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WO2010087193A1 - Composition de résine de polyamide ignifuge renforcée par des fibres de verre - Google Patents

Composition de résine de polyamide ignifuge renforcée par des fibres de verre Download PDF

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Publication number
WO2010087193A1
WO2010087193A1 PCT/JP2010/000534 JP2010000534W WO2010087193A1 WO 2010087193 A1 WO2010087193 A1 WO 2010087193A1 JP 2010000534 W JP2010000534 W JP 2010000534W WO 2010087193 A1 WO2010087193 A1 WO 2010087193A1
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Prior art keywords
polyamide resin
glass fiber
weight
resin composition
flame retardant
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English (en)
Japanese (ja)
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知英 中川
泰人 藤井
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Toyobo Co Ltd
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Toyobo Co Ltd
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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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • 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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a glass fiber reinforced flame retardant polyamide resin composition that achieves both high flame retardancy and mechanical properties by improving the adhesion between a polyamide resin and a flat cross-section glass fiber with a silane coupling agent.
  • Polyamide resin can exhibit not only high rigidity and high toughness but also high load deflection by being reinforced with glass fiber. Therefore, the glass fiber reinforced polyamide resin composition is widely used as an internal member and an external member in the field of electronic equipment and automobiles. In recent years, the level of flame retardancy required particularly for electronic electrical members has increased, and a flame retardant polyamide resin composition excellent in flame retardancy and mechanical properties has been demanded.
  • Patent Document 1 discloses a flame retardant polyamide resin composition
  • a flame retardant polyamide resin composition comprising (A) a polyamide resin, (B) a phosphorus-based flame retardant, and (C) a flat cross-section glass fiber.
  • the flame retardancy is UL16 standard V-0 when the thickness is 1/16 inch, but V-0 cannot be achieved when the thickness is 1/32 inch.
  • the Charpy impact strength (ISO 179), particularly the notched Charpy impact strength, is a level that should be greatly improved in practice.
  • comparing the example using the flat cross-section glass fiber and the comparative example using the normally used circular cross-section glass fiber disclosed the result that there is no significant difference in Charpy impact strength, The effect is not fully drawn out.
  • Patent Document 2 discloses a polyamide molding material that combines a low-viscosity polyamide resin and a glass fiber having a flat cross section and exhibits high Charpy impact strength. No physical properties such as strength are shown.
  • a halogen-free flame retardant increases the physical properties of the polyamide resin to make it flame retardant.
  • the low viscosity polyamide resin tends to melt and drop in a flame retardant test, especially at a thin thickness. It is difficult to achieve a high degree of flame retardancy.
  • the present invention was devised in view of the current state of the prior art described above, and its purpose is to use a non-halogen flame retardant to achieve high flame resistance and mechanical properties, particularly impact resistance (notched Charpy impact properties).
  • An object of the present invention is to provide a glass fiber reinforced flame retardant polyamide resin composition in which both are satisfied.
  • the present inventor has added a silane coupling agent at the time of melt-kneading a mixture of a specific polyamide resin, a non-halogen flame retardant, and a flat cross-section glass fiber, and the polyamide and the glass fiber. It was found that a polyamide resin composition having a high level of flame retardancy and a high mechanical property that contains a large amount of flat cross-section glass can be obtained by firmly bonding to each other, and the present invention has been completed.
  • the present invention employs the following configuration.
  • a glass fiber reinforced polyamide resin composition obtained by melt-kneading a mixture to which 30 to 70 parts by weight of a glass fiber bundle (C) having a loss on ignition of 0.5% by weight or less at 0.5 hr is added, the polyamide
  • the resin is a polycaproamide resin (a1) and / or a crystalline polyamide resin (a2) having a melting point 20 ° C.
  • the polyamide-reactive silane cup with respect to the mixture during the melt kneading Ing agent (D) is glass fiber reinforced flame-retardant polyamide resin composition characterized in that it is added in an amount of 0.1 to 1.0% by weight of the glass fiber bundle (C).
  • the polycaproamide resin (a1) has a relative viscosity in a 96% sulfuric acid solution of 1.2 to 2.0 and a terminal carboxyl group concentration of 70 meq / kg or more (1) or The glass fiber reinforced flame retardant polyamide resin composition according to (2).
  • Phosphorus flame retardants (B) other than red phosphorus are diphosphinic acid metal salt (b1), reaction product (b2) comprising melamine and phosphoric acid, phosphazene compound (b3) and phosphinic acid derivative (b4)
  • the glass fiber-reinforced flame-retardant polyamide resin composition according to any one of (1) to (3), wherein the composition is at least one selected from the above.
  • the glass fiber reinforced flame retardant polyamide resin composition exhibits flame retardancy of UL94 standard V-0 (1/32 inch thickness) and the Charpy of the glass fiber reinforced flame retardant polyamide resin composition
  • the area ratio of apparent fracture surface area (SA) / notch cross-sectional area (SB) is 2.2 to 4
  • SA apparent fracture surface area
  • SB notch cross-sectional area
  • the glass fiber reinforced flame retardant polyamide resin composition of the present invention is obtained by adding a silane coupling agent during melt kneading of a polyamide resin, a non-halogen flame retardant, and a flat cross-section glass fiber. Is strong and can be stably extruded even when the glass fiber has a high filling amount. As a result, the glass fiber reinforced flame retardant polyamide resin composition of the present invention contains a large amount of glass fiber and is flame retardant with a non-halogen flame retardant, while having high flame resistance and high resistance. The impact properties can be satisfied at the same time, and the mechanical properties such as other strength and rigidity are excellent, and the moldability is also excellent.
  • the glass fiber reinforced flame retardant polyamide resin composition of the present invention is used for automobile electrical components such as casing parts such as circuit breakers and magnet switches in the electronic and electric fields, personal computer, mobile phone casing parts, and other connector parts. Suitable for applications such as parts.
  • FIG. 1 is an explanatory view schematically showing a fracture state of an impact strength test piece and a test piece after the impact strength test.
  • (1-1) shows a notched Charpy impact strength test piece formed by cutting
  • (1-2) shows a fracture state after the impact strength test of a test piece of a comparative example
  • (1-3) shows The fracture state of the test piece of the present invention is shown.
  • FIG. 2 is a drawing-substituting photograph showing the fractured state of the test piece after the test.
  • (2-1) is an example of a test piece of the present invention
  • (2-2) is an example of a test piece of a comparative example.
  • FIG. 3 is an explanatory view showing an example of a projected image obtained by binarizing the image of the broken portion of the test piece.
  • FIG. 4 shows an example of fracture of the Charpy impact strength test piece of the present invention.
  • (4-1) is a drawing-substituting photograph showing a fracture example of the product of the present invention (Example 1)
  • (4-2) is an electron microscope (SEM) photograph showing the state of the tip of the fracture surface of the fracture example.
  • FIG. 5 shows an example of fracture of the Charpy impact strength test piece of the comparative example.
  • (5-1) is a drawing-substituting photograph showing a fracture example of Comparative Example 1
  • (5-2) is an electron microscope (SEM) photograph showing the state of the tip portion of the fracture surface of the fracture example.
  • FIG. 6 shows an explanatory diagram (6-1) of the crack angle and crack length of the test piece after the Charpy impact strength test, and an image of Charpy test (6-2).
  • the glass fiber reinforced flame retardant polyamide resin composition of the present invention is flat against 25 to 50 parts by weight of a polyamide resin (A) having a specific composition and 2 to 20 parts by weight of a phosphorus flame retardant other than red phosphorus (B).
  • a mixture of glass fiber bundles (C) 30 to 70 parts by weight with a loss of ignition of 0.8% by weight or less at 625 ° C. and 0.5 hr consisting of flat cross-section glass fibers having a degree of 1.5 to 8 is melt-kneaded.
  • the polyamide-reactive silane coupling agent (D) is added to the mixture at the rate of 0.1 to 1.0% by weight of the glass fiber bundle (C) during the melt-kneading. It is characterized by that.
  • the polyamide resin (A) in the present invention has a polycaproamide resin (a1) and / or a crystalline polyamide resin (a2) having a melting point 20 ° C. higher than the polycaproamide resin (a1) and an aromatic component.
  • Amorphous polyamide resin (a3) is mixed in a weight ratio of 90/10 to 35/65.
  • the polycaproamide resin (a1) is a polycaproamide resin usually obtained by polycondensation of ⁇ -caprolactam or 6-aminocaproic acid, which is called nylon 6.
  • the crystalline polyamide resin (a2) having a melting point 20 ° C. higher than the polycaproamide resin (a1) has an acid amide bond (—CONH—) in the molecule and has a melting point and glass point transfer.
  • a melting point when the temperature is raised at a rate of temperature rise of 20 ° C./min with a differential scanning calorimeter (DSC) is 20 ° C. or more higher than (a1), and a lactam or ⁇ -aminocarboxylic acid having a 3-membered ring or more
  • lactam and ⁇ -aminocarboxylic acid examples include ⁇ -enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, ⁇ -pyrrolidone, ⁇ -piperidine and the like.
  • dicarboxylic acid examples include terephthalic acid, isophthalic acid, adipic acid, and sebacic acid.
  • diamine examples include tetramethylene diamine, hexamethylene diamine, metaxylylene diamine, paraxylylene diamine, undecamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, trimethylhexamethylene diamine, aminoethylpiperazine, and bis.
  • polyamide 66 is preferable from the viewpoints of moldability, heat resistance, toughness and the like.
  • the amorphous polyamide resin (a3) having an aromatic component is made from trimethylhexamethylenediamine, hexamethylenediamine, metaxylenediamine, metaxylylenediamine, terephthalic acid, isophthalic acid, ⁇ -caprolactam, and the like. It is a polymer or copolymer obtained by condensation. Among these, (1) glass transition point is 100 ° C. or higher, (2) 160 ° C. ⁇ 1 hour differential scanning calorimeter (DSC) heated at a rate of 20 ° C./min. The thing of 3 J / g or less is preferable.
  • amorphous polyamide resin examples include a polymer of trimethylhexamethylenediamine and terephthalic acid, a polymer of trimethylhexamethylenediamine, terephthalic acid and ⁇ -caprolactam, trimethylhexamethylenediamine, terephthalic acid and isophthalic acid.
  • Polymers of hexamethylenediamine, terephthalic acid and isophthalic acid polymers of terephthalic acid, isophthalic acid, hexamethylenediamine and ⁇ -caprolactam, metaxylylenediamine and isophthalic acid And a polymer of terephthalic acid and ⁇ -caprolactam.
  • polyamide 6T / 6I is preferable from the viewpoints of moldability, heat resistance, toughness and the like.
  • the polycaproamide resin (a1) preferably has a low viscosity from the viewpoint of improving the fluidity of the resin composition during molding and improving the appearance of the molded product, and in particular, the relative viscosity in a 96% sulfuric acid solution is 2. It is preferable that it is 0 or less from a viewpoint of the production surface at the time of highly filling flat cross-section glass fiber and the fluidity at the time of shaping
  • the lower limit of the relative viscosity is preferably 1.2 or more from the viewpoint of maintaining a certain degree of toughness.
  • low-viscosity polyamide in the composition is preferred from the viewpoint of production and appearance of the molded product, and contributes to improving the wetting of the flat cross-section glass fiber and the polyamide as shown in Patent Document 2 cited above. Although it is possible, it is shown in a later experimental example that it is not an absolute condition. Further, the terminal carboxyl group concentration of the polycaproamide resin is preferably 70 meq / kg or more.
  • (A2) is preferably a crystalline resin having a high melting point from the viewpoint of imparting heat resistance, and is compatible with (a1) and extruded. If the temperature during molding is too high, there is a concern of causing decomposition of the flame retardant. Therefore, polyamide 66 is more preferable.
  • (A3) is preferably a polyamide resin that adjusts the rate of solidification and improves the strand property during production and the mold transfer property during injection molding, and is compatible with (a1) and / or (a2), In view of strength development, toughness retention, and rigidity development, polyamide 6T / 6I is particularly preferable. When the polyamide resin (A) is 100% by weight, (a1) is 95 to 20% by weight, (a2) is 0 to 80% by weight, and (a3) is 5 to 50% by weight. Particularly preferred from the viewpoints of moldability and heat resistance.
  • Phosphorus flame retardants (B) other than red phosphorus in the present invention include, for example, diphosphinic acid metal salt (b1), reaction product (b2) comprising melamine and phosphoric acid, phosphazene compound (b3), and phosphinic acid derivative (b4). ).
  • the diphosphinic acid metal salt (b1) is at least one of a phosphinic acid salt represented by the following general formula (1) and a diphosphinic acid salt represented by the general formula (2).
  • R 1 and R 2 are the same or different and are linear or branched alkyl having 1 to 6 carbon atoms and / or aryl, and R 3 is linear. Or a branched alkylene having 1 to 10 carbon atoms, arylene having 6 to 10 carbon atoms, alkyl arylene having 6 to 10 carbon atoms, or aryl alkylene having 6 to 10 carbon atoms, and M is a calcium ion, a magnesium ion, or an aluminum Either an ion and / or a zinc ion, m is 2 or 3, n is 1, 2 or 3, and x is 1 or 2. ]
  • R 1 and R 2 are preferably methyl, ethyl or n-propyl, isopropyl, n-butyl, tert-butyl, n-pentene and / or phenyl.
  • R 3 is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octene, n-dosylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butyl. Phenylene, methylnaphthylene, ethylnaphthylene, or tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene.
  • M is preferably an aluminum ion, a zinc ion or a calcium ion.
  • phosphinate encompasses phosphinates and diphosphinates and polymers thereof.
  • This phosphinic acid salt is produced in an aqueous solvent and is essentially a monomeric compound, but depending on the reaction conditions, polymeric phosphinic acid salts also form in specific environments. It can happen.
  • Suitable phosphinic acids as one component of the phosphinic acid salt include, for example, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylenephosphinic acid, methane-1,2-di (methylphosphinic acid), benzene 1,4- (dimethylphosphinic acid) methylphenylphosphinic acid and diphenylphosphinic acid.
  • the phosphinic acid salt in the present invention can be produced by a known method as described in European Patent Application No. 699708.
  • the phosphinic acid salt can be produced, for example, by reacting with a metal carbonate, metal hydroxide or metal oxide in an aqueous solution.
  • known compounds can be used, and among them, phosphinic acid aluminum salt is preferable.
  • the reaction product (b2) comprising melamine and phosphoric acid in the present invention is a cyanamide derivative having at least one amino group or a reaction product of the cyanamide derivative and phosphoric acid, specifically, an amino group and —N ⁇ C ⁇ N— or —N ⁇ C (—N ⁇ ) 2 is a compound having an amino group-containing triazine (amino group such as melamine, melam, melem, melon, guanamine, acetoguanamine, benzoguanamine) -Containing 1,3,5-triazines, amino group-containing 1,2,4-triazines such as 3-amino-1,2,4-triazine), amino group-containing triazoles (2,5-diamino-1) Cycyanamide derivatives such as amino group-containing 1,3,4-triazoles such as 1,3,4-triazole, etc .; guanidines [guanidine And acyclic cyanamide derivatives such as guanidine derivatives (
  • Preferred cyanamide derivatives are amino group-containing 1,3,5-triazines, guanidine or derivatives thereof, in particular melamine.
  • melamine melamine cyanurate can also be used as one of derivatives.
  • Such cyanamide derivatives can be used alone or in combination of two or more.
  • the cyanamide derivative having at least one amino group or the reaction product of phosphoric acid with at least one amino group in the present invention is preferably a condensation product of melamine, a reaction product of melamine or a condensation product of melamine and phosphoric acid, And at least one reaction product of melamine and phosphoric acid condensate, more preferably melamine polyphosphate, melem polyphosphate, melam polyphosphate, dimelamine pyrophosphate, particularly preferably It is a melamine polyphosphate (melamine polyphosphate) having a long chain length of 2 or more, particularly 10 or more and 50 or less. Melamine polyphosphate has an effect of increasing the crystallization speed of polyamide, and is also preferable in terms of improving moldability.
  • the phosphazene compound (b3) in the present invention is an organic compound having a —P ⁇ N— bond in the molecule, preferably a cyclic phenoxyphosphazene having a structure represented by the following general formula (3) in the molecule or a chain Or a crosslinked phenoxyphosphazene compound in which at least one phenoxyphosphazene is crosslinked by a crosslinking group.
  • cyclic phosphazenes such as trade name SPE-100 manufactured by Otsuka Chemical Co., Ltd., cyclic cyanophenoxyphosphazenes such as trade name FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd., and Otsuka Chemical.
  • SPH-100 manufactured by Co., Ltd. can be mentioned.
  • Chain phenoxyphosphazenes, cross-linked phenoxyphosphazenes, etc. have substituents at the molecular ends, so they generally have a lower phosphorus content than cyclic phosphazenes, but tend to suppress bleeding, etc., depending on the type of resin added It is necessary to use properly.
  • the aliphatic polyamide since the aliphatic polyamide has low compatibility with the phosphazene compound, it is preferable to apply the phosphazene compound as a flame retardant when the amount of MXD6 having relatively excellent compatibility is large.
  • X is a phenoxy group, and n is an integer of 3 to 10,000.
  • non-reactive phosphazenes may cause bleeding on the surface over time, may elute free phosphorus under the influence of hydrolysis under severe use conditions, or the insulation properties may deteriorate due to decomposition products. Therefore, more preferably, a reactive phosphazene having a functional group having an affinity for polyamide is selected. Specific examples thereof include cyclic hydroxyphenoxyphosphazene having a hydroxyl group.
  • the phosphinic acid derivative (b4) in the present invention is different from the phosphorus compound defined in the above (b1), (b2) and (b3), and preferably represented by the following general formula (4).
  • HCA 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • HCA-HQ 10- (2,5-dihydroxyphenyl) from Sanko Co., Ltd.
  • 10- (2,5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • BCA (10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • phenylphosphinic acid diphenylphosphinic acid, etc. It is below.
  • R represents a hydrogen atom, a phenoxy group or an alkyl group having 1 to 10 carbon atoms.
  • (B) (b1) and at least one selected from (b2), (b3), and (b4) are preferably used in combination as a phosphorus-based flame retardant other than red phosphorus.
  • the flat cross-section glass fibers used for the glass fiber bundle (C) include those having a substantially elliptical system, a substantially oval system, or a substantially bowl-shaped system in a cross section perpendicular to the length direction of the fiber. .5-8.
  • the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. In this case, the ratio of major axis / minor axis.
  • a glass fiber having a substantially oval cross section and a flatness of 2 to 5 is particularly preferable because it exhibits high mechanical properties.
  • the thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 ⁇ m and the major axis is about 2 to 100 ⁇ m.
  • the glass fiber is preferably a chopped strand which is a fiber bundle and is cut to a fiber length of about 1 to 20 mm.
  • the polyamide reaction is performed on the mixture of the polyamide resin (A), the phosphorus flame retardant (B) other than red phosphorus, and the glass fiber bundle (C) during melt-kneading. It is necessary to add the functional silane coupling agent (D) at a ratio of 0.1 to 1.0% by weight of the glass fiber bundle (C).
  • the functional silane coupling agent (D) As shown in Patent Documents 3 to 7, glass fibers are generally used as polyamide reinforcing agents in the form of chopped strands bundled with a sizing agent and cut to a certain length.
  • the amount of the aminosilane coupling agent that can be preliminarily attached to the fiber bundle has an upper limit so that the fiber bundle does not fail to be defibrated during extrusion, and is preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the glass fiber. 0.2 parts by weight.
  • a glass fiber bundle treating agent containing a silane coupling agent is evaluated as a non-volatile component at 125 ° C.
  • the content of the silane coupling agent is 2 to 20 parts by weight.
  • the non-volatile component at 125 ° C. of the chopped strand can be quantified by loss on ignition at 625 ° C. and 0.5 hr after drying the moisture, and is generally 0.2 to 1.5 for the glass fiber bundle for polyamide reinforcement. It is about wt%. If the loss on ignition is less than 0.2% by weight, it indicates that the amount of sizing agent for bundling the fiber bundle is small, and defibration during production causes production trouble.
  • the amount of the silane coupling agent is reduced, sufficient wettability with the resin cannot be ensured. If the loss on ignition exceeds 1.5% by weight, the fiber bundle is difficult to be defibrated and poor dispersion in the resin occurs. Furthermore, since components that do not contribute to the adhesion to the resin are gasified during extrusion, production becomes difficult particularly when a large amount of glass fiber is added as in the present invention. In the case of chopped strands of flat cross-section glass fibers, the flat planes overlap each other. Therefore, if the treatment with the bundling agent is increased, defibration defects are more likely to occur than the circular cross-section glass fiber bundles.
  • the bundling agent for the flat cross-section glass fiber bundle is suppressed to about 0.2 to 0.8% by weight with loss on ignition at 625 ° C. and 0.5 hr.
  • this amount of the silane coupling agent contained in the fiber bundle is 0.01 to 0.16% by weight of the glass fiber bundle, this amount of the silane coupling agent is a large amount of flat section glass as in the present invention.
  • the adhesion between the fiber and the polyamide resin cannot be sufficiently maintained.
  • a polyamide-reactive silane coupling agent (D) is newly added directly at the time of melt-kneading a mixture of the polyamide resin (A), a phosphorus flame retardant other than red phosphorus (B), and a glass fiber bundle (C).
  • the flat surface of the glass fiber is easily oriented in the surface direction of the molded product in the molded product, and this orientation phenomenon greatly affects the physical properties.
  • the coupling between the polyamide resin and the glass fiber is poor, if the flat surface of the glass fiber is oriented in the plane direction, the adhesion failure and defects at the interface between the glass fiber and the polyamide resin increase, resulting in a flat cross-section glass. Even if the fiber is highly filled, high rigidity and high physical properties cannot be obtained as intended.
  • the coupling between the glass fiber surface and the polyamide resin is good, the adhesion between the glass fiber and the polyamide resin is improved, and the surface reinforcing effect by the plane orientation of the flat cross-section glass fiber is added. As a result, a failure mode peculiar to the molded product is developed, and the impact energy absorption efficiency is improved.
  • the polyamide-reactive silane coupling agent (D) has a functional group that is reactive with polyamide, and can be chemically reacted with a carboxyl group or amino group that is a terminal group of the polyamide resin (A). It is an agent.
  • an aminosilane coupling agent having an amino group and an epoxysilane coupling agent having an epoxy group can be used. Of these, aminosilane coupling agents are particularly preferred from the viewpoint of interfacial adhesion between glass fiber and polyamide.
  • aminosilane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltriethoxysilane. Etc.
  • the addition amount of the polyamide-reactive silane coupling agent (D) at the time of melt-kneading with respect to the mixture of the polyamide resin (A), the phosphorus-based flame retardant other than red phosphorus (B), and the glass fiber bundle (C) is a glass fiber bundle. It is 0.1 to 1.0% by weight of (C), preferably 0.1 to 0.8% by weight. If the addition amount is less than the above range, the effect of improving the mechanical properties is small, and if it exceeds the above range, the amount of gas increases, which may cause problems during production and molding.
  • the glass fiber reinforced flame retardant polyamide resin composition of the present invention can be blended with a thermoplastic resin other than the polyamide resin for the purpose of suppressing bleeding of the flame retardant and improving paintability.
  • a thermoplastic resin other than the polyamide resin for the purpose of suppressing bleeding of the flame retardant and improving paintability.
  • polyester resins such as PET and PBT and styrene resins are effective for improving the compatibility, and phenolic resins for improving paintability.
  • polyphenylene ether resins are effective for the improvement.
  • These thermoplastic resins may be modified in order to improve the compatibility with the polyamide.
  • the thermoplastic resin is modified with an unsaturated carboxylic acid such as maleic acid or an acid anhydride thereof. .
  • the polyamide resin composition of the present invention is a weather resistance improver used for inorganic fillers other than the essential components described so far and ordinary polyamide resins within a range not impairing the characteristics of the present invention.
  • Carbon black, copper halide compounds and / or alkali metal halides, phenolic antioxidants, phosphorus antioxidants, mold release agents, crystal nucleating agents, lubricants, antistatic agents, pigments, dyes as light or heat stabilizers Etc. can be blended.
  • the polyamide resin (A), the phosphorus flame retardant other than red phosphorus (B), and the glass fiber bundle (C) 25: 2: 30 to 50:20:70 A mixture having a weight ratio was prepared, and then at least a part of the polyamide resin (A) was melted. In this molten mixture, a polyamide-reactive silane coupling agent (D) was added to the glass fiber bundle (C). And a method of melt kneading together by adding at a ratio of 1 to 1.0% by weight.
  • the components (A) and (B) or the components (A) and (C) are pre-blended with a blender and fed from a hopper into a uniaxial or biaxial melt kneading extruder, or (A) to (C) Component is fed into a single-screw or biaxial melt-kneading extruder using a feeder, and then (D) component is side-fed into the molten mixture in a state where at least a part of component (A) is melted.
  • a method of adding liquid by a method can be employed.
  • (C) component and (D) component are mixed beforehand, and the mixture of (C) component and (D) component is added by the side feed system in the melt of (A) and (B) component.
  • a method may be adopted.
  • the polyamide-reactive silane coupling agent (D) contacts the glass fiber bundle (C) during kneading, most of which reacts with the glass fiber surface, and the melt viscosity of the polyamide resin (A) is low. Therefore, even if a phosphorus-based flame retardant (B) other than red phosphorus is present, the polyamide resin (A) can easily come into contact with the glass fiber bundle (C), and the acid value above a certain level is a polyamide-reactive silane. Since the reaction with the coupling agent (D) suitably proceeds, it is considered that the adhesion between the polyamide resin (A) and the glass fiber bundle (C) becomes strong.
  • the glass fiber reinforced flame retardant polyamide resin composition of the present invention produced as described above has a high flame retardancy that can achieve V-0 at a measurement thickness of 1/32 inch according to UL94 standard.
  • Test piece after Charpy impact strength test (ISO 179-1 compliant, cutting notch) develops a specific failure mode, and the ratio of apparent fracture surface area (SA) / notch section area (SB) is conventional Much higher than technology.
  • FIG. 1 shows a notched Charpy impact strength test piece (1-1) formed by cutting, a fracture state after the impact strength test of a comparative test piece (1-2), and after the impact strength test of the test piece of the present invention.
  • 1 schematically shows the fracture state (1-3).
  • the fracture of the test piece of the prior art proceeds in a direction substantially perpendicular to the longitudinal direction of the test piece, starting from the notch, and the fracture surface becomes a filler or the like. Due to this, some unevenness is observed.
  • the test piece of the present invention does not progress in the direction perpendicular to the longitudinal direction (width direction) of the test piece, although it breaks starting from the notch tip.
  • the fracture proceeds in a direction closer to the longitudinal direction at an angle of 45 ° or more from the right angle direction, and then the complicated fracture such as once the fracture progresses in the opposite longitudinal direction to the notch in the longitudinal direction.
  • a cross section is formed.
  • the present inventor has caused the glass orientation of the Charpy test piece with a cutting notch and the adhesion between the glass and the polyamide resin to exhibit a specific fracture mode. It was confirmed.
  • the test piece in which the flat cross-section glass fiber has a large amount of surface orientation and is sufficiently adhered to the polyamide resin has a crack length at break (the length from the notch part tip to the opposite side of the notch part at the break start point). )
  • the thickness of the test piece it was confirmed that the fracture mode was such that the size of the fracture area was a certain level or more.
  • FIG. 2 shows a photograph of an example of the fracture after the test of the product of the present invention, taken from above the width surface.
  • FIG. 2 shows a photograph of a comparative product. The length of the fracture portion that can be read in these photographs is the fracture (crack) length, and the apparent fracture surface area (SA) is determined using this.
  • SA apparent fracture surface area
  • a notch part cross-sectional area (SB) is calculated by notch part width x test piece thickness. Then, the ratio of apparent fracture surface area (SA) / notch cross-sectional area (SB) is obtained.
  • SA apparent fracture surface area
  • SB notch cross-sectional area
  • the measurement of the fracture (crack) length is not limited to the method described above. In this projection image analysis method, there is no possibility of overestimating the apparent fracture area with respect to the actual fracture area due to the overlap in the thickness direction, so the difference in numerical value resulting from the measurement error between the projection image and the true crack length The accuracy as a parameter for detecting the crack fracture mode does not decrease.
  • FIG. 6 shows an explanatory diagram (6-1) of the crack angle and crack length of the test piece after the test, and a Charpy test image (6-2).
  • (6-2) in continuous cracks from the crack base point at the tip of the notch to the crack end point, n cracks having different traveling directions are defined as crack 1, crack 2... Crack n, and n cracks.
  • the crack length of the eye is Xn
  • the average crack angle is obtained as ( ⁇ 1 + ⁇ 2 +.
  • the total crack length is about 11 mm or less when the notch width is 8 mm.
  • the crack angle is 45 ° or less
  • the total crack length is about 11 mm or less when the notch width is 8 mm.
  • the crack angle is 45 ° or less
  • their crack angles are significantly larger than 45 °. Therefore, the crack length and the crack area are significantly increased, and the energy absorption is increased at the time of fracture. This is a peculiar failure mode obtained as a result of a significant improvement in surface impact due to a high addition amount of glass fiber and plane orientation of flat glass, and also a strong adhesive force between the glass and the resin interface.
  • the polyamide resin composition of the present invention has an apparent fracture surface area (SA) / notch cross-sectional area (SB) in the fracture surface of the test piece after the test in the Charpy impact strength test with cutting notch (in accordance with ISO 179-1). Ratio of 2.2 to 4.0, preferably 2.5 to 4.0 can be achieved. If the area ratio is less than the above range, it cannot be said that practical impact resistance is sufficient, and if it is attempted to obtain impact resistance exceeding the above range, it may be difficult to maintain the level of flame retardancy. .
  • SA apparent fracture surface area
  • SB notch cross-sectional area
  • the reason why the fracture surface of the test piece after the Charpy impact strength of the polyamide resin composition of the present invention is very specific is that the flat cross-section glass fiber is in the longitudinal direction of the test piece during the test and further to the surface. It is considered that the adhesion between the polyamide and the glass fiber is sufficiently high in addition to the plane orientation of the plane.
  • the flat orientation of the glass fiber is such that the notch-side surface of a notched Charpy test piece is polished to a depth of 2 mm from the surface (distance to the notch tip), and the polished surface is scanned with a scanning electron microscope (SEM). ) Etc. to confirm.
  • the numerical value represented by the apparent fracture surface area (SA) / notch cross-sectional area (SB) in the present invention improves the adhesion strength between the glass fiber and the matrix resin in the flat cross-section glass fiber resin composition. Can be reflected.
  • the melt drip at the time of combustion is easily suppressed in the flame retardancy of 1/32 inch thickness of UL94 standard, so that high flame retardancy is easily realized.
  • the present invention in the non-halogen flame retardant highly filled glass fiber reinforced polyamide resin composition, the impact strength of which is easily lowered by the addition of a non-halogen flame retardant, the apparent fracture surface area (SA) / notch section breaking is achieved.
  • SA apparent fracture surface area
  • SB The numerical value indicated by the area (SB) is 2.2 to 4.0, and a sufficient flame retardancy of V-0 can be imparted with a thickness of 1/32 inch, with high impact resistance and high difficulty. Both flammability can be achieved.
  • the impact strength of the glass fiber reinforced flame retardant polyamide resin composition of the present invention by a Charpy impact strength test is preferably 18 kJ / m 2 or more, more preferably 20 kJ. / M 2 or more, more preferably 22 kJ / m 2 or more.
  • the effect of improving the impact resistance of the polyamide resin composition of the present invention is largely due to the effect of reinforcing the plane strength of the flat cross-section glass fiber and sufficiently coupling with the resin. This is fundamentally different from the improvement method by adding a modified elastomer having excellent rubber elasticity.
  • a composition improved in impact resistance by an elastomer rapidly deteriorates in impact characteristics at a low temperature below the glass transition point of the elastomer, but the resin composition of the present invention does not depend on the addition of the elastomer, so There is no disadvantageous temperature dependence in and stable high impact characteristics can be obtained.
  • Terminal carboxyl group concentration (CEG) of polyamide resin 10 ml of benzyl alcohol was added to 0.2 g of polyamide resin and dissolved at 180 ° C. ⁇ 5 ° C. for 5 minutes. The solution was cooled in water for 15 seconds, titrated with ethanolic potassium hydroxide solution (adjusted to 1000 ml by adding ethanol to 0.5 ml of 0.5N-KOH) using phenolphthalein as an indicator, and the following formula was calculated.
  • CEG (meq / kg) ⁇ [(AB) ⁇ N ⁇ f] / (W ⁇ 1000) ⁇ ⁇ 10 6
  • W Weight of crystallized polyamide resin (g)
  • SA apparent fracture surface area
  • SB notch cross-sectional area
  • the apparent fracture surface area (SA) is calculated by the length of the fracture (crack) ⁇ the thickness of the Charpy impact test piece.
  • the apparent fracture surface area (SA) is an average value of 10 test pieces.
  • a notch part cross-sectional area (SB) is calculated by notch part width x test piece thickness. Then, the ratio of apparent fracture surface area (SA) / notch cross-sectional area (SB) is obtained.
  • B1 Used flame retardant (B) (B1) Aluminum phosphinate, “Exorit OP1230” manufactured by Clariant (B2) Melamine polyphosphate, “melapur 200/70” manufactured by Ciba Specialty Chemicals (B3) Cyclic phenoxyphosphazene, “SPE-100” manufactured by Otsuka Chemical Co., Ltd. (B4) 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, “BCA” manufactured by Sanko
  • Used glass fiber (C) (C1) “CSG3PA820S” manufactured by Nittobo Co., Ltd. as a flat cross-section glass fiber chopped strand, flatness 4, short diameter 7 ⁇ m, fiber length 3 mm, 625 ° C. ⁇ 0.5 hr ignition loss 0.54% by weight (C2) “MAFT2A” manufactured by Owen Corning as a glass fiber chopped strand having a circular cross section, a diameter of 13 ⁇ m, a fiber length of 3 mm, and a loss on ignition of 0.51 wt% at 625 ° C. ⁇ 0.5 hr.
  • Coupling agent used (D) (D1) “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as an aminosilane coupling agent (D2) “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd. as an epoxy silane coupling agent
  • Mold release agent manufactured by Clariant, Montanate ester wax “WE40” Stabilizer: “Irganox B1171” manufactured by Ciba Specialty Chemicals
  • Examples 1 to 15 and Comparative Examples 1 to 5 Dry blend of polyamide resin (A) and flame retardant (B) and other component (E) at the blending ratios shown in Tables 1 to 3, and vented twin screw extruder “TEX44 ⁇ ” (barrel) 14 block configuration) was melt-mixed under the extrusion conditions of a cylinder temperature of 280 ° C. and a screw rotation speed of 300 rpm, and then glass fiber (C) was supplied by a side feed method and melt-kneaded.
  • TEX44 ⁇ vented twin screw extruder
  • the method (I) of adding liquid from a block immediately after the glass fiber (C) is added or the polyamide resin (A) and the flame retardant (B) and other components (E) One of the methods (II) of dry blending together and charging from the main hopper was adopted. The strand extruded from the extruder was quenched and pelletized with a strand cutter. After the obtained pellets were dried at 100 ° C. for 12 hours, various test specimens were molded by an injection molding machine (Toshiba Machine Co., Ltd., IS80) at a cylinder temperature of 285 ° C. and a mold temperature of 100 ° C. for evaluation. Provided. The evaluation results are also shown in Tables 1 to 3.
  • test pieces of Examples 1 to 15 can achieve high flame retardancy, high strength, rigidity, and impact resistance.
  • test pieces of Comparative Examples 1 to 5 were inferior in any of the evaluation items as compared with those of Examples 1 to 15.
  • FIG. 1 An electron micrograph of the fracture surface of the Charpy impact strength test piece of Example 1 is shown in FIG.
  • the flat surface of the glass fiber well coated with resin is recognized, the resin and the flat cross-section glass have a strong coupling, and the flat cross-section glass fiber and the polyamide oriented in the plane direction are strong. Since it is bonded, the effect of reinforcing the surface is specifically high, and it can be confirmed that a crack is transmitted in the direction of the orientation surface.
  • FIG. 1 An electron micrograph of the fracture surface of the Charpy impact strength test piece of Comparative Example 1 is shown in FIG.
  • the coupling agent is blended in the composition, it can be seen that the glass fibers exposed on the fracture surface are hardly wetted by the matrix resin. Therefore, it can be understood why there is no reinforcing effect on the flat surface of the glass fiber and the mechanical properties and impact properties are remarkably inferior.
  • the glass fiber reinforced flame retardant polyamide resin composition of the present invention can achieve both high impact resistance and high flame retardant properties, despite being flame retardant with a non-halogen flame retardant.
  • Suitable for circuit breaker and switch cases, electric machines such as personal computers, electronic equipment cases and automotive electrical parts, and the resin composition of the present invention has a flat cross-section that can highly suppress warpage and deformation. Since glass fiber is used, the dimensional accuracy as a housing is outstanding.

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Abstract

L'invention porte sur une composition de résine de polyamide renforcée par des fibres de verre qui est obtenue par fusion et malaxage d'un mélange dans lequel 30 à 70 parties en poids de nappes de fibres de verre (C), qui sont composées de fibres de verre de section transversale plane présentant un degré de planéité de 1,5 à 8 et une perte au feu à 625 °C pendant 0,5 h inférieure ou égale à 0,8 % en poids, sont ajoutées à 25 à 50 parties en poids d'une résine de polyamide (A) et 2 à 20 parties en poids d'un agent ignifugeant au phosphore (B) qui n'est pas du phosphore rouge. La composition de résine de polyamide renforcée par des fibres de verre est caractérisée en ce que la résine de polyamide contient une résine de polycaproamide (a1) et/ou une résine de polyamide cristallin (a2) présentant un point de fusion supérieur d'au moins 20 °C à celui de la résine de polycaproamide (a1), et une résine de polyamide amorphe (a3) présentant un composant aromatique en un rapport pondéral ((a1) et/ou (a2))/(a3) de 90/10 à 35/65 et en ce qu'un agent de couplage de type silane réactif avec les polyamides (D) est ajouté dans le mélange à hauteur de 0,1 à 1,0 % en poids des nappes de fibres de verre (C) pendant le procédé de malaxage à l'état fondu. Malgré l'utilisation d'un agent ignifugeant non halogéné, la composition de résine de polyamide peut présenter à la fois des caractéristiques de résistance au choc élevées et un caractère ignifuge élevé, tout en atteignant une excellente productivité.
PCT/JP2010/000534 2009-01-29 2010-01-29 Composition de résine de polyamide ignifuge renforcée par des fibres de verre Ceased WO2010087193A1 (fr)

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WO2012152805A1 (fr) * 2011-05-10 2012-11-15 Basf Se Matière à mouler thermoplastique ignifuge
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JP2015017248A (ja) * 2013-06-13 2015-01-29 旭化成ケミカルズ株式会社 ガラス繊維強化ポリアミド樹脂組成物及び成形体
US9023922B2 (en) 2012-05-24 2015-05-05 Sabic Global Technologies B.V. Flame retardant compositions, articles comprising the same and methods of manufacture thereof
CN104987707A (zh) * 2015-07-29 2015-10-21 苏州新区华士达工程塑胶有限公司 一种增强阻燃汽车配件塑料
JP2018511685A (ja) * 2015-04-13 2018-04-26 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 難燃性ポリアミド組成物
JP2020530509A (ja) * 2017-08-11 2020-10-22 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 難燃性ポリアミド組成物およびそれらの使用
JP2022010813A (ja) * 2020-06-29 2022-01-17 東レ株式会社 樹脂組成物およびその成形品

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JP2013544921A (ja) * 2010-10-28 2013-12-19 クラリアント・ファイナンス・（ビーブイアイ）・リミテッド 難燃性ポリエステル化合物
WO2012152805A1 (fr) * 2011-05-10 2012-11-15 Basf Se Matière à mouler thermoplastique ignifuge
JP2014513191A (ja) * 2011-05-10 2014-05-29 ビーエーエスエフ ソシエタス・ヨーロピア 難燃化された熱可塑性成形材料
US9023922B2 (en) 2012-05-24 2015-05-05 Sabic Global Technologies B.V. Flame retardant compositions, articles comprising the same and methods of manufacture thereof
US8927661B2 (en) 2012-05-24 2015-01-06 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US9018286B2 (en) 2012-05-24 2015-04-28 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US8841367B2 (en) 2012-05-24 2014-09-23 Sabic Innovative Plastics Ip B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US9023923B2 (en) 2012-05-24 2015-05-05 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US8895649B2 (en) 2012-05-24 2014-11-25 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US9394483B2 (en) 2012-05-24 2016-07-19 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
JP2015017248A (ja) * 2013-06-13 2015-01-29 旭化成ケミカルズ株式会社 ガラス繊維強化ポリアミド樹脂組成物及び成形体
JP2018511685A (ja) * 2015-04-13 2018-04-26 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 難燃性ポリアミド組成物
CN104987707A (zh) * 2015-07-29 2015-10-21 苏州新区华士达工程塑胶有限公司 一种增强阻燃汽车配件塑料
JP2020530509A (ja) * 2017-08-11 2020-10-22 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 難燃性ポリアミド組成物およびそれらの使用
JP7252199B2 (ja) 2017-08-11 2023-04-04 クラリアント・インターナシヨナル・リミテツド 難燃性ポリアミド組成物およびそれらの使用
JP2022010813A (ja) * 2020-06-29 2022-01-17 東レ株式会社 樹脂組成物およびその成形品
JP7512708B2 (ja) 2020-06-29 2024-07-09 東レ株式会社 樹脂組成物およびその成形品

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