Classifications

• • 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
  • 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
  • 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
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/014—Stabilisers against oxidation, heat, light or ozone
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
• • 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
  • C08K9/00—Use of pretreated ingredients
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

• the present invention relates to a polyamide resin composition.
• polyamide resins Due to its excellent mechanical properties, heat resistance, and chemical resistance, polyamide resins are widely used as engineering plastics for automobile parts, mechanical parts, sliding parts, electrical and electronic parts, etc.
• Patent Documents 1 and 2 In order to improve slidability and strength when used for these applications, there is known a polyamide resin composition in which a cross-linking agent is added to a polyamide resin (see, for example, Patent Documents 1 and 2).
• Patent Documents 1 and 2 polyamide 46, polyamide 66, polyamide 6, polyamide 9T, polyamide 6/11, etc. are used as polyamide resins.
• a polyamide resin composition is irradiated with active energy rays to crosslink a crosslinking agent, thereby improving the slidability and strength.
• Patent Document 3 discloses a polyamide resin composition that contains a cross-linking agent but has improved creep properties without being directly irradiated with active energy rays.
• an object of the present invention is to provide a polyamide resin composition having good mechanical properties such as tensile properties, bending properties and impact resistance, low water absorption, and not too high density.
• the present invention is, for example, the following [1] to [8].
• the aliphatic polyamide resin (A) is polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene dodecamide ( At least one homopolymer selected from the group consisting of polyamide 1212), polyundecaneamide (polyamide 11), and polydodecanamide (polyamide 12), and polyamide 6/12 copolymer and polyamide 6/66/12 copolymer
• the cross-linking agent (C) is at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, diallyl phthalate, and diallylbenzene phosphonate
• the glass fiber (B) is surface-treated with a surface-treating agent and/or a binder.
• [7] A molded article of the polyamide resin composition according to any one of [1] to [6].
• [8] A crosslinked polyamide resin composition obtained by irradiating the molded body of the polyamide resin composition of [7] with active energy rays.
• the crosslinked polyamide resin composition of [8] having a density of 1.20 to 1.28 g/ml.
• the polyamide resin composition of the present invention has good mechanical properties such as tensile properties, bending properties and impact resistance, low water absorption, and not too high density.
• the polyamide resin composition of the present invention includes, in 100% by mass of the polyamide resin composition, an aliphatic polyamide resin (A) 55 to 78% by mass, a glass fiber (B) 20 to 35% by mass, and a cross-linking agent (C) 1 to 9. 0.1 to 1.5% by mass of a heat-resistant agent (D) and 0 to 6% by mass of an inorganic filler (E) other than glass fiber, and the aliphatic polyamide resin (A) contains one amide group.
• the average number of carbon atoms for is greater than 6.
• the said content is the value which rounded off the lower 1 digit of the value described.
• the polyamide resin composition contains an aliphatic polyamide resin (A).
• the aliphatic polyamide resin (A) has an average number of carbon atoms of more than 6 per amide group.
• Aliphatic polyamide resins include aliphatic homopolyamide resins and aliphatic copolyamide resins.
• An aliphatic homopolyamide resin is a polyamide resin composed of one type of structural unit derived from an aliphatic monomer.
• the aliphatic homopolyamide resin may consist of at least one aminocarboxylic acid that is one type of lactam and a hydrolyzate of the lactam, and consists of a combination of one type of diamine and one type of dicarboxylic acid. can be anything.
• Aliphatic copolyamide resins are polyamide resins composed of two or more structural units derived from aliphatic monomers.
• Aliphatic copolyamide resins are copolymers of two or more selected from the group consisting of combinations of diamines and dicarboxylic acids, lactams and aminocarboxylic acids.
• the combination of diamine and dicarboxylic acid is regarded as one type of monomer in combination of one type of diamine and one type of dicarboxylic acid.
• the aliphatic polyamide resin (A) is an aliphatic homopolyamide having an average number of carbon atoms of more than 6 per amide group; an aliphatic polyamide having an average number of carbon atoms of more than 6 per amide group.
• Aliphatic polyamide copolymers having more than 6 carbon atoms are preferred.
• An aliphatic homopolyamide resin having an average number of carbon atoms of more than 6 per amide group means that, when the constituent units of the polyamide are derived from lactam and aminocarboxylic acid, all the constituent units contain 6 carbon atoms. It means to exceed When the structural unit is derived from a combination of a diamine and a dicarboxylic acid, it means that the sum of the total number of carbon atoms contained in the diamine and the total number of carbon atoms contained in the dicarboxylic acid divided by 2 exceeds 6. That is, the average number of carbon atoms also includes the number of carbon atoms in the amide group.
• An aliphatic copolymerized polyamide resin having an average number of carbon atoms of more than 6 per amide group is obtained by determining the number of carbon atoms per amide group of each structural unit constituting the copolymer as described above, and It means that the average number of carbon atoms in the copolymer obtained by multiplying the molar concentration of each structural unit in the coalescence by the number of carbon atoms per amide group of each structural unit exceeds 6.
• the aliphatic polyamide resin (A) has an average number of carbon atoms of more than 6, preferably 7 to 12, more preferably 10 to 12, per amide group.
• the melting point of the aliphatic polyamide resin (A) is preferably 170-210°C, more preferably 175-200°C. Melting points are measured using a differential scanning calorimeter in accordance with ISO 11357-3 by heating a sample to a temperature above the expected melting point and then cooling the sample at a rate of 10°C per minute. , cooled to 30°C, left for about 1 minute, and then heated at a rate of 20°C per minute.
• the terminal amino group concentration of the aliphatic polyamide resin (A) is preferably in the range of 20 ⁇ mol / g or more, and 20 ⁇ mol / g or more and 60 ⁇ mol / g or less is more preferable, and the range of 25 ⁇ mol/g or more and 35 ⁇ mol/g or less is particularly preferable. Within the above range, sufficient moldability and mechanical properties can be obtained.
• Aliphatic homopolyamide resins having an average number of carbon atoms of more than 6 per amide group include polyenantholactam (polyamide 7), polyundecanelactam (polyamide 11), polylauryllactam (polyamide 12), polytetramethylenedodeca Polyamide (Polyamide 412), Polypentamethylene Adipamide (Polyamide 56), Polypentamethylene Azelamide (Polyamide 59), Polypentamethylene Sebacamide (Polyamide 510), Polypentamethylene Dodecamide (Polyamide 512), Polyhexamethylene Methylene Sveramide (Polyamide 68), Polyhexamethylene Azelamide (Polyamide 69), Polyhexamethylene Sebacamide (Polyamide 610), Polyhexamethylene Undecamide (Polyamide 611), Polyhexamethylene Dodecamide (Polyamide 612), Polyhexamethylene tetradecamide (polyamide 614), polyhexamethylene hexadecamide (
• aliphatic copolyamide resin having an average number of carbon atoms of more than 6 per amide group raw material monomers forming an aliphatic homopolyamide resin having an average number of carbon atoms of more than 6 per amide group are used.
• caprolactam/hexamethylenediaminoazelaic acid copolymer (polyamide 6/69), caprolactam/hexamethylenediaminosebacic acid copolymer (polyamide 6/610), caprolactam/hexamethylenediaminoundecane Dicarboxylic acid copolymer (polyamide 6/611), caprolactam/hexamethylenediaminododecanedicarboxylic acid copolymer (polyamide 6/612), caprolactam/aminoundecanoic acid copolymer (polyamide 6/11), caprolactam/lauryllactam copolymer Polymer (polyamide 6/12), caprolactam/hexamethylenediaminoadipic acid/lauryllactam copolymer (polyamide 6/66/12), caprolactam/hexamethylenediaminoadipic acid/hexamethylenediaminosebacic acid copolymer (polyamide 6/
• the aliphatic polyamide resin (A) is polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012). , at least one homopolymer selected from the group consisting of polydodecanamide (polyamide 1212), polyundecaneamide (polyamide 11), and polydodecanamide (polyamide 12), and polyamide 6/12 copolymer and polyamide At least one selected from the group consisting of at least one copolymer selected from the group consisting of 6/66/12 copolymers is preferred, and polydodecanamide (polyamide 12) is more preferred.
• the aliphatic polyamide resin (A) is contained in an amount of 55-78% by mass, preferably 58-70% by mass, in 100% by mass of the polyamide resin composition. If the content of the aliphatic polyamide resin (A) is less than the above range, molding is difficult, and if it exceeds the above range, mechanical properties are not sufficiently exhibited.
• the polyamide resin composition contains glass fibers (B).
• a fiber refers to a shape having a fiber length of 0.3 mm or more and an aspect ratio (fiber length/diameter ratio) of 10 or more.
• the glass fiber (B) in the polyamide resin composition includes broken glass fiber (B) due to melt-kneading, as described later. Therefore, the content of the glass fibers (B) in the polyamide resin composition includes those that do not meet the definition of "fiber” in this specification as a result of breaking.
• the content of the glass fiber (B) in the polyamide resin composition matches the blending amount of the raw material glass fiber.
• the glass fiber (B) may be surface-treated with a surface treatment agent and/or a binder.
• these surface treatment agents may be aggregated or granulated.
• Surface treatment agents and binders include various coupling agents such as silane coupling agents, titanium coupling agents, aluminum coupling agents, and zirconia coupling agents; water glass, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl Cellulose, starch, polyvinyl alcohol, acrylic resins, epoxy resins, phenol resins, polyvinyl acetate, polyurethane resins, epoxy compounds, isocyanate compounds, colloidal silica, colloidal alumina, fatty acids, surfactants and the like can be mentioned.
• the surface treatment agent and binder may be used alone or in combination of two or more.
• the surface treatment agent and the binder are applied to the glass fibers (B) in advance and dried for surface treatment or convergence treatment, or are added at the same time as the glass fibers (B) during preparation of the resin composition.
• the raw material glass fiber those with an average fiber diameter of 3 to 23 ⁇ m can be used.
• the average fiber diameter is preferably 6 to 23 ⁇ m, for example, 10 to 23 ⁇ m, from the viewpoint of dimensional stability and mechanical properties of molded articles made of the composition.
• the glass fibers may be used alone or in combination of two or more. Two or more types of glass fibers having different average fiber diameters may be used. Examples of combinations of glass fiber diameters include (B1) a glass fiber having an average fiber diameter of 6 to 11 ⁇ m and (B2) a glass fiber having an average fiber diameter of 13 to 25 ⁇ m.
• the raw material glass fiber length (cut length) is not particularly limited, and chopped strands of 1 mm to 50 mm can be used, and 3 mm to 10 mm is more preferable from the viewpoint of productivity.
• the average fiber length of the glass fibers in the polyamide resin composition is not particularly limited, and is preferably 50 ⁇ m to 1,000 ⁇ m. 100 ⁇ m to 500 ⁇ m, more preferably more than 200 ⁇ m and 400 ⁇ m or less, from the viewpoint of
• the above values for the average fiber diameter of the glass fiber and the raw glass fiber length (cut length) are the values before melting and kneading with the polyamide.
• the value of the average fiber length of the glass fibers in the polyamide resin composition is the value after melt-kneading with the polyamide.
• the value after melt-kneading takes into consideration the case where at least part of the glass fibers are broken and dispersed in the composition during the melt-kneading of raw materials in the production process of the polyamide composition.
• the average fiber diameter of the raw material glass fiber and the raw material glass fiber length (cut length) can be observed using an optical microscope.
• the average fiber diameter of the raw material glass fiber (B) and the raw material glass fiber length (cut length) may be catalog values.
• the average fiber length of the glass fibers in the polyamide resin composition can be observed with an optical microscope after dissolving the polyamide resin in the polyamide resin composition using a solvent and separating it from the glass fibers. About 1,000 arbitrarily selected glass fibers are measured from the observed image using image analysis software, and the average value is determined to be the average fiber length.
• glass fibers include Nippon Electric Glass Co., Ltd. under the product names ECS 03T-249, ECS 03T-249H, ECS 03T-275, ECS 03T-275H, ECS 03T-289, ECS 03T-289H, and ECS 03T-289DE. , ECS 03T-920EW, HP3610XM, product names of Nitto Boseki Co., Ltd. CS 3DE-456S, CSG 3J-820, CSG 3PA-820S, CS 3SH-223, CS 3PE-454, and the like.
• the glass fiber (B) is contained in an amount of 20 to 35% by mass, preferably 25 to 33% by mass, in 100% by mass of the polyamide resin composition. If the blending amount of the glass fiber (B) is less than the above range, the mechanical properties are poor. If the blending amount of the glass fiber (B) is more than the above range, moldability may become difficult.
• the polyamide resin composition contains a cross-linking agent (C).
• the cross-linking agent (C) include polyfunctional acrylic monomers, polyfunctional allyl monomers, mixed monomers thereof, and the like. More specific examples include, for example, polyfunctional acrylic monomers such as ethylene oxide-modified bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipentaerythritol hexa Acrylate, dipentaerythritol monohydroxy pentaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, EO-modified Trimethylolpropane triacrylate,
• polyfunctional allyl-based monomers examples include triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, diallyl phthalate, diallylbenzene phosphonate, and mixtures thereof.
• An initiator, catalyst, stabilizer, etc. can be added to the cross-linking agent as needed. These initiators, catalysts, stabilizers, etc. may be added to the cross-linking agent or to the polyamide resin.
• the cross-linking agent (C) is contained in an amount of 1 to 9% by mass, preferably 2 to 7% by mass, more preferably 3 to 6% by mass in 100% by mass of the polyamide resin composition. If the amount of the cross-linking agent (C) is less than the above range, the state of cross-linking will be insufficient, and strength such as tensile strength and tensile elastic modulus will be inferior. When the amount of the cross-linking agent (C) is more than the above range, it adversely affects impact resistance such as elongation and impact strength.
• the polyamide resin composition contains a heat resistant agent.
• a heat resistant agent those capable of improving the heat resistance and antioxidation resistance of the molded article can be used.
• Organic or inorganic heat-resistant agents can be used depending on the purpose, but inorganic heat-resistant agents are preferred. These may be used individually by 1 type, or may be used in combination of 2 or more types.
• Organic heat resistant agent examples include phenol compounds, phosphorus compounds, sulfur compounds, and nitrogen compounds. These may be used individually by 1 type, or may be used in combination of 2 or more types.
• a hindered phenolic compound is preferably used as the phenolic compound.
• hindered phenol refers to a compound having a substituent at the ortho-position (hereinafter also referred to as "o-position") of the hydroxyl group of phenol.
• the substituent at the o-position is not particularly limited, but includes an alkyl group, an alkoxy group, an amino group, a halogen, and the like.
• alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group and t-butyl group are preferred, and bulky i- A propyl group, a sec-butyl group, an i-butyl group and a t-butyl group are more preferred, and a t-butyl group is most preferred.
• it is preferable that both of the two o-positions with respect to the hydroxyl group of the phenol have a substituent.
• Hindered phenols having a t-butyl group at the o-position specifically include N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), pentaerythritol -tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate ], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetra oxaspiro[5.5]undecane, may be mentioned.
• a hindered phenol phosphite compound and a hindered phenol hypophosphite compound are preferable, and a hindered phenol phosphite compound having a t-butyl group at the o-position, A hindered phenol hypophosphite compound having a t-butyl group is more preferred, and a hindered phenol phosphite compound having a t-butyl group at the o-position is even more preferred.
• Phosphite ester compounds of hindered phenols having a t-butyl group at the o-position are specifically tris(2,4-di-t-butylphenyl) phosphite, bis(2,6-di-t -Butyl-4-methylphenyl)pentaerythritol diphosphite.
• hypophosphite ester compound of a hindered phenol having a t-butyl group at the o-position is p,p,p',p'-tetrakis(2,4-di-tert-butylphenoxy)-
• Commercially available products of these heat resistant agents include "Irgafos (registered trademark) 168" (BASF) and "Hostanox (registered trademark) P-EPQ” (Clariant Chemicals). These may be used individually by 1 type, or may be used in combination of 2 or more types.
• sulfur compound examples include distearyl-3,3-thiodipropionate, pentaerythrityltetrakis(3-laurylthiopropionate), and didodecyl(3,3'-thiodipropionate). These may be used individually by 1 type, or may be used in combination of 2 or more types.
• Nitrogen compounds include melamine, melamine cyanurate, benguanamine, dimethylol urea, and cyanuric acid. These may be used individually by 1 type, or may be used in combination of 2 or more types.
• the organic heat-resistant agent is preferably a phenol-based compound or a phosphorus-based compound, more preferably a hindered phenol-based compound.
• inorganic heat-resistant agents for heat-resistant agents include copper compounds and potassium halides, and copper compounds include cuprous iodide, cuprous bromide, and cupric bromide. , copper acetate and the like. Cuprous iodide is preferred from the viewpoint of heat resistance and suppression of metal corrosion. Potassium halides include potassium iodide, potassium bromide, potassium chloride and the like. Potassium iodide and/or potassium bromide are preferred from the viewpoint of heat resistance and long-term stability of the inorganic heat resistant agent. These may be used individually by 1 type, or may be used in combination of 2 or more types.
• cuprous iodide and potassium iodide and/or potassium bromide is preferred.
• nitrogen-containing compounds such as melamine, melamine cyanurate, benguanamine, dimethylol urea or cyanuric acid in combination.
• the heat-resistant agent (D) is 0.1 to 1.5% by mass, more preferably 0.2 to 1.3% by mass, more preferably 0.3 to 1.2% by mass %included. If the amount of the heat-resistant agent is less than the above range, the molded article may be thermally deteriorated.
• the polyamide resin composition preferably contains an inorganic filler other than glass fiber as an optional component.
• inorganic fillers include wollastonite, potassium titanate whiskers, zinc oxide whiskers, carbon fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, sericite, kaolin, mica.
• silicates such as clay, bentonite, asbestos, talc and alumina silicate; swelling layered silicates such as montmorillonite and synthetic mica; metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; glass flakes, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica; It is preferably at least one selected from the group consisting of talc and glass milled fibers. These may be used singly or in combination of two or more.
• the average particle size of talc is preferably 1-20 ⁇ m, more preferably 2-15 ⁇ m.
• the average particle size of talc is the average particle size determined by a particle size distribution measurement method using a laser diffraction/scattering method. Examples of the measuring device include laser diffraction particle size distribution measuring device SALD-7000 manufactured by Shimadzu Corporation. When using a commercial product as talc, the average particle size of talc adopts the catalog value of the commercial product.
• the average fiber length of the glass milled fiber is measured after pulverizing each fiber, preferably 10 to 200 ⁇ m, more preferably 30 to 150 ⁇ m.
• the average fiber length can be determined by, for example, a glass fiber length measuring machine, but when using a commercial product as the glass milled fiber, the catalog value of the commercial product is used.
• the fiber diameter of the glass milled fiber is preferably 2-30 ⁇ m, more preferably 5-15 ⁇ m.
• the fiber diameter of the glass milled fiber can be determined by an image analyzer using, for example, optical microscope observation. When using a commercial product as the glass milled fiber, the catalog value of the commercial product is used.
• the inorganic filler (E) other than glass fiber is contained in 0 to 6% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass in 100% by mass of the polyamide resin composition.
• the content of the inorganic filler (E) other than the glass fiber is within the above range, the mechanical properties of the molded product are improved.
• the polyamide resin composition may contain optional components such as dyes, pigments, particulate reinforcing materials, plasticizers, antioxidants, foaming agents, weathering agents, crystal nucleating agents, crystallization accelerators, lubricants, antistatic A functional agent such as an agent, a flame retardant, a flame retardant auxiliary, a coloring agent, and the like may be contained as appropriate.
• optional additive may be contained in an amount of preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on 100% by mass of the polyamide resin composition.
• the polyamide resin composition may contain a thermoplastic resin other than the aliphatic polyamide resin (A).
• the thermoplastic resin other than the aliphatic polyamide resin (A) is preferably 2% by mass or less in 100% by mass of the polyamide resin composition, more preferably less than 0.1% by mass, from the viewpoint of mechanical properties and moldability. , more preferably not included.
• the method for producing the polyamide resin composition is not particularly limited, and for example, the following method can be applied.
• Aliphatic polyamide resin (A), glass fiber (B), cross-linking agent (C), heat-resistant agent (D), and other optional components are mixed using a single-screw or twin-screw extruder or a Banbury mixer. , a kneader, and a mixing roll are generally used.
• a method of melt-kneading for example, using a twin-screw extruder, after blending all the raw materials, a method of melt-kneading, a method of blending a part of the raw materials, melt-kneading, further blending the remaining raw materials and melt-kneading, or part Any method may be used, such as a method of mixing the remaining raw materials using a side feeder during melt-kneading after blending the raw materials.
• the polyamide resin composition can be suitably used for producing an injection molded article by injection molding, an extruded article by extrusion molding, a blow molded article by blow molding, and a rotomolded article by rotational molding. Since the polyamide resin composition has good injection moldability, it can be preferably used for an injection molded article by injection molding.
• the method for producing an injection-molded article from the polyamide resin composition by injection molding is not particularly limited, and a known method can be used. For example, a method conforming to ISO294-1 is taken into consideration.
• the method for producing an extrudate from the polyamide resin composition by extrusion molding is not particularly limited, and known methods can be used. It is also possible to obtain a multi-layered structure by co-extrusion with polyolefin such as polyethylene or other thermoplastic resin, followed by blow molding. In that case, it is possible to provide an adhesive layer between the polyamide resin composition layer and another thermoplastic resin layer such as polyolefin. In the case of multilayer structures, the polyamide resin composition of the present invention can be used for both the outer layer and the inner layer.
• the method for producing a blow-molded article from a polyamide resin composition by blow molding is not particularly limited, and a known method can be used.
• blow molding may be carried out after the parison is formed using an ordinary blow molding machine.
• the preferred resin temperature during parison formation is preferably in the range of 10° C. to 70° C. higher than the melting point of the polyamide resin composition.
• the method for producing a rotomolded product from a polyamide resin composition by rotomolding is not particularly limited, and a known method can be used. For example, the method described in International Publication 2019/054109 is taken into consideration.
• the injection-molded body by injection molding, the extrusion-molded body by extrusion molding, the blow-molded body by blow molding, and the rotational-molded body by rotational molding are not particularly limited, but include spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, Automotive parts such as gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, and various other hoses, tubes, and tanks; mechanical parts such as power tool housings and pipes; - Suitable for various applications such as electronic parts, household/office supplies, building material-related parts, and furniture parts.
• parts that are used in environments where the temperature environment fluctuates greatly such as heat resistance and cold resistance.
• driving parts such as gears and belts in the field of vehicles such as automobiles
• sliding parts such as tire sidewalls and belts.
• driving parts such as gears and belts in the field of vehicles such as automobiles
• sliding parts such as tire sidewalls and belts.
• driving parts such as gears and belts in the field of vehicles such as automobiles
• sliding parts such as tire sidewalls and belts.
• it is preferably used for automobile parts, sliding parts or electrical/electronic parts.
• the polyamide resin composition has excellent gas barrier properties, it is suitably used for molded articles that come into contact with high-pressure gas, such as tanks, tubes, hoses, and films that come into contact with high-pressure gas.
• high-pressure gas such as tanks, tubes, hoses, and films that come into contact with high-pressure gas.
• the type of gas is not particularly limited, and includes hydrogen, nitrogen, oxygen, helium, methane, butane, propane, etc. Gases with low polarity are preferred, and hydrogen, nitrogen, and methane are particularly preferred.
• polyamide resin composition of the present invention can be used for both outer layers and inner layers.
• the density of the molded body made of the polyamide resin composition is preferably 1.20-1.28 g/ml, more preferably 1.22-1.26 g/ml. When the density is within the above range, the molded article has good mechanical properties.
• the polyamide resin composition as a crosslinked product of the polyamide resin composition by irradiating an active energy ray to a molded product made of the polyamide resin composition.
• active energy rays include ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, ion rays, particle rays, X rays, and ⁇ rays, and ultraviolet rays and electron rays are preferred.
• a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used as the ultraviolet light source.
• the irradiation time can be appropriately changed depending on conditions such as the type of compound having a polymerizable unsaturated bond, the type of photopolymerization initiator, the coating thickness, and the UV source. From the viewpoint of workability, it is preferable to irradiate for 1 to 60 seconds.
• heat treatment may be performed after irradiation with ultraviolet rays.
• the dose of ultraviolet rays used for curing the composition of the present invention is preferably 300 to 3,000 mJ/cm 2 from the viewpoints of rapid curing and workability.
• An electron beam or the like can also be used as an active energy ray.
• a photopolymerization initiator may not be added, and an electron beam accelerator having an energy of 100 to 500 eV is preferably used.
• the density of the crosslinked body of the polyamide resin composition after electron beam irradiation is preferably 1.20 to 1.28 g/ml, more preferably 1.22 to 1.26 g/ml. When the density is within the above range, the mechanical properties of the crosslinked product are good.
• the uses of the crosslinked polyamide resin composition include the same uses as the uses of the molded articles of the polyamide resin composition described above.
• ⁇ Relative viscosity> It is a value measured at 25° C. by dissolving 1 g of polyamide resin in 100 ml of 96% concentrated sulfuric acid according to JIS K6920-2.
• ⁇ Melting point> According to ISO 11357-3, a differential scanning calorimeter is used to heat a sample to a temperature above the expected melting point, then cool the sample at a rate of 10°C per minute to 30°C. After cooling to , and left as it is for about 1 minute, the temperature of the peak value of the melting curve measured by heating at a rate of 20°C per minute was taken as the melting point. A value of less than 200° C. before electron beam irradiation was considered acceptable, and a value of less than 200° C. after electron beam irradiation was considered acceptable.
• Tensile strength and tensile breaking strain Measured at 23° C. using an Instron tensile tester model 5567 according to ISO527. Regarding the tensile strength, a value of more than 120 MPa before electron beam irradiation was considered acceptable, and a value of 125 MPa or more after electron beam irradiation was considered acceptable. Regarding the tensile breaking strain, a value of 8% or less before electron beam irradiation was considered acceptable, and a value of 6% or less after electron beam irradiation was considered acceptable.
• Examples 1 to 4, Comparative Examples 1 to 5 Each component described in Table 1 is melt-kneaded with a twin-screw kneader ZSK32-Mc, cylinder diameter 32 mm L / D47, cylinder temperature 220 ° C., screw rotation 220 rpm, discharge rate 40 kg / hrs, and the desired polyamide resin composition material pellets were prepared.
• a test piece was prepared from the obtained polyamide resin composition pellets by the above method and used for evaluation before electron beam irradiation.
• the test piece used for evaluation before electron beam irradiation was irradiated with an electron beam of 100 kGy and an electron beam energy of 4.8 MeV, and used for evaluation after electron beam irradiation.
• Table 1 shows the results.
• the unit of composition in the table is % by mass, and the total resin composition is 100% by mass.
• PA12 (1) polyamide 12, relative viscosity 2.2, melting point 179 ° C., terminal amino group concentration 33 ⁇ mol / g, manufactured by Ube Industries, Ltd.
• PA12 (2) polyamide 12, relative viscosity 2.2, melting point 179 ° C., terminal Amino group concentration 22 ⁇ mol / g, manufactured by Ube Industries, Ltd.
• PA12 (3) polyamide 12, relative viscosity 2.5, melting point 178 ° C., terminal amino group concentration 23 ⁇ mol / g, manufactured by Ube Industries, Ltd.
• PA12 (4) polyamide 12, relative viscosity 1.9, melting point 179 ° C., terminal Amino group concentration 27 ⁇ mol / g
• PA6 manufactured by Ube Industries, Ltd. polyamide 6, relative viscosity 2.6, melting point 220 ° C., terminal amino group concentration 36 ⁇ mol / g
• Heat resistant agent 1:6 mixture of cuprous iodide and potassium iodide Crystallization accelerator (inorganic filler): Microace (registered trademark) L-1, average particle size D50: 5 ⁇ m (manufactured by Nippon Talc Co., Ltd.)
• Comparing Examples 1 to 5 with Comparative Example 1 it can be seen that when the amount of polyamide resin is less than the range of the present invention and the amount of glass fiber is greater, the density increases both before and after electron beam irradiation. . Comparing Examples 1 to 5 with Comparative Example 2, it can be seen that the density increases both before and after electron beam irradiation when the amount of glass fiber is larger than the range of the present invention without containing a cross-linking agent. Comparing Examples 1 to 5 with Comparative Example 3, it can be seen that the values of flexural strength and flexural modulus are low both before and after electron beam irradiation when the cross-linking agent is not included.
• Examples 1 to 5 and Comparative Example 4 A comparison between Examples 1 to 5 and Comparative Example 4 reveals that the use of polyamide 6 as the polyamide resin results in a high density before electron beam irradiation and a high water absorption rate. Comparing Examples 1 to 5 with Comparative Example 5, it can be seen that the flexural strength and flexural modulus values are low and the water absorption is high both before and after electron beam irradiation when glass fibers are not included. I understand.
• the polyamide resin composition can be used as an injection-molded article by injection molding, an extrusion-molded article by extrusion molding, a blow-molded article by blow molding, and a rotomolded article by rotational molding. These molded products and their crosslinked products are particularly suitable for automobile parts, sliding parts, or electric/electronic parts.

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• 2022
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