JP2006348057A - Polyamide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin excellent in vibration weld strength, heat stability during residence, low-temperature toughness, and transparency and capable of being produced from a biomass-derived raw material, to provide a polyamide resin composition, and to provide a vibration-welded molding, a self-hinging molding, a binding band, and a filament made therefrom. <P>SOLUTION: The polyamide resin is one that is composed of dicarboxylic acid units comprising adipic acid units and diamine units comprising pentamethylenediamine units and hexamethylenediamine units, wherein the weight ratio of the pentamethylenediamine units to the hexamethylenediamine units is 95:5 to 60:40. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a polyamide resin. Specifically, the present invention relates to a polyamide using a raw material containing adipic acid units, pentamethylenediamine units and hexamethylenediamine units as constituents and suppressing the generation of carbon dioxide (CO ₂ ) causing global warming. It relates to resin. The present invention further relates to a vibration welded molded article excellent in vibration weld strength using the polyamide resin, a hinged molded article and a binding band excellent in low temperature toughness, and a filament excellent in transparency.

  6 Nylon and 66 Nylon are resins with excellent moldability, heat resistance, chemical resistance, mechanical properties, etc., automobile / vehicle related parts, electrical / electronic related parts, home / office electrical product related parts, computer Used in a wide range of applications such as related parts, facsimile / copier-related parts, machine-related parts, packaging materials, and fishery-related materials. In particular, intake manifold, hinged clip (molded product with hinge), cable tie, resonator, air cleaner, engine cover, rocker cover, cylinder head cover, timing belt cover, gasoline tank, gasoline sub tank, radiator tank as automotive / vehicle related parts Application to automotive underhood parts such as intercooler tanks, oil reservoir tanks, oil pans, electric power steering gears, oil strainers, canisters, engine mounts, junction blocks, relay blocks, connectors, corrugated tubes, and protectors are being studied.

  These underhood parts for automobiles are required to have higher part strength in order to cope with complication of parts and thinning for the purpose of weight reduction. Among the underhood parts for automobiles, the intake manifold, which is a large size class, is highly effective in reducing the weight by reducing the thickness. However, when the internal pressure increases due to the engine backfire or the like, it is necessary to maintain safety without being damaged.

  In recent years, glass fiber reinforced 6 nylon is mainly used as a material for a resin intake manifold, and a vibration welding method is mainly used as a construction method. In addition, it has been proposed to use 56 nylon instead of 6 nylon as a material for the resin intake manifold (see, for example, Patent Document 1). However, 56 nylon is insufficient in vibration welding strength. Furthermore, since 56 nylon is inferior in staying heat stability, it is not suitable for a large molded product having a long molding cycle such as an intake manifold. Accordingly, there is a demand for a polyamide resin having vibration welding strength and residence heat stability superior to 56 nylon.

  Further, 56/66 nylon having a large amount of 66 nylon units containing a small amount of 56 nylon units (56/66 = 0.5 / 99.5 to 40/60 mol%, preferably 0.5 / 99.5 to 10 / 90 mol%) is also known (see, for example, Patent Document 2). Since this type of polyamide resin is intended to suppress the gelation of 66 nylon while maintaining the function of 66 nylon, the amount of 56 nylon added is small. Therefore, although the vibration welding strength is unknown, it is considered to be the same as 66 nylon, and further improvement is required for use in large thin molded products.

  As a molded article with a hinge, many are used in underhood parts for automobiles. At present, 66 nylon is used when high heat resistance is required, and 6 nylon is used when high toughness is required. 66 nylon has a high melting point of 264 ° C., but its toughness is somewhat low due to its high crystallinity, and it is easily broken when the hinge part is bent. On the other hand, nylon 6 has better toughness due to lower crystallinity than 66 nylon, but its melting point is 224 ° C. and 40 ° C. lower than 66 nylon.

  As a means for improving the hinge property of a molded article with a hinge, a method is known in which a boron nitride powder and an aliphatic carboxylic acid derivative are blended with a polyamide resin (see, for example, Patent Document 3). However, this type of resin composition is considered to have no improvement in heat resistance (melting point).

  A method of blending a polyamide resin with a polyolefin such as polypropylene or polyethylene is also known (see, for example, Patent Document 4). However, in this type of polyamide resin composition, mechanical properties such as heat resistance (melting point) and flexural modulus are lower than that of polyamide resin.

  The polyamide resin composition satisfying both the hinge property and the heat resistance (thermal deformation temperature) at the same time includes an aromatic polyamide resin, a modified polyolefin, a polymer containing an epoxy group, or an epoxidized diene block copolymer. (See, for example, Patent Documents 5 and 6). However, the bending elastic modulus of this type of polyamide resin composition is about 1500 to 1900 MPa, which is greatly inferior to the bending elastic modulus of ordinary 6 nylon (about 2550 MPa) and 66 nylon (about 2940 MPa), Rigidity important as mechanical properties is insufficient. Therefore, there is a demand for a polyamide resin having hinge properties and heat resistance (melting point) superior to 6 nylon, and at the same time having a rigidity (flexural modulus) equal to or higher than 6 nylon.

  In addition, naphtha, a so-called fossil raw material, is used as a raw material for polyamide. However, in order to prevent global warming by suppressing carbon dioxide emissions and to create a recycling-oriented society, the raw material for polyamide production is replaced with a raw material derived from biomass. It is envied to do. That is, it is desired to increase the biomass ratio (ratio of biomass-derived raw material in the used raw material of polyamide resin) as a raw material for polyamide.

  The fields where biomass-derived raw materials are desired are not limited to the automotive field, but there are various fields such as the electrical and electronic field, the film field, and the filament field. Specific parts include intake manifolds with excellent vibration welding strength as described above. And the like, vibration molded articles such as hinged molded articles excellent in low temperature toughness and binding bands, and filaments excellent in transparency.

  Nylon 56 is known as a polyamide resin produced by polymerization using biomass-derived raw materials. 56 nylon has substantially the same heat resistance and mechanical properties as compared with 6 nylon and 66 nylon. 56 Nylon is produced by heating polycondensation of diaminopentane and adipic acid (see, for example, Patent Document 7), or preparing a salt of diaminopentane and adipic acid and heating polycondensation (for example, Patent Document). 8) etc. are known. However, as described above, 56 nylon is inferior in vibration welding strength and residence heat stability. Therefore, there is a demand for a polyamide resin that can be polymerized using biomass-derived raw materials and can provide a hinged molded article excellent in low-temperature toughness, a binding band, and a filament excellent in transparency.

JP 2004-269634 A International Publication No. 93/00385 Pamphlet JP 7-82474 A JP-A-9-249808 JP-A-9-124934 JP 2000-204243 A JP 2003-292612 A U.S. Pat. No. 2,130,948

  The present invention has been made in view of the above circumstances, and its purpose is to provide a polyamide resin that is excellent in vibration welding strength, residence heat stability, low temperature toughness, and transparency, and can be produced using biomass-derived raw materials. It is to be.

  Another object of the present invention is to provide a polyamide resin composition containing the polyamide resin.

  Still another object of the present invention is to provide a vibration welded molded article, a hinged molded article, a binding band and a filament containing the polyamide resin or polyamide resin composition.

  In order to solve the above problems, the present inventors have intensively studied, and as a result, have a constituent component containing an adipic acid unit, a pentamethylenediamine unit and a hexamethylenediamine unit, and a pentamethylenediamine unit, a xamethylenediamine unit, It has been found that the above object can be achieved by a polyamide resin having a content ratio of within the specified range, and the present invention has been completed.

  A first gist of the present invention is a polyamide resin having a component containing an adipic acid unit as a dicarboxylic acid unit and a pentamethylenediamine unit and a hexamethylenediamine unit as a diamine unit, The weight ratio with respect to the hexamethylenediamine unit is 95: 5 to 5:95, and the pentamethylenediamine unit is lysine using lysine decarboxylase, cells producing lysine decarboxylase, or a treated product of the cell. The polyamide resin is characterized in that it is formed using pentamethylenediamine produced from

  The second gist of the present invention is a polyamide resin containing adipic acid units as dicarboxylic acid units and having constituents containing pentamethylenediamine units and hexamethylenediamine units as diamine units, It exists in the polyamide resin characterized by weight ratio with a hexamethylenediamine unit being 95: 5-60: 40.

  A third gist of the present invention is a polyamide comprising the above polyamide resin and an inorganic filler, wherein the content of the inorganic filler with respect to 100 parts by weight of the polyamide resin is 0.01 to 150 parts by weight. Resists in resin composition.

  The fourth gist of the present invention resides in a vibration welding molded article containing the above polyamide resin or the above polyamide resin composition.

  The fifth gist of the present invention resides in a hinged molded article containing the above polyamide resin or the above polyamide resin composition.

  The sixth gist of the present invention resides in a binding band containing the above polyamide resin or the above polyamide resin composition.

  The seventh gist of the present invention resides in a filament containing the above polyamide resin or the above polyamide resin composition.

  The polyamide resin or polyamide resin composition of the present invention is excellent in vibration welding strength, residence heat stability, low temperature toughness, and transparency. Moreover, it is possible to provide a vibration welded molded article, a molded article with a hinge, a binding band, and a filament using the polyamide resin or the polyamide resin composition of the present invention, and in particular, with a hinge made of the polyamide resin of the present invention. The molded product exhibits extremely high hinge characteristics. Furthermore, the polyamide resin of the present invention can be produced from biomass-derived raw materials, and can be expected to have a significant effect on reducing the environmental burden in various industries. The industrial value of the present invention is high.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. First, the polyamide resin described in the first and second aspects of the present invention will be described. The polyamide resin described in the first and second aspects of the present invention contains adipic acid units as dicarboxylic acid units, and has constituent components containing pentamethylenediamine units and hexamethylenediamine units as diamine units.

  The content of adipic acid units in the dicarboxylic acid units constituting the polyamide resin is usually 90% by weight or more, preferably 95% by weight or more, and may be composed of only adipic acid units. The total content of pentamethylenediamine units and hexamethylenediamine units in the diamine units constituting the polyamide resin is usually 90% by weight or more, preferably 95% by weight or more. Only pentamethylenediamine units and hexamethylenediamine units are included. May consist of:

  In the case of the polyamide resin described in the first aspect of the present invention, the weight ratio of the pentamethylenediamine unit to the hexamethylenediamine unit in the diamine unit is 95: 5 to 5:95, preferably 95: 5 to 60: 40, more preferably 90:10 to 70:30. In the case of the polyamide resin described in the second aspect of the present invention, the weight ratio of the pentamethylenediamine unit to the hexamethylenediamine unit in the diamine unit is 95: 5 to 60:40, preferably 92.5: 7. 5 to 65:35, more preferably 90:10 to 70:30. When the weight ratio of pentamethylenediamine exceeds 95, vibration welding strength, residence heat stability and filament transparency are lowered. On the other hand, when the content of pentamethylenediamine is less than the above range, vibration welding strength, residence heat stability, low temperature toughness, filament transparency and biomass ratio are lowered. In addition, the weight ratio of the pentamethylenediamine unit and the hexamethylenediamine unit in the polyamide resin can be obtained by, for example, the following method. That is, the polyamide resin is hydrolyzed with acid or alkali to be decomposed into the structural units pentamethylenediamine, hexamethylenediamine and adipic acid, and each component is contained using a calibration curve prepared in advance by liquid chromatography or the like. Find the ratio.

  The polyamide resin of the present invention may be a homopolyamide blend or a copolymer as long as it has the above structural units. That is, it may be a blend of polyamide 56 homopolymer and polyamide 66 homopolymer, or may be a copolymer polyamide having pentamethylene diamine, hexamethylene diamine, or adipic acid as a structural unit. It is particularly preferable for achieving the effect.

  The polyamide resin of the present invention contains pentamethylenediamine, hexamethylenediamine, and adipine, which are essential structural units, as long as they are usually less than 10% by weight, preferably less than 5% by weight, and do not impair the effects of the present invention. Copolymerization components other than acid may be contained. Examples of the copolymer component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, and lactams such as ε-caprolactam and ω-laurolactam.

  Dicarboxylic acids that are copolymerization components include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanediic acid. Examples thereof include aliphatic dicarboxylic acids such as acid, pentadecanedioic acid and octadecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.

  Examples of the diamine as a copolymerization component include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diamino. Decane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diamino Heptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, aliphatic diamines such as 2-methyl-1,5-diaminopentane, cyclohexanediamine, bis- (4- Aminohexyl) Alicyclic diamines such as methane, xylylenediamine, etc. Aromatic diamines.

  The degree of polymerization of the polyamide resin of the present invention is not particularly limited, and the relative viscosity of a 98% by weight sulfuric acid solution of polyamide resin (concentration of polyamide resin: 0.01 g / ml) at 25 ° C. is usually 1.5 to 8.0. , Preferably 1.8 to 5.0. When the relative viscosity is less than 1.5, the practical strength may be insufficient, and when it exceeds 8.0, the fluidity may be lowered and the moldability may be impaired.

  In the endothermic peak area obtained by DSC measurement, the ratio of the endothermic peak area of 240 ° C. or higher is usually 60% or less, preferably 50% or less, with respect to the total endothermic peak area. When the ratio of the endothermic peak area of 240 ° C. or higher exceeds 60%, vibration welding strength, residence heat stability, and low temperature toughness may be deteriorated. The DSC measurement is performed using “Robot DSC” manufactured by Seiko Denshi Kogyo. As a specific operation method, about 5 mg of the obtained polyamide resin was put in a sample pan, heated to 290 ° C. in a nitrogen atmosphere, and held for 3 minutes. Thereafter, the temperature is decreased to 30 ° C. at a temperature decreasing rate of 20 ° C./min. Subsequently, after holding at 30 ° C. for 3 minutes, an endothermic peak observed when the temperature is raised from 30 ° C. to 290 ° C. at a temperature rising rate of 20 ° C./min is determined to determine the endothermic peak area.

  The method for obtaining the endothermic peak area will be described with reference to FIGS. In the endothermic peak expressed at 200 ° C. or higher and 290 ° C. or lower, the endothermic peak temperature expressed at the lowest temperature is a (° C.), the endothermic peak temperature expressed at the highest temperature is b (° C.), and a-50 (° C.). The endothermic point is X1, and the endothermic point of b + 10 (° C.) is X2. Then, the area surrounded by the straight line (L) connecting the endothermic points X1 and X2 and the endothermic curve is defined as the endothermic peak area (see the hatched portion in FIG. 1). As shown in FIG. 2, when the straight line (L) connecting the endothermic points X1 and X2 (indicated by a one-dot chain line) intersects the endothermic curve between X1 and X2, the most endothermic between the endothermic peaks. The area of the part surrounded by the polygonal line (X1-C-X2) passing through the point c with a small amount and the endothermic curve (the hatched part in FIG. 2) is defined as the endothermic peak area.

  The melting point (Tm) on the high temperature side of the polyamide resin of the present invention is usually 225 to 255 ° C, preferably 230 to 253 ° C. Note that the melting point is the endothermic peak in the above DSC measurement, and when two or more endothermic peaks are detected, the melting point is a plurality of melting points.

  In the polyamide resin of the present invention, other components can be blended at any stage from the production (polycondensation) of the polyamide resin to the molding as long as the effects of the present invention are not impaired. Other components include antioxidants and / or heat stabilizers, weathering agents, crystal nucleating agents, mold release agents and / or lubricants, pigments, dyes, plasticizers, antistatic agents, flame retardants, and other polymers. Can be mentioned.

  Examples of the antioxidant and / or heat stabilizer include hindered phenols, hydroquinones, phosphites, and substituted products thereof, copper halides, iodine compounds, and the like. Examples of the weathering agent include resorcinol, salicylate, benzotriazole, benzophenone, hindered amine and the like. Examples of the crystal nucleating agent include inorganic fine particles such as talc, kaolin, silica, and boron nitride, metal oxides, high melting point nylon, and the like. Examples of release agents and / or lubricants include aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, and polyethylene waxes. Examples of the pigment include cadmium sulfide, phthalocyanine, carbon black and the like. Examples of the dye include nigrosine and aniline black. Examples of the plasticizer include octyl p-oxybenzoate and N-butylbenzenesulfonamide.

  Examples of the antistatic agent include an alkyl sulfate type anionic antistatic agent, a quaternary ammonium salt type cationic antistatic agent, a nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, and a betaine amphoteric antistatic agent. It is done. Flame retardants include hydroxides such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins or brominated flame retardants thereof. And a combination of antimony trioxide and the like. Other polymers include other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, and the like.

  Above all, when using a polyamide resin for non-strengthening for injection molding such as hinged molded articles and binding bands, crystal nucleating agents and mold release agents are dry blended within the range that does not impair the present invention in order to improve moldability. It is preferable to mix.

  As a method for producing the polyamide resin (homopolyamide and polyamide copolymer) of the present invention, known methods can be used, and specifically disclosed in “Polyamide Resin Handbook” (published by Nikkan Kogyo Co., Ltd .: Osamu Fukumoto). ing. As a method for producing the polyamide 56 copolymer, an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine is usually 90% by weight or more, preferably 95% by weight or more, and adipic acid is usually 90% by weight or more, preferably A method obtained by polycondensation with 95% by weight or more of a dicarboxylic acid is preferred. More specifically, a method of preparing a salt of pentamethylene diamine and adipic acid, a salt of hexamethylene diamine and adipic acid, mixing them in the presence of water, and heating them to advance the dehydration reaction (heat polycondensation) ) Is preferred. In this case, by changing the mixing ratio of the salt of pentamethylenediamine and adipic acid and the mixing ratio of the salt of hexamethylenediamine and adipic acid, the copolymerization composition ratio in the polyamide can be changed. It is preferable that the molar ratio of the aliphatic diamine to the dicarboxylic acid is usually in the range of 1.00 to 1.05: 1.

  In the present invention, the above-mentioned heat polycondensation is a method in which the maximum reached temperature of the polymerization reaction mixture during the production of the polyamide resin is increased to 200 ° C. or higher. The upper limit of the maximum temperature reached is usually 300 ° C. or lower in consideration of the thermal stability of the polyamide resin during the polymerization reaction. The polymerization method may be a batch method or a continuous method.

  The polyamide resin produced by the above method can be further subjected to solid phase polymerization after heat polycondensation. Thereby, the molecular weight of the polyamide resin can be increased. The solid phase polymerization can be performed by heating in a vacuum or an inert gas at a temperature of 100 ° C. or higher and a melting point or lower, for example.

  In the polyamide resin described in the first aspect of the present invention, pentamethylenediamine as a raw material component is produced from lysine using lysine decarboxylase, a cell that produces lysine decarboxylase, or a processed product of the cell. The Also in the polyamide resin described in the second aspect of the present invention, pentamethylenediamine as a raw material component is lysine using lysine decarboxylase, a cell producing lysine decarboxylase, or a treated product of the cell. Is preferably produced from Thereby, the biomass ratio (the ratio of the biomass-derived raw material in the used raw material of the polyamide resin) can be increased. The polyamide resin of the present invention preferably has a biomass ratio (ratio of biomass-derived raw material in the used raw material of the polyamide resin) of 5% or more. If it is less than 5%, the effect of suppressing the generation of carbon dioxide causing global warming cannot be obtained.

  Specifically, the above pentamethylenediamine can be produced, for example, by the following method. That is, lysine is subjected to enzymatic decarboxylation while adding an acid to the lysine solution so that the pH of the solution is maintained at a pH suitable for enzymatic decarboxylation. Examples of the acid used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid. Free pentamethylene diamine can be collected from the obtained reaction product solution by an ordinary separation and purification method. In addition, when a dicarboxylic acid such as adipic acid is used as the acid, pentamethylenediamine dicarboxylic acid salt as a raw material for producing polyamide can be directly collected. A method for producing pentamethylenediamine / adipate by enzymatic decarboxylation of lysine using adipic acid as an acid is described in JP-A-2005-6650.

  Next, the polyamide resin composition which is the 3rd summary of this invention is demonstrated. The polyamide resin composition of the present invention contains the polyamide resin of the first or second aspect of the present invention and an inorganic filler.

  Inorganic fillers include graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, Stainless steel, glass fiber, glass flake, glass bead, carbon fiber, talc, silica, kaolin, clay, wollastonite, mica, boron nitride, potassium titanate, aluminum borate, bentonite, montmorillonite, synthetic mica, etc. Glass fiber having a high reinforcing effect and relatively inexpensive is preferable.

  As a glass fiber, the glass fiber normally used for a thermoplastic resin can be used, Especially the chopped strand manufactured from E glass (non-alkali glass) is preferable. The fiber diameter is usually 1 to 20 μm, preferably 5 to 15 μm. The glass fiber is preferably surface-treated with a silane coupling agent or the like in order to improve adhesion with the polyamide resin.

  The blending of the inorganic filler into the polyamide resin can be carried out at any stage from the production (polycondensation) of the polyamide resin to the molding, but it is preferable to melt and knead using an extruder during the polyamide resin molding.

  The compounding amount of the inorganic filler with respect to 100 parts by weight of the polyamide resin is 0.01 to 150 parts by weight, preferably 0.01 to 100 parts by weight. If the blending amount of the inorganic filler exceeds 150 parts by weight, fluidity may be impaired.

  In the polyamide resin composition of the present invention, other components can be blended at any stage from the production (polycondensation) of the polyamide resin to molding within a range not impairing the effects of the present invention. As other components, antioxidants and / or heat stabilizers, weathering agents, crystal nucleating agents, release agents and / or lubricants described in the first and second aspects of the present invention, pigments, dyes, plasticizers Antistatic agents, flame retardants, and other polymers can be used.

  Next, a vibration welded molded product that is the fourth gist of the present invention, a molded product with a hinge that is the fifth gist of the present invention, a binding band that is the sixth gist of the present invention, and a seventh gist of the present invention. The filament which is is demonstrated. The vibration welding molded product, hinged molded product, binding band and filament of the present invention contain the polyamide resin of the first or second aspect of the present invention or the polyamide resin composition of the third aspect of the present invention.

  The vibration welding molded product in the present invention is obtained by the following method. First, a plurality of parts are each primary molded using a polyamide resin or a polyamide resin composition. The molding method of the primary molded product is not particularly limited, and any molding method such as injection molding, film molding, melt spinning, blow molding, vacuum molding, or the like can be used, and among these, injection molding is preferable. The shape of the primary molded product is not particularly limited, and a desired shape is possible. The plurality of primary molded products may have the same shape or different shapes.

  Next, a plurality of primary molded products are joined by vibration welding to obtain a vibration welding molded product. In vibration welding, the frequency of vibration is usually 100 to 300 Hz, and the amplitude is usually 0.5 to 2.0 mm, preferably 0.8 to 1.6 mm. The welding pressure is usually 0.5 to 10 MPa, preferably 0.8 to 6 MPa. If the welding pressure is too high or too low, the welding strength may decrease. In particular, when the welding pressure is too low, there are places where welding is insufficient, and when the molded product is a hollow body, it causes a hermetic failure. The welding time under a predetermined pressure is set so that a desired welding allowance is obtained, and the holding time after the vibration is stopped is set so that the welded portion is sufficiently solidified.

  The hinged molded product and the binding band of the present invention are formed into a desired shape by an arbitrary molding method in the same manner as the molding method of the primary molded product in the vibration welded molded product, using the polyamide resin or the polyamide resin composition of the present invention. It can be obtained by molding. As the molding method, injection molding is particularly preferable.

  Specific examples of the hinged molded article and the binding band include a hinged clip, a hinged connector, a hinged binding band, and the like. The thickness of the hinge part is usually 0.2 to 0.8 mm, preferably 0. 3 to 0.6 mm. When the thickness of the hinge part is less than 0.2 mm, the fluidity of the polyamide resin in the hinge part may deteriorate. If the thickness of the hinge part exceeds 0.8 mm, the crystallinity in the hinge part increases, and the hinge part may be easily broken when bent.

  The filament of the present invention is obtained by molding the filament resin or polyamide resin composition of the present invention into a filament shape by a melt spinning molding method. The filament of the present invention is preferably used in a pile yarn portion in a constituent layer (base fabric, pile yarn and packing layer) of the mat. In particular, in a mat that requires antifouling properties, it is preferable to add a crystal nucleating agent such as talc, silica, kaolin, or clay to the filament of the present invention. The filament of the present invention can be suitably used as a raw yarn for household carpets, office carpets, automobile carpets, clothing, etc., in addition to the mat layer.

  As described above, the polyamide resin and the polyamide resin composition of the present invention can be molded into a desired shape by any molding method such as injection molding, film molding, melt spinning, blow molding, vacuum molding, for example, an injection molded product. It can be used for films, sheets, filaments, tapered filaments, fibers and the like, and can also be used for adhesives, paints, and the like.

  Specific application examples include intake manifolds, hinged clips (molds with hinges), cable ties, resonators, air cleaners, engine covers, rocker covers, cylinder head covers, timing belt covers, gasoline as automobile / vehicle related parts. Tanks, gasoline sub tanks, radiator tanks, intercooler tanks, oil reservoir tanks, oil pans, electric power steering gears, oil strainers, canisters, engine mounts, junction blocks, relay blocks, connectors, corrugated tubes, protector and other automotive underhood parts, doors Handles, fenders, hood bulges, roof rail legs, door mirror stays, bumpers, spoilers, wheel covers, etc. Instrumentation components, cup holders, console boxes, accelerator pedals, clutch pedals, shift lever pedestals, automobile interior parts such as a shift lever knob and the like.

  Furthermore, the polyamide resin and the polyamide resin composition of the present invention include fishing-related materials such as fishing lines and fishing nets, switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, binding bands, connectors, connector housings, Connector shell, IC socket, coil bobbin, bobbin cover, relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, caster, terminal block, power tool housing , Insulation parts of starters, fuse boxes, terminal housings, bearing retainers, speaker diaphragms, heat-resistant containers, microwave oven parts, rice cooker parts, printer ribbon guides, etc. Goods, household and office electric appliances parts, computer-related parts, facsimile-copier-related parts, can be used in various applications such as machine-related parts.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. Below, the evaluation method of the various characteristics of a polyamide resin, a polyamide resin composition, and its molded article is demonstrated.

(1) Relative viscosity (ηr):
A 98% sulfuric acid solution of polyamide resin (concentration: 0.01 g / ml) was prepared and measured at 25 ° C. using an Ostwald viscometer.

(2) DSC (differential scanning calorimetry):
This was performed using a “Robot DSC” manufactured by Seiko Denshi Kogyo. First, about 5 mg of polyamide resin was placed in a sample pan, heated to 290 ° C. in a nitrogen atmosphere, held for 3 minutes and completely melted, and then cooled to 30 ° C. at a rate of 20 ° C./min. The temperature of the observed exothermic peak is defined as the cooling crystallization temperature (Tc [° C.]). Subsequently, after holding at 30 ° C. for 3 minutes, an endothermic peak observed when the temperature was raised from 30 ° C. to 290 ° C. at a temperature rising rate of 20 ° C./min was measured to obtain an endothermic peak area. The temperature of the observed endothermic peak was defined as the melting point (Tm), and when a plurality of endothermic peaks were detected, the melting point was defined as a plurality of melting points.

(3) Stability thermal stability:
7 g of polyamide resin was put into a test tube having a capacity of 18 cc, and the test tube was immersed in an oil bath having a melting point + 30 ° C. in a sealed atmosphere in a nitrogen atmosphere. The sample was collected after 9 hours and the relative viscosity was measured. The viscosity retention was calculated from the relative viscosity before and after the residence test.

(4) Vibration welding test:
(4-1) Pressure resistance test of hollow body:

<Primary molding of hollow body parts>
A glass fiber reinforced polyamide resin composition was used to obtain a pair of hollow body parts (thickness: 2 mm, welded surface width: 4 mm), which are primary molded products shown in FIGS. Molding was performed using an IS350 type injection molding machine manufactured by Toshiba Machine Co., Ltd. at a resin temperature of 270 ° C. and a mold temperature of 80 ° C.

<Vibration welding of hollow body parts>
Using a vibration welding machine “VIBRATION WELDER Model 2800” manufactured by Emerson Japan, the above-mentioned pair of hollow body parts was vibration welded. The vibration welding conditions are the welding pressure shown in Table 1, the frequency 240 Hz, the amplitude 1.5 mm, the welding allowance 1.5 mm, the holding pressure is the same as the welding pressure immediately before the vibration stop, the holding time 5.0 seconds, and shown in FIG. A vibration welding molded product (hollow body) was obtained. At this time, a CX132 non-contact WDC welding size control device manufactured by Nippon Emerson Co., Ltd. was used to control the melting allowance.

<Pressure test of hollow body>
The obtained hollow body was subjected to a pressure resistance test. Using a pressure tester manufactured by Toyo Seiki Seisakusho, close the upper opening (1) and (1 ') (opening: 32 mmφ) of the hollow body, and from the lower opening (2) (opening: 32 mmφ) Pressurization was performed with a water pressure of a pressure ramp rate of 980 kPa / min, and the pressure at the time of bursting of the vibration welded product was measured. The test was performed three times for each welding pressure, and the average value was taken as the pressure strength.

  (4-2) Vibration welding strength test of strip type test piece:

<Primary molding of strip-shaped test pieces>
Two primary molded products having a rectangular parallelepiped shape having a bottom of 25 mm × 4 mm and a height of 60 mm were prepared using a glass fiber reinforced polyamide resin composition. Molding was performed using a J75-ED type injection molding machine manufactured by Nippon Steel Works, at a resin temperature of 270 ° C. and a mold temperature of 80 ° C.

<Vibration welding of strip type test piece>
Using the vibration welding machine “VIBRATION WELDER Model 2800” manufactured by Emerson Japan, the vibration welding between the bottom surfaces of the two primary molded products was performed. The vibration welding conditions are as follows: welding pressure shown in Table 1, frequency 240 Hz, amplitude 1.5 mm, welding allowance 1.5 mm, holding pressure is the same as the welding pressure just before vibration stop, holding time 5.0 seconds, and two primary moldings A vibration welding molded product was obtained in which the products were welded at the bottom. At this time, a CX132 non-contact WDC welding size control device manufactured by Nippon Emerson Co., Ltd. was used to control the melting allowance.

<Vibration welding strength test of strip type test piece>
The vibration welding strength test was performed on the obtained vibration welding molded product. Using “Tensilon UTM-III-2500” manufactured by A & D, a tensile test was performed at a distance between chucks of 60 mm and a tensile speed of 5 mm / min, and the strength at break was measured. The test was performed on six molded articles for each welding pressure, and the average value was defined as the vibration welding strength.

(5) Mechanical property evaluation (tensile test, bending test, notched Charpy test):
Glass fiber reinforced polyamide resin compositions and non-reinforced polyamide resin compositions were used, and ISO test pieces were molded in accordance with ISO standards. For the molding, a J75EII type injection molding machine manufactured by Nippon Steel Co., Ltd. is used. In the case of a glass fiber reinforced polyamide resin composition, the resin temperature is 270 ° C., the mold temperature is 80 ° C., and in the case of an unreinforced polyamide resin composition, the resin temperature. Each was performed at 265 ° C. and a mold temperature of 80 ° C. Using the obtained ISO test pieces, a tensile test, a bending test, and a notched Charpy test were performed in accordance with ISO standards.

(6) Low temperature hinge property:
Using the non-reinforced polyamide resin composition, a molded article with a hinge shown in FIG. 5 and a binding band shown in FIG. 6 were molded. The molded article with the hinge was molded using a PS40 type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. at a resin temperature of 265 ° C. and a mold temperature of 80 ° C. The binding band was molded using a SE50D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a resin temperature of 265 ° C. and a mold temperature of 80 ° C. The hinge part had a length of 2 mm, a width of 40 mm, and a wall thickness of 0.4 mm.

  The hinged molded product was cooled for 2 hours at the temperature shown in Table 2 in a thermostatic bath. In addition, the thermostat used the big thing which a tester entered and can test in. After cooling for 2 hours, the measurer enters the room, waits for 10 minutes in the thermostatic bath to completely eliminate the influence of the temperature change at the time of entry, and then, as shown in FIG. The test was performed from a bent state) to 180 degrees (a flat state with respect to the floor surface). Specifically, a test was performed in which the horizontal surface of the molded product was held with one hand and the vertical surface of the molded product was quickly bent with the other hand. The test was performed on 20 hinged molded articles at each temperature, and the number of hinge parts that did not break was used as a measured value.

(7) Low temperature band foldability:
The binding band was cooled for 2 hours at the temperature shown in Table 2 in a thermostatic bath. In addition, the thermostat used the big thing which a tester entered and can test in. After cooling for 2 hours, the measurer enters the room, waits for 10 minutes in the thermostat to completely eliminate the influence of temperature change at the time of entry, and then inserts one end of the band provided at the other end as shown in FIG. A test was conducted in which one end was pulled strongly while inserting into the hole and holding the other end with one hand. The test was performed on 20 hinged molded articles at each temperature, and the number of cracked parts was counted.

(8) Transparency of monofilament:
A gear pump and a nozzle with a diameter of 0.6 mm and a number of holes of 18 were attached to the tip of a Uniplus 40 mmφ single-screw extruder to obtain a spinning extruder. The polyamide resin is melted at a temperature of the melting point of the polyamide resin + 20 ° C., the polyamide resin is melt-spun, passed through a 20 ° C. cooling water bath, cooled and solidified, subjected to wet heat stretching at 98 ° C., and hot air stretching at 172 ° C. Second-stage stretching was performed in a tank, and heat setting was performed in a hot air stretching tank at 168 ° C. to obtain a monofilament having a diameter of 0.079 mm. The transparency of the obtained monofilament was visually evaluated.

  In the following examples and comparative examples, Rhodia “AH salt” was used as an equimolar salt of hexamethylenediamine and adipic acid. Further, an equimolar salt of pentamethylenediamine and adipic acid was prepared according to the method described in Examples 1 to 3 of JP-A-2005-6650.

Example 1 (Polyamide resin composition and vibration welded article):
After adding 25 kg of water to 25 kg of a mixture of equimolar salts of pentamethylenediamine and adipic acid and equimolar salts of hexamethylenediamine and adipic acid (see Table 1 for weight ratio), 1.25 g of phosphorous acid is added, The mixture was completely dissolved under a nitrogen atmosphere to obtain a raw material aqueous solution. The raw material aqueous solution was transferred to an autoclave which had been previously purged with nitrogen by a plunger pump. The jacket temperature was adjusted to 280 ° C., the autoclave pressure was adjusted to 1.47 MPa, and the contents were heated to 270 ° C. Next, after gradually releasing the pressure in the autoclave, the pressure was further reduced and the reaction was terminated when a predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. The obtained pellets were dried under the conditions of 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% or less to obtain a polyamide resin. Various characteristics evaluation was performed with respect to the obtained polyamide resin.

  To 100 parts by weight of the obtained polyamide resin, 43 parts by weight of “T249H” manufactured by Nippon Electric Glass Co., Ltd. was blended as a glass fiber to obtain a glass fiber reinforced polyamide resin composition. A TEM-35B type twin screw kneader manufactured by Toshiba Machine Co., Ltd. was used for blending. In order to suppress breakage, the glass fibers were side-fed and the melt kneading temperature was 270 ° C. The obtained polyamide resin composition was subjected to vibration welding test and mechanical property evaluation. The results are shown in Table 1.

Comparative Example 1:
A polyamide resin was obtained in the same manner as in Example 1 except that the monomer composition of the raw material salt was changed as shown in Table 1 in Example 1. Glass fibers were blended into the obtained polyamide resin in the same manner as in Example 1 to obtain a glass fiber reinforced polyamide resin composition. The obtained polyamide resin composition was subjected to vibration welding test and mechanical property evaluation. The results are shown in Table 1.

Example 2 (Polyamide resin composition, molded article with hinge and binding band):
Into 100 parts by weight of the polyamide resin obtained in Example 1, 0.02 part by weight of talc having an average particle size of 3.0 μm as a crystal nucleating agent was blended and then dry blended to obtain an unreinforced polyamide resin composition. Each evaluation of low temperature hinge property, low temperature band bending property, and mechanical property was performed with respect to the obtained polyamide resin composition. The results are shown in Table 2.

Comparative Example 2:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 1 in Example 1. The obtained polyamide resin was blended with talc in the same manner as in Example 2 and then dry blended to obtain a non-reinforced polyamide resin composition. Each evaluation of low temperature hinge property, low temperature band bending property, and mechanical property was performed with respect to the obtained polyamide resin composition. The results are shown in Table 2.

Comparative Example 3:
25 kg of caprolactam manufactured by Mitsubishi Chemical Co., Ltd., 0.75 kg of water, and 1.74 g of disodium hydrogen phosphite pentahydrate were put in a container, purged with nitrogen, and dissolved at 100 ° C. This raw material aqueous solution was transferred to an autoclave, the jacket temperature was set to 280 ° C., and heating was started. After the temperature of the contents was raised to 270 ° C., the pressure in the autoclave was gradually released, and then the pressure was further reduced and the polycondensation reaction was completed when the predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. Unreacted monomers and oligomers were extracted and removed from the obtained pellets using boiling water 1.5 times the amount of the obtained pellets. The pellets from which the unreacted substances had been removed were dried at 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% or less to obtain a polyamide resin. Various characteristics evaluation was performed with respect to the obtained polyamide resin.

  In the same manner as in Example 2, talc was blended and then dry blended to obtain a non-reinforced polyamide resin composition. Each evaluation of low temperature hinge property, low temperature band bending property, and mechanical property was performed with respect to the obtained polyamide resin composition. The results are shown in Table 2.

Examples 3 to 8 (polyamide resin and filament):
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Tables 3 and 4 in Example 1. Various characteristics evaluation was performed with respect to the obtained polyamide resin. Furthermore, monofilaments were prepared for the obtained polyamide resin as described in the item of transparency evaluation, and the transparency was evaluated. The results are shown in Tables 3 and 4.

Comparative Example 4:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 5 in Example 1. Various characteristics evaluation was performed with respect to the obtained polyamide resin. Furthermore, monofilaments were prepared for the obtained polyamide resin as described in the item of transparency evaluation, and the transparency was evaluated. The results are shown in Table 5.

Comparative Example 5:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 5 in Example 1. Various characteristics evaluation was performed with respect to the obtained polyamide resin. Furthermore, monofilaments were prepared for the obtained polyamide resin as described in the item of transparency evaluation, and the transparency was evaluated. The results are shown in Table 5.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is not limited to the embodiments disclosed herein. It should be understood that the present invention can be modified as appropriate without departing from the spirit or concept of the invention as read from the claims and the entire specification, and that such changes are also within the technical scope of the present invention. . In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2004-152059) for which it applied on May 23, 2004, The whole is used by reference.

It is explanatory drawing of the method of calculating | requiring an endothermic peak area. It is explanatory drawing of the method of calculating | requiring an endothermic peak area. It is a side view by the side of the welding of each hollow body part which is the primary molded product used for the vibration welding test in the Example of this invention, (a) is a hollow body part which has the convex-shaped part used as a welding allowance in a welding part. The figure shown, (b) is a figure which shows the hollow body components with a flat welding part. It is a perspective view of the hollow body used for the vibration welding test in the Example of this invention. It is the side view (a) and top view (b) of the molded article with a hinge used for the low temperature hinge property test in the Example of this invention. It is the side view (a) and top view (b) of the binding band used for the low temperature band foldability test in the Example of this invention. It is explanatory drawing of the low temperature hinge property test in the Example of this invention. It is explanatory drawing of the low-temperature band bending property test in the Example of this invention.

Explanation of symbols

1: Upper opening 1 ': Upper opening 2: Lower opening

Claims (14)

  A polyamide resin containing adipic acid units as dicarboxylic acid units and having constituents containing pentamethylenediamine units and hexamethylenediamine units as diamine units, wherein the weight ratio of pentamethylenediamine units to hexamethylenediamine units is 95: 5 to 5:95, wherein the pentamethylenediamine unit is a lysine decarboxylase, a cell that produces lysine decarboxylase, or a pentamethylenediamine produced from lysine using a treated product of the cell. A polyamide resin characterized by being formed by use.   A polyamide resin containing adipic acid units as dicarboxylic acid units and having constituents containing pentamethylenediamine units and hexamethylenediamine units as diamine units, wherein the weight ratio of pentamethylenediamine units to hexamethylenediamine units is A polyamide resin characterized by being in the range of 95: 5 to 60:40.   The adipic acid unit content in the dicarboxylic acid unit is 90% by weight or more, and the total content of the pentamethylenediamine unit and the hexamethylenediamine unit in the diamine unit is 90% by weight or more. The polyamide resin described in 1.   4. The polyamide resin according to claim 1, wherein in the endothermic peak area obtained by DSC measurement of the polyamide resin, the ratio of the endothermic peak area of 240 ° C. or more is 60% or less with respect to the total endothermic peak area.   The polyamide resin is a copolymer obtained by polycondensation of an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine and a dicarboxylic acid containing adipic acid. Polyamide resin.   The polyamide resin according to claim 5, wherein the polycondensation is heating polycondensation.   The polyamide resin of Claim 5 or 6 obtained by polycondensing the salt of the said aliphatic diamine and the said dicarboxylic acid.   The polyamide resin according to any one of claims 5 to 7, wherein pentamethylenediamine is produced from lysine using lysine decarboxylase, a cell producing lysine decarboxylase, or a treated product of the cell.   A polyamide comprising the polyamide resin according to any one of claims 1 to 8 and an inorganic filler, wherein the content of the inorganic filler with respect to 100 parts by weight of the polyamide resin is 0.01 to 150 parts by weight. Resin composition.   The polyamide resin composition according to claim 9, wherein the inorganic filler is glass fiber.   A vibration weld-molded article containing the polyamide resin according to any one of claims 1 to 8 or the polyamide resin composition according to claim 9 or 10.   A molded article with a hinge containing the polyamide resin according to any one of claims 1 to 8 or the polyamide resin composition according to claim 9 or 10.   A binding band containing the polyamide resin according to any one of claims 1 to 8 or the polyamide resin composition according to claim 9 or 10.   The filament containing the polyamide resin in any one of Claims 1-8, or the polyamide resin composition of Claim 9 or 10.

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