WO2012070598A1 - Composition de résine polyamide - Google Patents

Composition de résine polyamide Download PDF

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Publication number
WO2012070598A1
WO2012070598A1 PCT/JP2011/076977 JP2011076977W WO2012070598A1 WO 2012070598 A1 WO2012070598 A1 WO 2012070598A1 JP 2011076977 W JP2011076977 W JP 2011076977W WO 2012070598 A1 WO2012070598 A1 WO 2012070598A1
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WIPO (PCT)
Prior art keywords
resin
nylon
resin composition
flame retardant
composition
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PCT/JP2011/076977
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English (en)
Japanese (ja)
Inventor
洋平 椛島
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ユニチカ株式会社
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Priority to JP2012545777A priority Critical patent/JPWO2012070598A1/ja
Publication of WO2012070598A1 publication Critical patent/WO2012070598A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • the present invention is a resin composition mainly comprising a polyamide resin containing a plant-derived polyamide resin and containing a flame retardant and / or glass fiber, and particularly, for electrical / electronic parts, automotive parts, etc.
  • the present invention relates to a polyamide resin composition that can be suitably used as a component material.
  • PC polycarbonate
  • ABS acrylonitrile-butadiene-styrene copolymer
  • nylon 11 resin and / or nylon 1010 resin is used as the polyamide resin that is excellent in impact resistance and manufactured from plant-derived raw materials.
  • a polyamide resin composition containing glass fibers having an effect of improving impact properties and rigidity has been proposed (see Patent Document 1).
  • the glass fiber may be raised on the surface of the molded product when it is molded, which results in poor light reflection on the surface of the molded product, resulting in poor surface appearance. There was a problem of becoming.
  • the present invention solves the problems as described above, and is a resin composition using plant-derived materials in consideration of the environment, and has excellent impact resistance and rigidity, and has excellent surface appearance. It is a technical problem to provide a polyamide resin composition that can be used for casing parts of electronic devices typified by notebook computers, mobile phones, and OA devices. Is.
  • the gist of the present invention is the following (1) to (4).
  • a resin composition comprising a nylon 11 resin and / or a nylon 1010 resin (A1), a nylon 6 resin (A2), and a phosphorus flame retardant containing no halogen element (B), Phosphorus flame retardant (B) having a mass ratio (A1: A2) of nylon 11 resin and / or nylon 1010 resin (A1) to nylon 6 resin (A2) of 1: 4 to 4: 1 and containing no halogen element Of nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2) is 15 to 60 parts by mass with respect to the total amount of 100 parts by mass of nylon 6 resin (A2).
  • (2) A resin composition comprising nylon 11 resin and / or nylon 1010 resin (A1), nylon 6 resin (A2), and glass fiber (C), wherein the nylon 11 resin and / or nylon
  • the mass ratio (A1: A2) of the 1010 resin (A1) and the nylon 6 resin (A2) is 1: 4 to 4: 1, and the glass fiber (C) content is nylon 11 resin and / or nylon 1010 resin.
  • the total amount of (A1) and nylon 6 resin (A2) is 20 to 180 parts by mass, and the melt viscosity of nylon 6 resin (A2) is 5 to 170 Pa ⁇ s.
  • Polyamide resin composition is 20 to 180 parts by mass, and the melt viscosity of nylon 6 resin (A2) is 5 to 170 Pa ⁇ s.
  • a phosphorus flame retardant (B) containing no halogen element is contained, and the content of the phosphorus flame retardant (B) containing no halogen element is such that the nylon 11 resin and / or the nylon 1010 resin (A1 ) And nylon 6 resin (A2) in a total amount of 100 parts by mass, the polyamide resin composition according to (2), which is 15 to 60 parts by mass.
  • a hindered phenolic antioxidant (D) is further contained, and the content of the hindered phenolic antioxidant (D) is nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6
  • the polyamide resin composition as described in (1) or (3) which is 0.05 to 3.0 parts by mass with respect to 100 parts by mass of the total amount of the resin (A2).
  • the polyamide resin component which is the main component of the polyamide resin composition of the present invention uses nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2) having a specific range of melt viscosity at a specific ratio. Therefore, the resin composition containing these is excellent in compatibility, excellent in fluidity, and can provide a molded product excellent in impact resistance. Further, the polyamide resin of the present invention contains a phosphorous flame retardant (B) containing no halogen element in a polyamide resin component comprising nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2).
  • the main polyamide resin component is excellent in fluidity, the dispersibility of the flame retardant (B) is excellent, and the effect of the flame retardant (B) is sufficiently exhibited. For this reason, the content of the flame retardant (B) can be relatively reduced, and by suppressing the thermal decomposition of the flame retardant (B) during molding, the generation of gas is reduced and the surface appearance is excellent. A molded product can be obtained.
  • the polyamide resin composition of the present invention containing glass fiber (C) in the polyamide resin component comprising nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2) is the main component. Since the polyamide resin component is excellent in fluidity, the dispersibility of the glass fiber (C) is excellent.
  • the polyamide resin composition of the present invention containing the flame retardant (B), when the hindered phenol-based antioxidant (D) is contained, the generation of gas at the time of extrusion or molding can be reduced, Furthermore, it becomes possible to prevent surface contamination of the obtained molded product.
  • the polyamide resin composition of the present invention is excellent in rigidity, excellent in flame retardancy and impact resistance, and can provide a molded product excellent in surface appearance. For this reason, it can be suitably used for a housing part of an electronic device represented by a personal computer, a mobile phone, an electronic dictionary, an OA device, and the like.
  • the polyamide resin composition of the present invention is a resin composition comprising a polyamide resin component and a phosphorus-based flame retardant (B) containing no halogen element (hereinafter sometimes referred to as composition 1), and A resin composition containing a polyamide resin component and glass fibers (C) (hereinafter sometimes referred to as composition 2).
  • the polyamide resin component which becomes a main component in the composition 1 and the composition 2 of this invention contains nylon 11 resin and / or nylon 1010 resin (A1), and nylon 6 resin (A2).
  • nylon 11 resin and / or nylon 1010 resin (A1) will be described.
  • the nylon 11 resin include those obtained by polycondensing 11-aminoundecanoic acid using ricinoleic acid in natural castor oil as a raw material.
  • the production method is not particularly limited, and the nylon 11 resin can be produced according to a known method, and various catalysts, heat stabilizers and other additives may be used during the production.
  • Examples of commercially available nylon 11 resins include “Rilsan BESN” manufactured by Arkema.
  • nylon 1010 resin natural castor oil is used as a raw material, and sebacic acid and decamethylenediamine are polycondensed.
  • the nylon 1010 resin used in the present invention desirably has a biomass carbon content of 50% or more measured in accordance with ASTM (D6866) in consideration of environmental load.
  • Nylon 11 resin and nylon 1010 resin are excellent in flexibility, and by using these resins, a resin composition excellent in impact resistance can be obtained.
  • the melt viscosity of nylon 11 resin or nylon 1010 resin is preferably in the range of 500 to 5000 Pa ⁇ s. If it is this range, compatibility with nylon 6 resin (B2) will become favorable, and it has the outstanding characteristic of both resin, and can obtain the molded article excellent in impact resistance.
  • nylon 6 resin (A2) is obtained by ring-opening polymerization of caprolactam, and its production method is not particularly limited, and can be performed according to a known method. Moreover, you may use additives, such as various catalysts and a heat stabilizer, in the case of the manufacture.
  • Nylon 6 resin (A2) is a resin having excellent rigidity. For this reason, the resin composition obtained by mixing nylon 11 resin and / or nylon 1010 resin (A1) with nylon 6 resin (A2) is also excellent in rigidity. Specifically, a resin composition having a high bending elastic modulus and bending strength can be obtained.
  • Nylon 6 resin (A2) needs to have a melt viscosity of 5 to 170 Pa ⁇ s, and preferably 10 to 50 Pa ⁇ s.
  • the melt viscosity of the nylon 6 resin (A2) exceeds 170 Pa ⁇ s, the fluidity of the resulting resin composition decreases, and in the case of the composition 1, the dispersibility of the flame retardant (B) decreases, and the flame retardant The effect of (B) cannot be exhibited sufficiently.
  • the dispersibility of the glass fiber (C) is lowered, and it becomes difficult to suppress breakage of the glass fiber and floating on the surface, and the impact resistance is lowered.
  • melt viscosity of the nylon 6 resin (A2) is less than 5 Pa ⁇ s, the molecular weight of the nylon 6 resin (A2) becomes too low, and the resulting resin composition has low rigidity, and the flexural modulus and The bending strength is low.
  • the mass ratio (A1: A2) of the nylon 11 resin and / or nylon 1010 resin (A1) to the nylon 6 resin (A2) needs to be 1: 4 to 4: 1, among which 1: 3 to 3 Is preferably 1: 1, and more preferably 1: 2 to 2: 1.
  • the resin composition obtained is ( A1) and (A2) are mixed with good compatibility and excellent in fluidity. Therefore, the polyamide resin composition of the present invention has excellent characteristics of both resins by mixing (A1) and (A2) with good compatibility even in the polyamide resin component as the main component alone, A molded product excellent in impact resistance and rigidity can be obtained.
  • the amount of nylon 11 resin and / or nylon 1010 resin (A1) is less than the above range, the amount of plant-derived components decreases, so that an environmentally friendly resin composition cannot be obtained, and impact resistance is high. It will be inferior.
  • the amount of the nylon 6 resin (A2) is less than the above range, the resin composition has low rigidity, and the bending elastic modulus and bending strength are low.
  • the polyamide resin component which is the main component in the composition 1 and the composition 2 of the present invention may contain an amorphous polyamide resin (A3) in addition to the above (A1) and (A2).
  • amorphous polyamide resin (A3) polycondensate of isophthalic acid / terephthalic acid / hexamethylenediamine, polycondensate of isophthalic acid / terephthalic acid / hexamethylenediamine / bis (3-methyl-4-aminocyclohexyl) methane Or a polycondensate of terephthalic acid / 2,2,4-trimethylhexamethylenediamine / 2,4,4-trimethylhexamethylenediamine, or isophthalic acid / terephthalic acid / hexamethylenediamine / bis (3-methyl-4- Aminocyclohexyl) methane polycondensate and terephthalic acid / 2,2,4-trimethylhex
  • amorphous polyamide resins ( A3) can also be used in combination of two or more.
  • preferred is a polycondensate of isophthalic acid / terephthalic acid / hexamethylenediamine, a polycondensate of isophthalic acid / terephthalic acid / hexamethylenediamine / bis (3-methyl-4-aminocyclohexyl) methane, or a mixture thereof.
  • the heat resistance of the resin composition can be improved and the processability can be improved.
  • the glass transition temperature of the amorphous polyamide resin (A3) is preferably 80 to 200 ° C., and more preferably 110 to 170 ° C. If the glass transition temperature is less than 80 ° C., the polyamide resin composition is solidified when it is molded, so that a mold release failure occurs or a molding cycle becomes long, which is not preferable.
  • the glass transition temperature exceeds 200 ° C.
  • the polyamide resin composition when the polyamide resin composition is molded, solidification is too early and appearance defects such as sink marks and glass floatation are likely to occur, and the melt viscosity at the time of kneading is high. Therefore, uniform kneading becomes difficult, which is not preferable.
  • the dispersibility of the glass fiber (C) in the resin composition is further improved by containing the amorphous polyamide resin (A3), and molding. It is possible to prevent the glass fiber from floating on the surface of the molded product when it is made into a product, and it is possible to obtain a molded product superior in surface gloss.
  • the total mass of the nylon 11 resin and / or the nylon 1010 resin (A1) and the nylon 6 resin (A2) and the mass ratio of the amorphous polyamide resin (A3) [(A1 + A2 ) :( A3)] is preferably 7: 3 to 9: 1.
  • the amount of the amorphous polyamide resin (A3) is larger than the above range, the crystallinity of the resin composition is lowered, so that the molding cycle in injection molding or the like may be extended to lower the productivity.
  • Amorphous polyamides generally have a high glass transition temperature, so that molded articles with excellent surface gloss may not be obtained unless they are molded with a high-temperature mold.
  • the amount of the amorphous polyamide resin (A3) is less than the above range, the effect of improving the surface gloss as described above is poor.
  • the composition 1 is a resin composition comprising the polyamide resin component as described above and a phosphorus-based flame retardant (B) that does not contain a halogen element.
  • the content of the phosphorus-based flame retardant (B) containing no halogen element is 15 to 60 masses with respect to 100 mass parts of the total amount of nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2). Part of which is preferably 20 to 55 parts by weight, more preferably 30 to 50 parts by weight.
  • the content of the flame retardant (B) is less than 15 parts by mass, sufficient flame retardancy cannot be imparted.
  • content of a flame retardant (B) exceeds 60 mass parts the operativity at the time of extrusion will fall, or the intensity
  • the flame retardant (B) Since the polyamide resin component containing the nylon 11 resin and / or the nylon 1010 resin (A1) and the nylon 6 resin (A2) is excellent in fluidity, the flame retardant (B) has good dispersibility in the polyamide resin component. It is excellent and can fully exert the effect of the flame retardant. For this reason, even if there is little content of a flame retardant (B), sufficient flame retardance can be provided. When the content of the flame retardant (B) is small, a resin composition excellent in flame retardancy is obtained without reducing the operability during kneading and without reducing the mechanical properties of the resin composition. Can do.
  • the flame retardant contained in the composition 1 needs to be a phosphorus-based flame retardant (B) not containing a halogen element.
  • B phosphorus-based flame retardant
  • the flame retardancy is not sufficiently improved, and the physical properties are reduced. Defects in surface appearance are likely to occur when processed into a molded body.
  • Examples of the phosphorus-based flame retardant (B) that does not contain a halogen element include phosphinates and diphosphinates and polymers thereof, melamine polyphosphate, red phosphorus, phosphate ester, condensed phosphate ester, and phosphazene compound. .
  • diphosphinic acid salts and phosphinic acid salts are preferably used from the viewpoints of stability during processing, dispersibility in kneading with a resin, and flame retardant effect, and phosphinic acid salts are particularly preferable.
  • Diphosphinic acid suitable as a component of diphosphinate includes methandi (methylphosphinic acid), benzene-1,4-di (methylphosphinic acid) and the like, and metal components include calcium ion, magnesium ion, aluminum Examples thereof include metal carbonates, metal hydroxides or metal oxides containing ions and / or zinc ions.
  • diphosphinic acid salt examples include, for example, methanedi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4-di (Methylphosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, benzene-1,4-di (methylphosphinic acid) zinc Methanedi (methylphosphinic acid) aluminum and methanedi (methylphosphinic acid) zinc are preferable.
  • Phosphinates are also produced in aqueous solutions using phosphinic acid and metal carbonates, metal hydroxides or metal oxides and are essentially present as monomers, but depending on the reaction conditions, condensation It may also exist in the form of a polymeric phosphinate having a degree of 1-3.
  • Phosphinic acid suitable as a component of the phosphinic acid salt includes dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, isobutylmethylphosphinic acid, octylmethylphosphinic acid, methylphenylphosphinic acid and Diphenylphosphinic acid etc. are mentioned, Preferably diethyl phosphinic acid is mentioned.
  • the metal component include metal carbonates, metal hydroxides or metal oxides containing calcium ions, magnesium ions, aluminum ions and / or zinc ions.
  • phosphinates include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethyl Zinc methylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinic acid
  • Magnesium phosphate aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphin
  • aluminum diethylphosphinate, zinc diethylphosphinate, and more preferably aluminum diethylphosphinate are particularly preferably used.
  • Clariant's Exolit OP1230, Exolit OP1311, Exolit OP1312, and Exolit OP1314 can be suitably used.
  • melamine polyphosphate or melamine cyanurate may be blended.
  • melamine polyphosphate or melamine cyanurate in combination, an expansion layer is formed on the surface of the material when the material is burned, so that the heat insulation effect is improved.
  • the effect of preventing the diffusion of combustible low-molecular substances generated during combustion is also improved. These effects lead to the effect of improving the flame retardancy with a small addition amount and shortening the combustion time.
  • the blending ratio of melamine polyphosphate or melamine cyanurate is preferably 10 to 30% by mass in the flame retardant.
  • the melamine polyphosphate is a general term for a melamine phosphate condensate, and examples thereof include melamine pyrophosphate, melamine triphosphate, and melamine tetraphosphate, or a mixture thereof.
  • Commercial products of melamine polyphosphate include Melapur 200/70 manufactured by Ciba Specialty Chemicals, PMP-100 manufactured by Nissan Chemicals, and the like.
  • Melamine cyanurate is an equimolar reaction product of melamine and cyanuric acid.
  • an aqueous solution of cyanuric acid and an aqueous solution of melamine are mixed, and the precipitate formed under stirring at a temperature of 90 to 100 ° C. is filtered. It is a white fine powder obtained.
  • the purity of melamine cyanurate is lowered, the effect as a flame retardant is lowered, so that the purity is 99% by mass or more.
  • MC-50 purity 99.4 mass%) manufactured by DSM
  • MC440 purity 99.8 mass%) manufactured by Nissan Chemical Co., Ltd.
  • MC25 manufactured by Ciba Specialty Chemicals
  • the phosphorus-based flame retardant (B) containing no halogen element as described above, it is preferable to use a powdery one having an average particle diameter (D50) of 100 ⁇ m or less, preferably 50 ⁇ m or less.
  • D50 average particle diameter
  • the particle size in the present invention is defined as the particle size value when the mass accumulation is 50% when the particle size distribution is measured using a particle size distribution measuring device such as a laser scattering particle size distribution meter. .
  • composition 2 is a resin composition comprising the polyamide resin component as described above and glass fiber (C).
  • glass fiber (C) contains (A1) and (A2) It is contained with good dispersibility in the polyamide resin component. For this reason, the impact resistance and the improvement effect of rigidity by including glass fiber become more remarkable. Furthermore, since the breakage of the glass fiber and the float on the surface during molding can be suppressed, a molded product having an excellent surface appearance can be obtained.
  • the glass fiber (C) content needs to be 20 to 180 parts by mass with respect to 100 parts by mass of the total amount of nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2). In particular, the amount is preferably 50 to 150 parts by mass.
  • the content of glass fiber (C) is less than 20 parts by mass, the effect of improving impact resistance and rigidity is inferior.
  • content of glass fiber (C) exceeds 180 mass parts, the dispersion state in a resin composition will fall and it will become difficult to obtain resin composition itself. Moreover, even if it is obtained, when formed into a molded product, the glass fiber floats on the surface of the molded product, resulting in a molded product having a poor surface appearance.
  • vertically with respect to the longitudinal direction of the glass fiber (C) in this invention is a flat shape. More specifically, a flat shape having a major axis / minor axis ratio of 1.5 to 10 is preferable, and a ratio of major axis / minor axis is preferably 2.0 to 6.0. Since the glass fiber (C) has such a flat shape, the molded product obtained can be obtained rather than using a glass fiber having a cross-sectional shape close to a circle such that the ratio of major axis / minor axis is less than 1.5. The impact resistance is improved, and the heat resistance and flame retardancy are also improved.
  • a glass fiber having a flat cross section with a ratio of major axis / minor axis of 1.5 to 10 has a larger surface area per unit mass than a glass fiber having a circular section, and thus a molded product after molding a resin composition. Since the ratio of the glass fiber which occupies for the surface increases, it is thought that the above performance is improved.
  • the major axis of the glass fiber (C) is preferably 10 to 50 ⁇ m, more preferably 15 to 40 ⁇ m, and even more preferably 20 to 35 ⁇ m.
  • the ratio (aspect ratio) between the average fiber length and the average fiber diameter of the glass fiber (C) is preferably 2 to 120, more preferably 2.5 to 70, and 3 to 50. It is more preferable.
  • the aspect ratio is less than 2, the impact resistance and rigidity are not sufficiently improved.
  • the aspect ratio exceeds 120, the anisotropy increases and the appearance of the molded product tends to deteriorate.
  • the average fiber diameter of glass fiber means the number average fiber diameter when converting a flat cross-sectional shape into a perfect circle of the same area.
  • the glass fiber (C) in the present invention a fiber having a general glass fiber composition such as E glass is used, but any composition can be used as long as the glass fiber can be formed.
  • glass fiber (C) As glass fiber (C), it is manufactured by a known glass fiber manufacturing method, and for improving adhesion to matrix resin and uniform dispersibility, silane coupling agent, titanium coupling agent, zirconia coupling agent, etc. Coupling agent of the above is used in the form of chopped strands which are bundled by a known sizing agent containing at least one kind of antistatic agent and film forming agent, and the bundled glass fiber strands are collected and cut to a certain length. It is preferred that
  • the composition 2 of the present invention has flame retardancy by containing a flame retardant.
  • the composition 2 preferably contains a phosphorus-based flame retardant (B) that does not contain the halogen element contained in the composition 1.
  • the content of the phosphorus-based flame retardant (B) containing no halogen element in the composition 2 is 100 parts by mass of the total amount of nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2).
  • the amount is preferably 15 to 60 parts by mass, more preferably 20 to 55 parts by mass, and further preferably 30 to 50 parts by mass.
  • the content of the phosphorus-based flame retardant (B) not containing a halogen element is less than 15 parts by mass, it becomes difficult to impart sufficient flame retardancy.
  • the operability during extrusion is lowered, and the strength and surface appearance of the obtained molded product are lowered.
  • the hindered phenol antioxidant (D) is contained in the composition 1 or the composition 2 of the present invention.
  • the effect of drastically reducing the gas generated during molding can be obtained.
  • the cause of gas generation during molding is often the monomer or various additives in the resin composition. Therefore, it is effective to add the hindered phenol-based antioxidant (D) to the composition 1 or the composition 2 containing the phosphorus-based flame retardant (B) containing no halogen element.
  • the mold surface By reducing the gas generated during molding, the mold surface can be prevented from being soiled.
  • the gas vent of the mold is not easily clogged, and long-term continuous molding becomes possible. Further, the surface of the molded product due to gas can be prevented from being stained, and a molded product having an excellent surface appearance can be obtained.
  • the hindered phenol antioxidant (D) is easily mixed uniformly with the phosphinate and diphosphinate preferably used as the phosphorus flame retardant (B) not containing a halogen element, and prevents decomposition of the flame retardant. Does not impair flame retardancy.
  • the phosphinate and diphosphinate preferably used as the phosphorus flame retardant (B) not containing a halogen element, and prevents decomposition of the flame retardant. Does not impair flame retardancy.
  • the hindered phenolic antioxidant (D) means at least one position containing at least one phenol group, the aromatic part of which is directly adjacent to the carbon having a phenolic hydroxyl group as a substituent, preferably Means an organic compound substituted at both positions.
  • the substituent adjacent to the hydroxyl group is an alkyl radical suitably selected from alkyl groups having 1 to 10 carbon atoms, preferably a tertiary butyl group.
  • the appropriate molecular weight of the hindered phenol is 260 or more, preferably 500 or more, more preferably 600 or more. Most preferred is a hindered phenol having low volatility at high temperature, particularly low volatility at the processing temperature used for molding the compound, and heating from room temperature to 400 ° C. at a temperature rising rate of 10 ° C./min.
  • the 10% TGA weight loss temperature is 290 ° C. or higher, more preferably 300 ° C. or higher, and most preferably 310 ° C. or higher.
  • Examples of the hindered phenol antioxidant (D) include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (2 -Methyl-4-hydroxy-5-tert-butylphenyl) butane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5 -Tert-butyl-4-hydroxy-hydrocinnamamide), ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], N, N'-hexane- 1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)] etc.
  • Irganox 1010 ⁇ pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ⁇ manufactured by Ciba Specialty Chemicals, Inc.
  • Irganox 1098 ⁇ N, N '-Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)] ⁇ can be used.
  • the hindered phenol antioxidant (D) is 100 parts by mass of the total amount of nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2). It is preferably contained in an amount of 0.05 to 3.0 parts by mass, and more preferably 0.1 to 2.0 parts by mass.
  • the content of the hindered phenol antioxidant (D) is less than 0.05 parts by mass, the effect of drastically reducing the gas generated during molding as described above is poor.
  • the content exceeds 3.0 parts by mass, the stability during extrusion, formability, and mechanical properties tend to be reduced.
  • the polyamide resin composition of the present invention contains pigments, heat stabilizers, weathering agents, plasticizers, lubricants, mold release agents, antistatic agents, fillers, crystal nucleating agents, etc., as long as the properties are not significantly impaired. It may be added.
  • the polyamide resin composition of the present invention is excellent in dispersibility of these additives because the main polyamide resin component is excellent in fluidity. For this reason, even when these additives are added in a small amount, a sufficient effect can be obtained.
  • Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, Examples thereof include zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, and carbon fiber.
  • Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir shell, bran, and modified products thereof.
  • the polyamide resin composition of the present invention contains nylon 11 resin and / or nylon 1010 resin (A1) and nylon 6 resin (A2), but other than these as long as the effect is not impaired. It may contain a resin. Examples thereof include polycarbonate, polyester, polyolefin, polyphenylene ether and the like.
  • examples of means for mixing the nylon 1010 resin (A1), the nylon 6 resin (A2), and the glass fiber (C) include a melt kneading method using a uniaxial or biaxial extruder. From the viewpoint of improving the kneading state, it is preferable to use a twin screw extruder.
  • the kneading temperature during melt kneading is preferably 190 to 270 ° C.
  • the kneading time for melt kneading is preferably 20 seconds to 30 minutes.
  • the polyamide resin composition of the present invention can be formed into various molded products by molding methods such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing.
  • molding methods such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing.
  • it is suitable for the injection molding method, and can be used for gas injection molding, injection press molding, etc. in addition to general injection molding.
  • Examples of molded products obtained from the polyamide resin composition of the present invention include injection molded products, extrusion molded products, blow molded products, films, fibers, and sheets. These molded articles can be used for various applications such as electric / electronic parts, machine parts, optical equipment, building members, automobile parts, and daily necessities. According to the polyamide resin composition of the present invention, a molded product having excellent rigidity, impact resistance and appearance can be obtained, and therefore, it can be used for various products. Molded products obtained from the polyamide resin composition of the present invention include, for example, various molded products for electrical, electronic and automotive applications such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, switches, and various parts around PCs. And housings, mobile phone parts and housings, and other resin parts for appliances such as OA equipment parts.
  • the method for measuring the melt viscosity of the raw material nylon resin and the method for measuring and evaluating the characteristic values of the resin compositions obtained in the examples and comparative examples are as follows.
  • the nylon 6 resin, nylon 11 resin, and nylon 1010 resin have a melt viscosity of 230 ° C. and a flow rate of 10 mm / min according to the plastic flow characteristics test method specified in JIS K7199. The viscosity was measured using a viscometer “Capillograph 1B” (trade name).
  • the material which comprises the resin composition used in the Example and the comparative example is shown.
  • decamethylene diammonium sebacate 100 parts by mass of decamethylene diammonium sebacate and 33 parts by mass of water were charged into an autoclave, and after substitution with nitrogen, heating was started while stirring at a preset temperature of 240 ° C. and 25 rpm. After holding at a pressure of 2 MPa for 2 hours, the water vapor was exhausted and the pressure was reduced to normal pressure. After stirring at normal pressure to 0.02 MPa for 2 to 3 hours, the mixture was allowed to stand for 1 hour and then discharged. Then, it dried under reduced pressure and obtained nylon 1010 resin.
  • melt viscosity 2000 Pa ⁇ s ⁇ Nylon 6 resin: Unitika A1012, melt viscosity 10 Pa ⁇ s Nylon 6 resin: A1020 BRL manufactured by Unitika, melt viscosity 50 Pa ⁇ s -Nylon 6 resin: Unitika A1030 HRS, melt viscosity 160 Pa.s ⁇ Nylon 6 resin: Unitika A1030 BRL, melt viscosity 180 Pa ⁇ s
  • Amorphous polyamide resin polycondensate of isophthalic acid / terephthalic acid / hexamethylenediamine (X21 manufactured by Mitsubishi Engineering Plastics, glass transition temperature 138 ° C.)
  • Glass fiber having a flat fiber cross-sectional shape: CSG3PA820S manufactured by Nittobo Co., Ltd., major axis 28 ⁇ m, minor axis 7 ⁇ m, fiber length 3 mm, silane-based surface treatment; Diameter 10 ⁇ m, fiber length 3mm
  • Melamine polyphosphate Melapur 200/70 manufactured by Ciba Specialty Chemicals, particle size 20 ⁇ m
  • Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]: Irganox 1010 manufactured by Ciba Specialty Chemicals
  • Phosphorus antioxidant Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite: Adeka Stab PEP-36 manufactured by Adeka
  • the polyamide resin compositions (Composition 1) of Examples 1 to 31 have high bending strength and flexural modulus, excellent rigidity, high Charpy impact value, and excellent impact resistance. It was. Furthermore, it was possible to obtain a molded product having excellent flame retardancy and little occurrence of surface contamination. Among them, the resin compositions of Examples 15 to 16 are further blended with melamine polyphosphate or melamine cyanurate as a flame retardant, so that flame retardancy is improved and the total afterflame time is shortened compared to Example 13. We were able to. In addition, since the resin compositions of Examples 18 to 20 were blended with a hindered phenolic antioxidant, the gas generated during molding was drastically reduced and no hindered phenolic antioxidant was blended.
  • Example 22 Compared to Example 3 and Example 21 containing other antioxidants, a molded article having almost no surface contamination was obtained. Moreover, since the resin composition of Example 22 was also blended with a hindered phenol antioxidant, it was possible to suppress the occurrence of surface contamination compared to Example 14.
  • the resin compositions of Comparative Examples 1, 3, and 15 have a low blending ratio of the nylon 11 resin and the nylon 1010 resin, so that the amount of plant-derived components is small and the resin composition is environmentally friendly. In addition, it was inferior in impact resistance.
  • the resin compositions of Comparative Examples 2, 4, 12, and 16 were low in rigidity and low in flexural modulus and bending strength because the blending ratio of nylon 6 resin was low. Since the resin compositions of Comparative Examples 5 to 9 used a nylon 6 resin having a high melt viscosity, the fluidity of the resin composition is lowered, the dispersibility of the flame retardant is lowered, and the effect of the flame retardant is sufficiently obtained. In addition, the surface of the obtained molded product was soiled.
  • the resin composition of Comparative Example 10 is inferior in flame retardancy because the amount of the flame retardant is small, and the resin composition of Comparative Example 11 is obtained because the amount of the flame retardant is large. Dirt was generated on the surface of the product. Since the resin compositions of Comparative Examples 13 to 14 used magnesium hydroxide as a flame retardant, they were inferior in flame retardancy, and the magnesium hydroxide floated on the surface of the molded product, resulting in contamination.
  • the resin compositions of Examples 32 to 61 have high bending strength and flexural modulus and excellent rigidity, and high Charpy impact value and excellent impact resistance. It was. Furthermore, it was possible to obtain a molded product having excellent surface gloss and less surface contamination.
  • the resin compositions of Examples 49 to 50 contain an amorphous polyamide resin, the dispersibility of the glass fibers is further improved, and the glass fibers on the surface of the molded product can be prevented from floating when formed into a molded product. In comparison with Example 46, which did not contain an amorphous polyamide resin, a molded article excellent in surface glossiness could be obtained.
  • the resin compositions of Comparative Examples 17, 19, and 27 have a low blending ratio of the nylon 11 resin and the nylon 1010 resin, so that the amount of plant-derived components is small and the resin composition is environmentally friendly. In addition, it was inferior in impact resistance.
  • the resin composition of Comparative Examples 18, 20, and 28 had a low blending ratio of nylon 6 resin, it had low rigidity and was inferior in bending elastic modulus and bending strength. Since the resin compositions of Comparative Examples 21 to 24 used nylon 6 resin having a high melt viscosity, the fluidity of the resin composition was lowered, and the dispersibility of the glass fiber was lowered. It became difficult to suppress the floating of the surface, and surface glossiness and impact resistance were lowered.
  • the resin composition of Comparative Example 25 is inferior in bending strength, flexural modulus, and impact resistance because of the small amount of glass fiber, and the resin composition of Comparative Example 26 has a glass fiber content. Since there were many, the obtained molded article was inferior in surface glossiness by the glass fiber floating on the surface.
  • the resin compositions of Examples 62 to 88 (Composition 2 containing a flame retardant) have high bending strength and flexural modulus, excellent rigidity, high Charpy impact value, and impact resistance. It was also excellent. Furthermore, it was possible to obtain a molded product having excellent flame retardancy and surface glossiness and less surface contamination.
  • the resin compositions of Examples 72 to 73 were improved by adding melamine polyphosphate or melamine cyanurate as a flame retardant, and the total afterflame time was shortened compared to Example 63. We were able to.
  • the resin compositions of Examples 74 to 75 are blended with a hindered phenolic antioxidant, the gas generated at the time of molding is drastically reduced.
  • Example 76 Compared with Example 76 in which an agent was blended, a molded article having almost no surface contamination was obtained. Further, since the resin composition of Example 82 was also blended with a hindered phenol-based antioxidant, a molded product with almost no surface contamination was obtained as compared with Example 81. In addition, since the resin compositions of Examples 80 to 81 contain an amorphous polyamide resin, the dispersibility of the glass fiber is further improved, and the glass fiber on the surface of the molded product is prevented from floating when formed into a molded product. Compared with Example 78 which does not contain an amorphous polyamide resin, a molded article excellent in surface glossiness could be obtained.
  • the resin composition of Comparative Examples 29 and 31 has a low blending ratio of nylon 11 resin, the amount of plant-derived components is small, and it cannot be made into an environmentally friendly resin composition. It was inferior in impact.
  • the resin compositions of Comparative Examples 30 and 32 were low in rigidity and low in flexural modulus and bending strength because the blending ratio of nylon 6 resin was low. Since the resin compositions of Comparative Examples 33 to 35 used a nylon 6 resin having a high melt viscosity, the fluidity of the resin composition was lowered, and the dispersibility of the glass fiber and the flame retardant was lowered. The effect of the flame retardant could not be fully exhibited, and the surface of the obtained molded product was soiled.
  • the resin composition of Comparative Example 36 is inferior in flame retardancy because the amount of flame retardant is small, and the resin composition of Comparative Example 37 is a molded product obtained because of the large amount of flame retardant Dirt was generated on the surface. Since the resin compositions of Comparative Examples 38 to 39 used magnesium hydroxide as a flame retardant, they were inferior in flame retardancy, and the magnesium hydroxide floated on the surface of the molded product, resulting in contamination.
  • the resin composition of Comparative Example 40 is inferior in bending strength, flexural modulus, and impact resistance because the amount of glass fiber is small, and the resin composition of Comparative Example 41 has a large amount of glass fiber. For this reason, the obtained molded product was inferior in surface glossiness due to glass fiber floating on the surface.

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  • 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)

Abstract

La présente composition de résine, qui comprend une résine nylon 11 et/ou une résine nylon 1010 (A1), une résine nylon 6 (A2), et un agent ignifugeant à base de phosphore (B) ne contenant pas d'éléments halogénés, est caractérisée en ce que : le rapport massique (A1:A2) de la résine nylon 11 et/ou de la résine nylon 1010 (A1) par rapport à la résine nylon 6 (A2) est compris entre 1:4 et 4:1 ; la quantité incluse d'agent ignifugeant à base de phosphore (B) n'incluant pas d'éléments halogénés étant de 15 à 60 pour chaque fraction entière de 100 masses de la résine nylon 11 et/ou de la résine nylon 1010 (A1) et de la résine nylon 6 (A2) ; et la viscosité à l'état fondu de la résine nylon 6 (A2) étant comprise entre 5 et 170 Pa·s.
PCT/JP2011/076977 2010-11-26 2011-11-24 Composition de résine polyamide WO2012070598A1 (fr)

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CN103214843A (zh) * 2013-04-28 2013-07-24 安特普工程塑料（苏州）有限公司 一种长纤维增强长碳链尼龙及其制备方法
JP2017014397A (ja) * 2015-07-01 2017-01-19 旭化成株式会社 ポリアミド組成物、成形品、及びｌｅｄ用反射板
WO2020178342A1 (fr) * 2019-03-06 2020-09-10 Basf Se Compositions de moulage en polyamide pour applications à brillance
CN111961340A (zh) * 2020-08-04 2020-11-20 会通新材料(上海)有限公司 一种无卤阻燃生物基尼龙56复合材料及其制备方法
WO2021039259A1 (fr) * 2019-08-28 2021-03-04 東洋紡株式会社 Film de polyamide barrière au gaz
CN114364746A (zh) * 2019-09-10 2022-04-15 朗盛德国有限责任公司 高压部件

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CN103214843A (zh) * 2013-04-28 2013-07-24 安特普工程塑料（苏州）有限公司 一种长纤维增强长碳链尼龙及其制备方法
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WO2020178342A1 (fr) * 2019-03-06 2020-09-10 Basf Se Compositions de moulage en polyamide pour applications à brillance
CN113544213A (zh) * 2019-03-06 2021-10-22 巴斯夫欧洲公司 用于高光泽应用的聚酰胺模塑组合物
JP7513626B2 (ja) 2019-03-06 2024-07-09 ビーエーエスエフ ソシエタス・ヨーロピア 高光沢用途のためのポリアミド成形組成物
WO2021039259A1 (fr) * 2019-08-28 2021-03-04 東洋紡株式会社 Film de polyamide barrière au gaz
CN114364746A (zh) * 2019-09-10 2022-04-15 朗盛德国有限责任公司 高压部件
CN111961340A (zh) * 2020-08-04 2020-11-20 会通新材料(上海)有限公司 一种无卤阻燃生物基尼龙56复合材料及其制备方法
CN111961340B (zh) * 2020-08-04 2022-12-09 会通新材料(上海)有限公司 一种无卤阻燃生物基尼龙56复合材料及其制备方法

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