high-density polyethylene (HDPE) can be used.
  • HDPE high-density polyethylene
  • MDPE Medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • UHMWPE ultra high molecular weight polyethylene
  • PP polypropylene
  • EPR ethylene / propylene copolymer
  • EBR butene copolymer
  • 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 2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5 -Compounds containing functional groups such as epoxy groups such
  • the production method of the composition of the present invention is not particularly limited, and usually the following production 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
  • composition of the present invention is preferably used for slidable parts because it has low dimensional stability, coefficient of friction, and wear during actual use.
  • 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.
  • an injection molded product is preferable.
  • sliding parts are preferable, and among the sliding parts, one type selected from the group consisting of gears, pulleys, cams and bearings is preferable.
  • Molding and measurement were performed by the following methods.
  • Relative viscosity ( ⁇ r) The relative viscosity was measured at 25 ° C. with an Oswald viscometer using a solution in which the solvent was 96% by mass sulfuric acid and the polyamide resin concentration was 1.0 g / dl.
  • test piece The obtained resin composition was put into an injection molding machine, and a test piece was prepared at a resin temperature of 300 ° C and a mold temperature of 95 ° C.
  • the dimensions of the test piece were 128 mm ⁇ 12.7 mm ⁇ 6.2 mm for the test specimen for measuring the deflection temperature under load, 100 mm ⁇ 30 mm ⁇ 1 mm for the test piece for measuring water absorption, and 80 mm ⁇ 80 mm ⁇ for the test piece for electrical characteristics. 3 mm.
  • the string-like PA92 was immediately cooled with water and pelletized by a pelletizer.
  • the relative viscosity was 3.13.
  • 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%
  • the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 83:17 to 86:14.
  • the temperature inside the system was increased. After the internal temperature was raised to 170 ° C. over about 1 hour, 30.2 kg (149 mol) of dibutyl oxalate of dicarboxylic acid (a) was supplied into the reaction vessel at a flow rate of 1.49 L / min with 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 generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 190 ° C. Thereafter, the temperature was raised to 250 ° C. Meanwhile, the internal pressure was adjusted to 0.5 MPaG while the generated butanol was extracted from the pressure release port.
  • the string-like PA92 / 62 was immediately cooled with water and pelletized by a pelletizer.
  • the relative viscosity was 2.78.
  • the content of the unit derived from oxalic acid compound is 100 mol%, and in the total amount of units derived from all diamine (b)
  • the total content of units derived from 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,6-hexamethylenediamine is 100 mol%, and 1,9-nonanediamine,
  • the weight ratio of -methyl-1,8-octanediamine and 1,6-hexamethylenediamine is 50: 8.8: 41.2 to 52: 9.2: 38.8.
  • the polyphenylene ether resin is a polyphenylene ether modified with fumaric acid, Zarek (registered trademark) CX-1 (hereinafter also referred to as fumaric acid-modified PPE) manufactured by Idemitsu Kosan Co., Ltd. Was used.
  • Example 1 70 mass% of PA92 and 30 mass% of fumaric acid-modified PPE are fed to a twin screw extruder, melt-kneaded under conditions of a cylinder temperature of 300 ° C., extruded as a strand, cooled and solidified, and then put into a pelletizer. To obtain a pellet-shaped resin composition. The pellet of the obtained resin composition was dried. Test pieces of dried pellets were prepared, and the deflection temperature under load, impact strength, saturated water absorption, dielectric constant, and dielectric loss tangent were measured. The results are shown in Table 1.
  • Example 2 The procedure was the same as Example 1 except that PA92 was changed to 50% by mass and fumaric acid-modified PPE was changed to 50% by mass. The results are shown in Table 1.
  • Example 3 Example 1 was repeated except that PA92 / 62 was used instead of PA92. The results are shown in Table 1.
  • Example 4 Example 2 was repeated except that PA92 / 62 was used instead of PA92. The results are shown in Table 1. The results are shown in Table 1.
  • Example 4 The same procedure as in Example 1 was carried out except that polyamide 66 manufactured by Ube Industries, Ltd. instead of PA92 and 2020B (hereinafter also referred to as PA66) was used and kneaded at a cylinder temperature of 290 ° C. The results are shown in Table 1.
  • 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.
  • the internal pressure was adjusted to 1.0 MPaG while extracting the generated butanol from the pressure release port.
  • 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.
  • 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.
  • 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 to 86:14.
  • Polyamide resins other than polyamide resins made from oxalic acid compounds Polyamide 66
  • Polyamide 66 PA66-1) (hereinafter sometimes referred to as (PA66-1))
  • 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))
  • Examples 1 and 2 Comparative Examples 1 and 2
  • the polyamide resin and glass fiber described in Table 2 were kneaded by a 44 mm ⁇ vented twin-screw extruder set at a barrel temperature of 260 ° C. at the ratio described in Table 2, pelletized by a pelletizer, and the composition pellets were Obtained.
  • 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 2.
  • composition containing polyamide resin and glass fiber made from an oxalic acid compound is excellent in dimensional stability and wear resistance.
  • the resin composition containing the polyamide resin and the polyphenylene ether resin of the first invention has low water absorption, excellent heat resistance and molding processability, and low dielectric constant and dielectric loss tangent. .
  • the resin composition of the present invention can be used in a wide range of fields such as electric / electronic parts, OA parts, vehicle parts, and machine parts.
  • the composition of 2nd invention can be used conveniently as various sliding members, such as a motor vehicle, an electric / electronic, an industrial material, an industrial material, daily necessities, and household goods.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

Selon un premier aspect, cette invention concerne une composition de résine qui contient une résine polyamide (A) et une résine poly(éther de phénylène). La résine polyamide (A) contient un motif dérivé d'un acide dicarboxylique (a) et un motif dérivé d'une diamine (b), l'acide dicarboxylique (a) contient un composé d'acide oxalique, la diamine (b) contient deux diamines ou plus choisies dans le groupe constitué par la 1,6-hexanediamine, la 1,9-nonane- diamine et la 2-méthyl-1,8-octanediamine, et la teneur en résine poly(éther de phénylène) est inférieure à 60 % en poids sur la base de la quantité totale de la résine polyamide (A) et de la résine poly(éther de phénylène). Selon un second aspect, cette invention concerne une composition pour composant glissant, et la composition contient une résine polyamide et des fibres de verre, et est caractérisée en ce que la résine polyamide contient une résine polyamide obtenue par utilisation d'un composé d'acide oxalique comme matière première.
PCT/JP2012/008164 2012-01-18 2012-12-20 Composition de résine, et composition contenant une résine polyamide et des fibres de verre WO2013108344A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2012007596 2012-01-18
JP2012-007596 2012-01-18
JP2012-118496 2012-05-24
JP2012118496A JP2013245258A (ja) 2012-05-24 2012-05-24 ポリアミド樹脂とガラス繊維を含む組成物
JP2012-268975 2012-12-10
JP2012268975A JP2013166916A (ja) 2012-01-18 2012-12-10 樹脂組成物

Publications (1)

Publication Number Publication Date
WO2013108344A1 true WO2013108344A1 (fr) 2013-07-25

Family

ID=48798797

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/008164 WO2013108344A1 (fr) 2012-01-18 2012-12-20 Composition de résine, et composition contenant une résine polyamide et des fibres de verre

Country Status (1)

Country Link
WO (1) WO2013108344A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108034242A (zh) * 2017-12-27 2018-05-15 南京鸿瑞塑料制品有限公司 一种玻纤增强高耐磨pa66/ppo复合材料及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009151145A1 (fr) * 2008-06-10 2009-12-17 宇部興産株式会社 Nouvelle composition de résine de polyamide et produit contenant de la résine de polyamide
WO2011013536A1 (fr) * 2009-07-27 2011-02-03 Ntn株式会社 Palier d'arbre rotatif et dispositif de support de section rotative d'une eolienne
WO2011016535A1 (fr) * 2009-08-07 2011-02-10 宇部興産株式会社 Composition de résine polyamide conductrice
JP2011063695A (ja) * 2009-09-16 2011-03-31 Ube Industries Ltd ポリアミド樹脂を用いた透明部材
JP2011116889A (ja) * 2009-12-04 2011-06-16 Ube Industries Ltd Ｓｍｔコネクタ用ポリアミド樹脂組成物
WO2011111713A1 (fr) * 2010-03-08 2011-09-15 宇部興産株式会社 Composition de résine de polyamide
JP2011231167A (ja) * 2010-04-26 2011-11-17 Ube Industries Ltd 熱処理による密度変化が小さい自動車部品又は電気・電子部品用ポリアミド樹脂

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009151145A1 (fr) * 2008-06-10 2009-12-17 宇部興産株式会社 Nouvelle composition de résine de polyamide et produit contenant de la résine de polyamide
WO2011013536A1 (fr) * 2009-07-27 2011-02-03 Ntn株式会社 Palier d'arbre rotatif et dispositif de support de section rotative d'une eolienne
WO2011016535A1 (fr) * 2009-08-07 2011-02-10 宇部興産株式会社 Composition de résine polyamide conductrice
JP2011063695A (ja) * 2009-09-16 2011-03-31 Ube Industries Ltd ポリアミド樹脂を用いた透明部材
JP2011116889A (ja) * 2009-12-04 2011-06-16 Ube Industries Ltd Ｓｍｔコネクタ用ポリアミド樹脂組成物
WO2011111713A1 (fr) * 2010-03-08 2011-09-15 宇部興産株式会社 Composition de résine de polyamide
JP2011231167A (ja) * 2010-04-26 2011-11-17 Ube Industries Ltd 熱処理による密度変化が小さい自動車部品又は電気・電子部品用ポリアミド樹脂

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108034242A (zh) * 2017-12-27 2018-05-15 南京鸿瑞塑料制品有限公司 一种玻纤增强高耐磨pa66/ppo复合材料及其制备方法

Similar Documents

Publication Publication Date Title
US6884485B2 (en) Molding composition based on polyetheramides
CN111448257B (zh) 聚酰胺树脂组合物
TWI804479B (zh) 聚醯胺樹脂組成物、成形品及聚醯胺樹脂丸粒之製造方法
WO2014109300A1 (fr) Composition polyamide, et article moulé
CN110964316B (zh) 聚酰胺组合物、成型品和半芳香族聚酰胺
WO2016002682A1 (fr) Composition de résine de polyamide et article moulé comprenant cette dernière
WO2012043640A1 (fr) Composition de résine de polyamide et objet moulé la comprenant
JP2013028798A (ja) ポリアミド樹脂組成物およびそれを成形してなる成形体
JP2015155543A (ja) プラスチック容器および導管
JP6369608B2 (ja) ガラス繊維強化ポリアミド樹脂組成物
CN112313288B (zh) 树脂组合物和成型品
WO2013108344A1 (fr) Composition de résine, et composition contenant une résine polyamide et des fibres de verre
JP6843698B2 (ja) ポリアミド組成物及び成形品
JP2019178261A (ja) ポリアミド組成物及び成形品
JP2019026670A (ja) ポリアミド組成物および成形品
KR102208253B1 (ko) 박육 제품 사출성형용 폴리아미드 수지 조성물 및 이의 성형품
JP2013095777A (ja) プリント基板表面実装部品用ポリアミド樹脂組成物及びそれを成形して得たプリント基板表面実装部品
JP2013166916A (ja) 樹脂組成物
KR20200120703A (ko) 액체 보조 사출 성형 응용분야를 위한 폴리아미드 조성물
JP2019127500A (ja) ポリアミド組成物及び成形品
JP2015000966A (ja) ポリアミド樹脂組成物及びそれを用いて製造される成形品
JP7223159B2 (ja) 強化樹脂組成物、成形品及び高温時引張強度の向上方法
JP2013245258A (ja) ポリアミド樹脂とガラス繊維を含む組成物
WO2023037937A1 (fr) Composition de résine de polyamide
JP2022051850A (ja) ポリアミド組成物及び成形品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12865624

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12865624

Country of ref document: EP

Kind code of ref document: A1