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WO2006003998A1 - Résine polyamide et moulages à couches multiples - Google Patents

Résine polyamide et moulages à couches multiples Download PDF

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Publication number
WO2006003998A1
WO2006003998A1 PCT/JP2005/012092 JP2005012092W WO2006003998A1 WO 2006003998 A1 WO2006003998 A1 WO 2006003998A1 JP 2005012092 W JP2005012092 W JP 2005012092W WO 2006003998 A1 WO2006003998 A1 WO 2006003998A1
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WIPO (PCT)
Prior art keywords
polyamide resin
polyamide
resin according
polymer
acid
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PCT/JP2005/012092
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English (en)
Japanese (ja)
Inventor
Kazunobu Sato
Tomomichi Kanda
Masashi Kurokawa
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Mitsubishi Gas Chemical Company, Inc.
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Application filed by Mitsubishi Gas Chemical Company, Inc. filed Critical Mitsubishi Gas Chemical Company, Inc.
Publication of WO2006003998A1 publication Critical patent/WO2006003998A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/46—Post-polymerisation treatment

Definitions

  • the present invention relates to a polyamide resin having a specific composition and a multilayer molded article that has been subjected to a specific heat treatment. Specifically, the present invention relates to barrier properties, mechanical properties, chemical resistance, heat resistance and the like. In addition, the present invention relates to a heat-treated polyamide resin having excellent moldability and a multilayer molded body.
  • Polyamides are widely used as materials for injection molded articles such as automobiles and electric / electronic parts because they have excellent mechanical performance. It is also used as a packaging material for food, beverages, medicines, electronic components, and so on.
  • polyamides obtained by polycondensation reaction of xylylenediamine and aliphatic dicarboxylic acids hereinafter referred to as “MX nylon”
  • MX nylon polyamides obtained by polycondensation reaction of xylylenediamine and aliphatic dicarboxylic acids
  • polyamides polyamides that can also obtain metaxylylenediamine and adipic acid power
  • MXD6 metaxylylenediamine and adipic acid power
  • MXD6 has low permeability to gaseous substances such as oxygen and carbon dioxide, it is used as a gas barrier material in molded articles such as films and bottles.
  • Fuel containers are usually molded by the direct blow method. Since the conventional noria materials described above are inferior in heat resistance, gels are liable to occur due to the retention of the resin if the temperature of the resin increases during molding. For this reason, it is difficult to recycle burrs generated during molding, or it is necessary to switch to a resin with excellent thermal stability when operating and shutting down the equipment. There is a problem with effective use. In particular, in direct pro-molding, if the melt viscosity of the resin is low, drawdown occurs, resulting in problems such as the thickness of the resulting product being too thin or uneven thickness. On the other hand, if the molding temperature is too high, the polyolefin used for the outer layer is melted to lower the viscosity and cause drawdown, which is not preferable.
  • Patent Document 1 Japanese Patent Laid-Open No. 3-32815
  • Patent Document 2 JP-A-5-345349
  • Patent Document 3 JP-A-6-340033
  • Patent Document 4 JP-A-9-29904
  • Patent Document 5 Japanese Patent Laid-Open No. 2001-97053
  • the present invention is intended to solve the above-mentioned problems of the prior art and to provide a noria material excellent in barrier properties, mechanical properties, chemical resistance, heat resistance and moldability.
  • polyamide resin having a specific monomer composition ratio obtained by melt polycondensation by further heat-treating under specific conditions.
  • the present inventors have found that polyamide resin has excellent barrier properties, mechanical properties, chemical resistance, heat resistance and moldability, and have completed the present invention.
  • the present invention comprises a diamine unit and a dicarboxylic acid unit
  • 70 is the mole 0/0 or more force xylylene ⁇ Min units, 70 mole 0/0 or more of the dicarboxylic acid unit having 4 to 20 carbon atoms a, .omega.-linear aliphatic dicarboxylic acid unit and isophthalic acid unit
  • Polymer ⁇ obtained by melt polycondensation which is a mixed dicarboxylic acid unit having a molar ratio of 30: 70-95: 5, is present in the presence of 1 to 30% by weight of water with respect to polymer A, and Crystallization by maintaining at 70 to 120 ° C for 0.5 to 4 hours under an inert gas stream or under reduced pressure, and then the melting point of polymer A—50 ° C. to melting point of polymer A—10
  • the present invention relates to a polyamide resin (heat treated polyamide resin) obtained by heat treatment for 1 to 12 hours at a temperature of °
  • the present invention also relates to a multilayer molded body comprising at least one barrier layer made of the heat-treated polyamide resin and another layer having another thermoplastic resin power.
  • the heat-treated polyamide resin of the present invention is obtained by crystallizing a polyamide resin (polymer A) obtained by polycondensation of a diamine component and a dicarboxylic acid component in a molten state, and further calo-heat-treating under specific conditions. Is obtained.
  • heat-treated polyamide resin 70 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more (including 100 mol% of each) of diamine units is metaxylylenediamine units.
  • diamine components other than metaxylylenediamine include aliphatic diamines such as tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, otamethylene diamine, nonamethylene diamine, para-phenylenediamine, And diamines having an aromatic ring such as paraxylylenediamine; and alicyclic diamines such as bis (aminomethyl) cyclohexane.
  • Heat treatment polyamide ⁇ is a unit derived from di Amin components other than the m-xylylenediamine ⁇ Min, may contain 30 mole 0/0 following total Jiamin units (including zero).
  • 70 mol% or more of dicarboxylic acid units preferably 80 mol% or more, more preferably 90 mol% or more (each including 100 mol%) is a 4 or 20 carbon atoms, ⁇ —A mixed dicarboxylic acid unit consisting of a linear aliphatic dicarboxylic acid unit and an isophthalic acid unit.
  • the molar ratio of ⁇ , ⁇ -linear aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms and isophthalic acid unit is 30:70 to 95: 5, preferably 40:60 to 95: 5, more preferably 50: 5 0 to 90:10, more preferably 60:40 to 85:15.
  • Isophthalic acid units within this range When included, the barrier properties against methanol, ethanol and methyl tert butyl ether (M TBE) are improved.
  • a, ⁇ linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid. Etc. can be illustrated. Of these, adipic acid is preferred.
  • the melting point of the heat-treated polyamide resin is reduced compared to the case where only the ex, ⁇ linear aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms is included. Since molding can be performed at a low temperature, the molding energy can be reduced and the molding cycle can be shortened. In addition, the melt viscosity of the heat-treated polyamide resin increases and molding defects such as drawdown can be avoided, so that molding processability is improved.
  • dicarboxylic acid components other than oc, ⁇ -linear aliphatic dicarboxylic acid and isophthalic acid having 4 to 20 carbon atoms include phthalic acid compounds such as terephthalic acid and orthophthalic acid, 1, 2 naphthalenedicarboxylic acid, 1, 3 Naphthalene dicarboxylic acid, 1, 4 naphthalene dicarboxylic acid, 1, 5 naphthalene dicarboxylic acid, 1, 6 naphthalene dicarboxylic acid, 1, 7 naphthalene dicarboxylic acid, 1, 8 naphthalene dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6 Naphthalenedicarboxylic acid such as isomers such as naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid.
  • phthalic acid compounds such as terephthalic acid and orthophthalic acid, 1, 2 naphthalenedicarbox
  • Heat treatment polyamide ⁇ is, oc of the 4 to 20 carbon atoms, a unit derived from a dicarboxylic acid component other than ⁇ -linear aliphatic dicarboxylic acid and isophthalic acid, the total dicarboxylic acid monomer position of 3 ⁇ mole o / 0 or less ( (Including zero).
  • the heat-treated polyamide resin is obtained by polymerizing the diamine component and the dicarboxylic acid component in a molten state to produce a polymer soot, crystallizing the polymer A, and further heat-treating under specific conditions. Manufactured from Yuko.
  • monocarboxylic acids such as benzoic acid, propionic acid and butyric acid
  • polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid
  • carboxylic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride, etc.
  • An amino acid such as an acid is effective for the present invention. It can be added within the range.
  • melt polycondensation for example, a nylon salt composed of metaxylylenediamine, adipic acid and isophthalic acid is heated in the presence of water under pressure, and polymerized in a molten state while removing the added water and condensed water. It can be done by a method.
  • metaxylylenediamine can be directly added to a molten adipic acid and isophthalic acid mixture and polycondensed under normal pressure.
  • methylylenediamine is continuously added to raise the reaction system so that the reaction temperature during the polycondensation is maintained above the melting point of the generated oligoamide and polyamide. It is preferable to proceed the polycondensation while warming.
  • Polymer A obtained by melt polycondensation has a terminal amino group concentration of 30-: LOO equivalent Zg, a terminal carboxyl group concentration of 100-30 equivalent Zg, a number average molecular weight of 11000-20000, and a melting point of 160-235 ° C.
  • the melt viscosity is preferably 200 to 2500 Pa's (100 sec_1 ).
  • the polymer A is gently heated in the presence of water in an inert gas atmosphere or under reduced pressure. After heating, and crystallizing while avoiding fusion; further heat treatment; using a grooved stirring and heating device, heating in an inert gas atmosphere to crystallize, then hopper shape A heat treatment in an inert gas atmosphere using a heating apparatus of the above; a method of performing a calorie heat treatment using a batch heating apparatus such as a rotating drum after crystallization using a groove type stirring heating apparatus, etc. Is mentioned. In particular, a method of crystallization and heat treatment using a batch heating apparatus is preferred.
  • the polymer A obtained by the melt polycondensation has a low crystallization rate, there is a risk of problems such as adhesion to the heating apparatus and adhesion between the pellets during the heat treatment. Therefore, it is preferable to perform the heat treatment after the crystallization treatment of the polymer A in advance. 1 to 30 weight 0/0 of water of the polymer A Ka ⁇ E, and gently heated at a heating rate of 0. 1 to 3 ° CZ min to around at 70 to 120, 0 at a temperature within the range. By maintaining for 5 to 4 hours, the crystallization of the polymer A proceeds, and the phenomenon of adhesion can be prevented if fusion occurs.
  • Crystallization may be carried out in air, but is preferably carried out in an inert gas atmosphere or under reduced pressure (preferably 0.1 to 3.5 kPa).
  • the number average molecular weight and viscosity of the polyamide resin increase, and draw-down when producing multilayer containers such as films, sheets, and bottles, sheet edges As a result, it is possible to obtain a heat-treated polyamide resin having excellent moldability.
  • the heat treatment is performed at a temperature ranging from the melting point of the polymer A—50 ° C. to the melting point of the polymer A 10 ° C. for 1 to 12 hours in an inert gas atmosphere or under reduced pressure (preferably 0.01 to 1.33 kPa). Preferably it is done.
  • the heat treatment temperature is lower than the melting point—50 ° C., the heat treatment is insufficient and the effect of improving the characteristics becomes insufficient.
  • the melting point is higher than 10 ° C
  • the polyamide resin adheres to the inner wall of the apparatus.
  • the treatment time is less than 1 hour, there is a problem that the heat treatment is insufficient, and if it exceeds 12 hours, the effect of improving the characteristics is small for the time.
  • the heat-treated polyamide resin of the present invention preferably has a number average molecular weight of 16000 to 50000, more preferably 17000 to 45000 force S. When the number average molecular weight is within the above range, mechanical properties, alcohol resistance, and processability are good.
  • the melting point of the heat-treated polyamide resin is preferably 160 to 230 ° C, more preferably 170 to 220 ° C, and still more preferably 180 to 210 ° C.
  • the melt viscosity at the shear rate lOOsec — 1 at the molding temperature (usually 165 to 235 ° C) of the heat-treated polyamide resin is preferably 2000 to 8000 Pa's, more preferably 2500 to 700. OPa's.
  • the melt viscosity of the heat-treated polyamide resin is within the above range, it is possible to avoid a drawdown and a decrease in mechanical strength when producing a multilayer molded body by a hollow molding method or the like. Polyamide resin exceeding the above range is preferable because it is difficult to produce and an excessive load force S is applied during molding.
  • the glass transition point of the heat-treated polyamide resin is preferably 90 to 130 ° C. When the glass transition point is 90 ° C or higher, it is excellent in the noria characteristics at high temperatures. Further, the fuel permeation amount of the heat-treated polyamide resin measured by the method used in the following examples is preferably 5 gZday or less, more preferably 0.1 to 5 gZday, and still more preferably 0.1 to 2 gZday.
  • the terminal amino group concentration is preferably 10 to 80 eq / g, more preferably 60 to 80 eq / g, still more preferably 60 to 75 eqZg, and the terminal carboxyl group concentration is preferably more preferably 80 to 10 eq. Is 50 to 10 eqZg, more preferably 40 to 15 eqZg.
  • the heat-treated polyamide resin may contain smectite (organic swelling smectite) treated with an organic swelling agent.
  • Smectite is a 2-octahedron-type or 3-octahedral-type layered silicate having a charge density of 0.25 to 0.6.
  • the 2-octahedron type includes montmorillonite, sidelite, etc. Hectrite, saponite, etc. are mentioned as the face type. Among these, montmorillonite is preferable.
  • the organic swollen smectite is obtained by expanding an interlayer of the layered silicate by bringing an organic swelling agent such as a polymer compound or an organic compound into contact with the layered silicate in advance.
  • a quaternary ammonium salt can be preferably used, but preferably a quaternary ammonia having at least one alkyl group or alkenyl group having 12 or more carbon atoms.
  • Umu salts particularly preferably quaternary ammonium halides (chloride, bromide, etc.) are used.
  • organic swelling agents include:
  • Trimethyl dodecyl ammonium salt Trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyloctadecyl ammonium salt, trimethyl alkyl ammonium salt such as trimethylecoyl ammonium salt salt;
  • Trimethyl alcohol hum salt such as trimethyl octadecerium salt, trimethyl octadedecaluminum salt; Triethyl dodecyl ammonium salt, triethyl tetradecyl ammonium salt, trihexahexadecyl ammonium salt, triethyloctadecyl ammonium salt, etc.
  • Tributyl diolenorequinoleum salt such as tributyl dodecyl ammonium salt, tributyl tetradecyl ammonium salt, tribubutyl hexadecyl ammonium salt, tributyl octadecyl ammonium salt;
  • Dimethyldidecammonium salt dimethylditetradecylammonium salt, dimethylditetradecylammonium salt, dimethyldihexadecylammonium salt, dimethyldioctadecylammonium salt, dimethylditalamoammum salt, etc. -Um salt;
  • Dimethyl dikeel ammonium salt such as dimethyl diocta de ammonium salt, dimethyl diocta de ammonium salt, etc .;
  • Diethyldialkyl ammonium salts such as Jetyldidodecyl ammonium salt, Jetyl ditetradecyl ammonium salt, Jetyl dihexadecyl ammonium salt, Jetyl dioctadecyl ammonium salt, etc.
  • Diethyldialkylammonium salts such as Jetyldidodecyl ammonium salt, Jetyl ditetradecyl ammonium salt, Jetyl dihexadecyl ammonium salt, Jetyl dioctadecyl ammonium salt, etc.
  • Dibutyldialkylammonium salts such as tildihexadecylammonium salt and dibutyldioctadecylammonium salt;
  • Methylbenzyl dialkyl ammonium salts such as methyl benzyl dihexadecyl ammonium salts
  • Dibenzyldialkyl ammonium salts such as dibenzyldihexadecyl ammonium salts
  • Trialkylmethyl ammonium salts such as tridodecyl methyl ammonium salts, tritetradecyl methyl ammonium salts, trioctadecyl methyl ammonium salts;
  • a trialkylethyl ammonium salt such as tridodecylethyl ammonium salt
  • a trialkylbutyl ammonium salt such as tridodecylbutyl ammonium salt
  • alkyl represents an alkyl group having 12 or more carbon atoms such as dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc.
  • PAG is a polyalkylene glycol residue, preferably A quaternary ammonium salt containing at least one alkylene glycol residue, such as a polyethylene glyco
  • These organic swelling agents can be used alone or as a mixture of a plurality of types.
  • the blending ratio of the organic swollen smectite is preferably 1 to 20% by weight, more preferably 1.5 to 15% by weight, based on the total of the heat-treated polyamide resin and the organic swollen smectite. If the blending ratio is 1% by weight or more, an effect of improving the barrier property appears, and if it exceeds 20% by weight, an appropriate barrier property improving effect cannot be expected.
  • the organic swollen smectite needs to be uniformly dispersed without locally agglomerating in the heat-treated polyamide resin.
  • uniformly dispersed means that the layered silicate is separated into flat plates in the heat-treated polyamide resin, and 50% or more of them have an interlayer distance of 5 nm or more. This interlayer distance is the distance between the centers of gravity of the flat objects. The greater the distance, the better the dispersion state, and the transparency when finally made into a film, sheet, or hollow container.
  • the barrier properties against gaseous substances such as oxygen and carbon dioxide can be improved.
  • a method of adding organic swollen smectite to heat-treated polyamide resin a method of adding organic swollen smectite during melt polymerization for polymer A production, stirring, a single screw or twin screw extruder, etc.
  • Examples include a method of melt-kneading heat-treated polyamide resin and organic swollen smectite using various commonly used extruders. Among these, a twin-screw extruder is used in terms of productivity and versatility. The melt kneading method used is preferred.
  • the melt kneading temperature was adjusted to 180 to 260 ° C, the residence time was adjusted to 5 minutes or less, and the screw had at least one reverse screw element and Z or one ding disk, It is preferable to carry out while partly retaining in the part.
  • melt-kneading temperature is within the above range, the organic swollen smectite is well dispersed. Moreover, the dispersibility of layered silicate improves by providing a retention part in a screw.
  • the melt kneading time is preferably adjusted to 1 to 5 minutes from the viewpoint of dispersibility, thermal decomposition, and gel generation.
  • the heat-treated polyamide resin of the present invention includes other thermoplastic resins such as polyolefin, polystyrene, polyester, polycarbonate, and polyamides such as nylon 6, nylon 66, and nylon 666, as long as the effects of the present invention are not impaired. Fats, elastomers, modified polyolefins, ionomers, lubricants, mold release agents, heat stabilizers, antioxidants, UV absorbers, layered silicates, glass fibers, Co, Mn, Zn and other inorganic or organic metal salts Additives such as complexes can be added.
  • other thermoplastic resins such as polyolefin, polystyrene, polyester, polycarbonate, and polyamides such as nylon 6, nylon 66, and nylon 666, as long as the effects of the present invention are not impaired. Fats, elastomers, modified polyolefins, ionomers, lubricants, mold release agents, heat stabilizers, antioxidants, UV absorbers,
  • thermoplastic resin used in the multilayer molded article of the present invention examples include polyolefin, polystyrene, polyester, polycarbonate, and polyamides such as nylon 6, nylon 66, and nylon 666.
  • Polyolefins include linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight high density polyethylene, polypropylene, or two or more types of olefins selected from ethylene, propylene, butene, etc. Examples thereof include copolymers and mixtures thereof.
  • ultra high molecular weight high density polyethylene is preferably used because it is excellent in prevention of drawdown during hollow molding, impact resistance, fuel swell resistance, and water resistance.
  • plastic fats can be mixed with each other, mixed with other resins such as elastomers, and other materials such as carbon black and flame retardants. It is also possible to use it in admixture with additives.
  • the multilayer molded article of the present invention is a bottle-shaped, cup-shaped, tray-shaped, tan, or the like formed by laminating at least one layer of heat-treated polyamide resin and at least one thermoplastic resin layer.
  • examples include multi-layer containers such as cups.
  • These molding methods are not particularly limited, but they are manufactured by a method of further thermoforming after extrusion molding, a melt molding method such as blow molding, a co-injection molding called sandwich molding and two-color molding.
  • a multilayer sheet is manufactured using a T-die extruder, thermoformed, a container is obtained by adhesion or welding, a cylindrical parison is formed using an injection molding machine or an extruder, It is manufactured by a method of professionally molding the nozzle, co-injection molding or the like in which two or more types of molten resin are sequentially injected into a mold.
  • each layer varies depending on the shape of the multilayer molded body.
  • the thickness of the barrier layer is selected from the range of 0.001 to Lmm
  • the thickness of the thermoplastic resin layer is selected from the range of 0.01 to 20 mm.
  • An adhesive resin layer (adhesive layer) can be provided between the barrier layer and the thermoplastic resin layer constituting the multilayer molded body.
  • the adhesive resin constituting the adhesive layer is, for example, maleic acid, acrylic acid, methacrylic acid, itaconic acid, or these acids if a thermoplastic resin layer made of polyolefins is bonded.
  • Polyethylene, polypropylene, or a copolymer of olefins such as ethylene, propylene, and butene modified with an anhydride or the like can be used.
  • thermoplastic resin layer is made of polyester or polycarbonate, an ethylene acetate butyl copolymer, an alkali or alkaline earth metal crosslinked ethylene acrylate copolymer, and an ethylene acrylate ester
  • the power that can be exemplified by a copolymer is not particularly limited.
  • the noria layer of the multilayer molded body may be formed by mixing the heat-treated polyamide resin of the present invention and the thermoplastic resin.
  • the heat-treated polyamide resin of the present invention it is preferable to use olefin and Z or styrene copolymer modified with the above-mentioned adhesive resin, unsaturated power rubonic acid or its anhydride as a compatibilizing agent.
  • heat-treated polyamide resin has viscosity and thermoplastic resin. It is desirable to adjust the mixing amount and take a dispersed state in which the heat-treated polyamide resin forms a continuous layer.
  • the mixing method if it is a publicly known method, fine resin pellets are driven and dispersed with an extruder, a method in which a resin powder is mixed and dispersed in an extruder, and dispersion is performed using a mixer. Although the method of performing etc. is mentioned, it does not specifically limit.
  • burrs and molding defects can be melted again and introduced into the multilayer molded body as a recycled layer.
  • the recycled layer is preferably disposed on the outer layer than the barrier layer in view of the strength of the multilayer molded body.
  • each of the resin layers of the multilayer molded body of the present invention has a lubricant.
  • Mold release agents heat stabilizers, antioxidants, UV absorbers, layered silicates, inorganic or organic metal salts such as Co, Mn, Zn, complexes, etc. can be added.
  • terminal amino group concentration and terminal carboxyl group concentration were calculated from the following equations.
  • Number average molecular weight 2 x 10 so (concentration of terminal carboxyl group + concentration of terminal amino group) [0042] (4) Melting point of polyamide resin
  • the mixture was filtered through a PTFE membrane filter (pore size: 3 ⁇ m) with a known weight, and the filter was washed with HFIP.
  • This filter was dried with a hot air dryer for 30 minutes under conditions of Z120 ° C, and after weighing the filter, the weight percentage of HFIP insoluble matter was calculated as the gel concentration.
  • Polyamide resin was charged into a single screw extruder with a diameter of 20 mm, and a 70 ⁇ m thick film was prepared at a preset temperature of 170 to 240 ° C. Two pieces of the obtained film were cut into 11 ⁇ 13 cm squares, and each was put together, and the three pieces were heat-sealed with a seal width of 10 mm to produce a bag.
  • the fuel-filled bag was left in an explosion-proof constant temperature and humidity chamber adjusted to 40 ° C / 65% RH, the fuel-filled bag was measured every day, and the amount of weight change per day was recorded. The maximum amount of weight change per day was used as the fuel permeation.
  • an injection molded piece of polyamide resin was prepared and measured according to ASTM D638.
  • High density polyethylene resin layer Z adhesive resin layer Z polyamide resin layer Z adhesive Resin layer Z High density polyethylene resin layer 300 /
  • a multilayer sheet consisting of 40/100/40/300 ⁇ m was prepared.
  • the obtained sheet was cut into a 3 ⁇ 7 cm square and allowed to stand for 3 weeks at 23 ° C. and 50% RH. Next, after immersing in ethanol for 10 minutes, the degree of peeling was observed.
  • a 50-liter reactor equipped with a stirrer, a condenser, a condenser, a dripping tank, and a nitrogen gas inlet tube was charged with 12 kg (82. llmol) adipic acid and 3.41 kg (20. 53 mol) isophthalic acid. After sufficiently replacing the inside of the reactor with nitrogen, adipic acid and isophthalic acid were melted at 160 ° C under a small amount of nitrogen flow. To this, 13.75 kg (100.95 mol) of metaxylylenediamine was added dropwise over 210 minutes with stirring. During this time, the internal temperature continuously increased to 254 ° C.
  • Polyamide 3 was obtained in the same manner as in Comparative Example 1 except that 13.92 kg (102.20 mol) of metaxylylenediamine was added dropwise. The results are shown in Table 2.
  • a polyamide 4 was obtained in the same manner as in Example 1 except that the polyamide 3 obtained in Comparative Example 2 was used. The results are shown in Table 1.
  • Example 2 After dry blending 97 parts by weight of the polyamide 4 obtained in Example 2 and 3 parts by weight of montmorillonite (trade name “Orben” manufactured by Shiroishi Kogyo Co., Ltd.) treated with an organic swelling agent, the mixture The compound was fed by a weighing feeder at a speed of 12 kgZ to a twin-screw extruder set with a tough-type screw having a cylinder diameter of 37 mm and a retention part due to a reverse element.
  • montmorillonite trade name “Orben” manufactured by Shiroishi Kogyo Co., Ltd.
  • Table 3 shows the measurement results for ethylene-vinyl alcohol copolymer (Kuraray, trade name “EVAL F-101BJ”).
  • Example 1 Example 2
  • Example 3 Polyamide 2 (heavy iron) 1 00
  • Comparative Example 1 Comparative Example 2 Polyamide 1 (parts by weight) 100 1 Polyamide 3 (parts by weight) 1 100 Terminal amino group concentration ( ⁇ equivalent / g) 41 86 Terminal carboxyl group concentration ( ⁇ equivalent / g) 95 65 Number average Molecular weight 15000 1 3000 Melting point (° C) 207 207 Melt viscosity (P a ⁇ s) 1 100 1000 Gel concentration (%) 0 0 Fuel permeation (gZd ay) 0.7 0.7 Measurement period showing maximum weight change (Day to Day) 2 to 3 2 to 3 Tensile elongation at break (%) 6 6 Ethanol resistance 1
  • the heat-treated polyamide resin of the present invention is excellent in barrier properties, mechanical properties, chemical resistance, heat resistance, and moldability, so it can be used as a packaging material for foods, beverages, chemicals, etc., and as a barrier material for fuel containers. Is preferred. In particular, it is suitable as a noria material for alcohol. Therefore, the industrial significance of the present invention is great.

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  • Polyamides (AREA)

Abstract

Une résine polyamide obtenue en soumettant un polyamide produit par polycondensation à chaud à une cristallisation et un traitement à chaud successivement. Le polyamide de départ produit par polycondensation à chaud est constitué d’unités de diamine et d’unités dicarboxyliques, dans lesquelles les unités de m-xylylènediamine représentent a moins 70 % en mole des unités de diamine et un mélange d’unités dicarboxyliques consistant en unités dicarboxyliques aliphatiques en C4-20 α,ω-à chaîne droite et d’unités isophtaliques à un rapport molaire de 30/70 à 95/5 représente au moins 70 % en mole des unités dicarboxyliques. La cristallisation est réalisée en maintenant le polyamide de départ en présence de 1 à 30 % en poids d’eau sur la base du polyamide entre 70 et 120 °C pendant 0,5 à 4 heures. Le traitement à chaud est réalisé en maintenant le polyamide de départ soit dans une atmosphère de gaz inerte, soit sous une pression réduite à une température allant du point de fusion du polyamide de départ moins 50 °C à celui-ci moins 10°C pendant 1 à 12 heures.
PCT/JP2005/012092 2004-07-02 2005-06-30 Résine polyamide et moulages à couches multiples WO2006003998A1 (fr)

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JP2004-196227 2004-07-02
JP2004196227 2004-07-02

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WO2006003998A1 true WO2006003998A1 (fr) 2006-01-12

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873587A (ja) * 1994-09-08 1996-03-19 Mitsubishi Gas Chem Co Inc ポリアミドの乾燥方法および固相重合方法
JP2000234022A (ja) * 1999-02-16 2000-08-29 Mitsubishi Gas Chem Co Inc ポリアミドの固相重合体
JP2001233958A (ja) * 2000-02-24 2001-08-28 Mitsubishi Gas Chem Co Inc ポリアミドの固相重合体
JP2001329169A (ja) * 2000-05-19 2001-11-27 Mitsubishi Gas Chem Co Inc ポリアミド複合材料の製造法
JP2003012023A (ja) * 2001-04-27 2003-01-15 Toyo Seikan Kaisha Ltd 保存性に優れた多層プラスチック容器

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873587A (ja) * 1994-09-08 1996-03-19 Mitsubishi Gas Chem Co Inc ポリアミドの乾燥方法および固相重合方法
JP2000234022A (ja) * 1999-02-16 2000-08-29 Mitsubishi Gas Chem Co Inc ポリアミドの固相重合体
JP2001233958A (ja) * 2000-02-24 2001-08-28 Mitsubishi Gas Chem Co Inc ポリアミドの固相重合体
JP2001329169A (ja) * 2000-05-19 2001-11-27 Mitsubishi Gas Chem Co Inc ポリアミド複合材料の製造法
JP2003012023A (ja) * 2001-04-27 2003-01-15 Toyo Seikan Kaisha Ltd 保存性に優れた多層プラスチック容器

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