JP2009298865A - Fuel tank component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel tank component excellent in fuel permeation resistance, although having a low water absorption properties, capable of obtaining a higher molecular weight by melt polymerization, having a wide moldable temperature width estimated by the difference of its melting point and decomposition temperature, excellent in melt moldability, and excellent in chemical resistance and hydrolysis resistance. <P>SOLUTION: The fuel tank component contains a polyamide resin of which the dicarboxylic acid consists of oxalic acid, and the diamine component consists of 1,9-nonane diamine and 2-methyl-1,8-octane diamine, and having a (1:99) to (99:1) molar ratio of the 1,9-nonane diamine to the 2-methyl-1,8-octane diamine. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fuel tank component containing a novel polyamide resin. Specifically, it contains a polyamide resin whose dicarboxylic acid component is oxalic acid, has excellent fuel permeation resistance, has low water absorption, can be made to have a high molecular weight by melt polymerization, has a wide moldable temperature range, and excellent moldability. In addition, the present invention relates to a fuel tank component having excellent chemical resistance and hydrolysis resistance.

  Polyamide resins typified by crystalline polyamides such as nylon 6 and nylon 66 are widely used as clothing, industrial material fibers, or general-purpose engineering plastics because of their excellent characteristics and ease of melt molding. In particular, polyamide resins are required to have excellent fuel permeation resistance for use in fuel tank parts. In addition, these polyamide resins have been pointed out to have problems such as changes in physical properties due to water absorption, deterioration in acid, high-temperature alcohol, and hot water, resulting in a polyamide with superior dimensional stability and chemical resistance. The demand is growing.

  As a technique for providing a component having excellent fuel permeation resistance, for example, Patent Document 1 discloses a fuel that is made of a crystalline polyamide resin in which amino terminal group concentration> carboxyl terminal group concentration and excellent in fuel resistance of a welded portion. Parts attached to any of tanks, fuel hoses and canisters have been proposed. However, this technique has a problem that it is difficult to achieve both low water absorption, chemical resistance, hydrolysis resistance, molding processability and fuel permeation resistance.

  On the other hand, a polyamide resin using oxalic acid as a dicarboxylic acid component is called a polyoxamide resin, and is known to have a higher melting point and lower water absorption than other polyamide resins having the same amino group concentration (Patent Document 2). It is expected to be used in fields where the use of conventional polyamide, where the change in physical properties due to water absorption has been a problem, is difficult.

  So far, polyoxamide resins using various aliphatic linear diamines as diamine components have been proposed. However, for example, a polyoxamide resin using 1,6-hexanediamine as a diamine component has a melting point (about 320 ° C.) higher than the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.) (non-patent document). 1) Melt polymerization and melt molding were difficult and could not withstand practical use.

  For a polyoxamide resin (hereinafter abbreviated as PA92) whose diamine component is 1,9-nonanediamine, L. Franco et al. Discloses a production method and crystal structure when diethyl oxalate is used as the oxalic acid source ( Non-patent document 2). The PA 92 obtained here is a polymer having an intrinsic viscosity of 0.97 dL / g and a melting point of 246 ° C., but only a low molecular weight product that can not be molded into a tough molded body that can withstand practical use is obtained. Patent Document 3 shows that PA92 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. was produced when dibutyl oxalate was used as the dicarboxylic acid ester. In this case as well, there is a problem that only a low molecular weight body that cannot form a tough molded body is obtained.

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988) JP 2002-370551 A JP 2006-57033 A Japanese National Patent Publication No. 5-506466

  The problems to be solved by the present invention are excellent in fuel permeation resistance, low water absorption, high molecular weight by melt polymerization, and wide moldable temperature range estimated from the difference between melting point and thermal decomposition temperature. An object of the present invention is to provide a fuel tank component that is excellent in melt moldability and excellent in chemical resistance and hydrolysis resistance.

  The inventors of the present invention have found that a polyamide resin composed of oxalic acid as a dicarboxylic acid component and 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component has a low water absorption and is highly melt-polymerized. It has already been found that the molecular weight can be increased, the moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature is wide, the melt moldability is excellent, and the chemical resistance and hydrolysis resistance are also excellent. As a result of intensive studies to solve the above problems, the dicarboxylic acid component is composed of oxalic acid, the diamine component is composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9 -By using a polyamide resin having a molar ratio of nonanediamine and 2-methyl-1,8-octanediamine of 1:99 to 99: 1, the fuel permeability is excellent, the water absorption is low, and melt polymerization is used. Higher molecular weight is possible, and the temperature range that can be estimated by the difference between the melting point and the thermal decomposition temperature is as wide as, for example, 50 ° C or more, and it has excellent melt moldability and fuel tank parts with excellent chemical resistance and hydrolysis resistance. The present invention has been completed. That is, the present invention is as follows.

  [1] The dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl-1,8-octanediamine A fuel tank component comprising a polyamide resin having a molar ratio of 1:99 to 99: 1.

  [2] The polyamide resin has a relative viscosity (ηr) of 1.8 to 6.0 when measured at 25 ° C. using a polyamide resin solution having a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent. The fuel tank component according to [1] above.

  [3] 1% weight loss temperature in thermogravimetric analysis of polyamide resin measured at 10 ° C./min in nitrogen atmosphere and differential scanning measured at 10 ° C./min in nitrogen atmosphere The fuel tank component according to the above [1] or [2], wherein the temperature difference from the melting point measured by a calorimetric method is 50 ° C. or more.

  [4] Any of [1] to [3] above, wherein the diamine component has a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine of 5:95 to 95: 5. Fuel tank parts as described in.

[5] The amino terminal group concentration of the polyamide resin is 1.5 × 10 ⁻⁵ eq / g to 1.0 × 10 ⁻⁴ eq / g, according to any one of the above [1] to [4]. Fuel tank parts.

  The fuel tank component of the present invention has excellent fuel permeation resistance and low water absorption, but can be made to have a high molecular weight by melt polymerization, and has a wide range of moldable temperature estimated from the difference between the melting point and the thermal decomposition temperature. Since it is excellent in moldability and excellent in chemical resistance and hydrolysis resistance, it can be widely used as a fuel tank part attached to the fuel tank.

  The fuel tank component of the present invention is a component attached to the fuel tank, and examples thereof include various valves, various connection nozzles, various separators, and more specifically, a fuel gender unit, a tank valve component, a canister, Examples include a fuel tank cap, a fuel filler flap, a fuel pump, a fuel tank valve, and the like.

(I) Polyamide resin (1) Constituent component of polyamide resin In the polyamide resin used in the present invention, the dicarboxylic acid component is composed of oxalic acid, and the diamine component is composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. And a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 1:99 to 99: 1.

  As the oxalic acid source used in the production of the polyamide resin, oxalic acid diesters can be employed, and there is no particular limitation as long as they have reactivity with amino groups. Dimethyl oxalate, diethyl oxalate, di-n-oxalate (or i-) oxalic acid diesters of aliphatic monohydric alcohols such as propyl, di-n- (or i-, or t-) butyl oxalate, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, and aromatic alcohols such as diphenyl oxalate Examples include oxalic acid diesters.

  Among the oxalic acid diesters, oxalic acid diesters of aliphatic monohydric alcohols having more than 3 carbon atoms, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols are preferred, and among them, dibutyl oxalate and diphenyl oxalate are particularly preferred.

  As the diamine component, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is used. Furthermore, the molar ratio of the 1,9-nonanediamine component and the 2-methyl-1,8-octanediamine component is 1:99 to 99: 1, preferably 5:95 to 95: 5, more preferably 5: It is 95-40: 60 or 60: 40-95: 5, Most preferably, it is 5: 95-30: 70 or 70: 30-90: 10. By copolymerizing 1,9-nonanediamine and 2-methyl-1,8-octanediamine in the above-mentioned specific amount, it is possible to increase the molecular weight by melt polymerization while having low water absorption, and the molding temperature range is wide. A polyamide having excellent melt moldability and excellent chemical resistance and hydrolysis resistance can be obtained.

  In particular, when the molar ratio is 5:95 to 40:60, and further 5:95 to 30:70, the crystallinity is excellent, so that the low water absorption and mechanical properties are particularly excellent, and liquid and / or gas (for example, For example, the permeability of alcohol and the like is low, and the water absorption is lower than when the content of 1,9-nonanediamine is higher than the content of 2-methyl-1,8-octanediamine, for example. It also has the advantage of. On the other hand, when the molar ratio is 60:40 to 95: 5, further 70:30 to 95: 5, and further 70:30 to 90:10, low water absorption and mechanical properties are particularly excellent, and good transparency. The advantage that the property is imparted is obtained.

The amino terminal group concentration of the polyamide resin used in the present invention is 1.5 × 10 ⁻⁵ eq / g to 1.0 × 10 ⁻⁴ eq / g in that the fuel permeation resistance and the welding property are particularly good. Preferably there is.

(2) Components that can be blended in the production of polyamide resin When producing the polyamide resin used in the present invention, other dicarboxylic acid components can be mixed within a range not impairing the effects of the present invention. Other dicarboxylic acid components other than succinic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3, Aliphatic dicarboxylic acids such as 3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and terephthalic acid , Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, dibenzoic acid Acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfuric acid Down-4,4'-dicarboxylic acid, 4,4'-biphenyl and the like alone aromatic dicarboxylic acids such as dicarboxylic acids, or may be added to any mixture thereof during the polycondensation reaction. Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used as long as melt molding is possible. It is preferable that the usage-amount of another dicarboxylic acid component is 5 mol% or less of the whole dicarboxylic acid component.

  Moreover, when manufacturing the polyamide resin used in this invention, another diamine component can be mixed in the range which does not impair the effect of this invention. Examples of diamine components other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, and 1,8-octanediamine. 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1 , 6-hexanediamine, aliphatic diamines such as 5-methyl-1,9-nonanediamine, cyclohexanediamine, methylcyclohexanediamine, and cycloaliphatic diamines such as isophoronediamine, p-phenylenediamine, m-phenylenediamine, p -Xylenediamine, m-xylenediamine, 4,4'-diamy Diphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-and aromatic diamines, such as diaminodiphenyl ether by itself, or may be added to any mixture thereof during the polycondensation reaction. It is preferable that the usage-amount of another diamine component is 5 mol% or less of the whole diamine component.

  The polyamide resin used in the present invention may be one in which a part thereof is replaced with another polymer component as long as the effects of the present invention are not impaired. As other polymer components, the dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl-1, Polyamides such as polyoxamides, aromatic polyamides, aliphatic polyamides, and alicyclic polyamides as thermoplastics other than polyamides having a molar ratio with 8-octanediamine of 1:99 to 99: 1, and thermoplastics other than polyamides Examples thereof include polymers. In the polyamide resin used in the present invention, the dicarboxylic acid component is composed of oxalic acid, the diamine component is composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl- The proportion of polyamide having a molar ratio with 1,8-octanediamine of 1:99 to 99: 1 is preferably more than 50% by mass, and more preferably 70% by mass or more.

(3) Properties and properties of polyamide resin The molecular weight of the polyamide resin used in the present invention is not particularly limited, but the relative viscosity measured at 25 ° C. using a 96% concentrated sulfuric acid solution with a polyamide resin concentration of 1.0 g / dl. ηr is preferably in the range of 1.8 to 6.0, more preferably 2.0 to 5.5, and particularly preferably 2.5 to 4.5. If ηr is lower than 1.8, the molded product tends to be brittle and the physical properties tend to decrease. On the other hand, when ηr is higher than 6.0, the melt viscosity becomes high and the molding processability tends to deteriorate.

  The polyamide resin used in the present invention uses oxalic acid as the dicarboxylic acid component, and copolymerizes 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component, so that oxalic acid and 1,9-nonanediamine are copolymerized. It is possible to increase the relative viscosity, that is, increase the molecular weight as compared with the polyamide. The moldable temperature range represented by the difference (Td−Tm) between the 1% weight loss temperature (hereinafter abbreviated as Td) and the melting point (hereinafter abbreviated as Tm), which is a substantial thermal decomposition index, is oxalic acid. And a moldable temperature range can be preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even 90 ° C. or higher. The polyamide resin used in the present invention has a Td of preferably 280 ° C. or higher, more preferably 300 ° C. or higher, still more preferably 320 ° C. or higher, and has high heat resistance.

(4) Manufacture of polyamide resin The polyamide resin used in the present invention can be manufactured using any method known as a method of manufacturing polyamide. According to the study by the present inventors, a polyamide resin can be obtained by polycondensation reaction of diamine and oxalic acid diester in a batch or continuous manner. Specifically, it is preferable to carry out in the order of (i) pre-polycondensation step and (ii) post-polycondensation step as shown by the following operations.

  (I) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then diamine (diamine component) and oxalic acid diester (oxalic acid source) are mixed. When mixing, a solvent in which both the diamine and the oxalic acid diester are soluble may be used. The solvent in which both the diamine component and the oxalic acid source are soluble is not particularly limited, but toluene, xylene, trichlorobenzene, phenol, trifluoroethanol, and the like can be used, and particularly, toluene can be preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this. At this time, the charging ratio of the oxalic acid diester and the diamine is oxalic acid diester / the diamine, 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), more preferably 0. .99 to 1.01 (molar ratio).

  The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature is, for example, 3 to 6 hours.

  (Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature rising process, the final temperature of the prepolycondensation step, that is, from 80 to 150 ° C, is finally 220 ° C to 300 ° C, preferably 230 ° C to 280 ° C, more preferably 240 ° C to 270 ° C. Let reach the range. It is preferable to carry out the reaction for 1 to 8 hours including the temperature raising time, preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final ultimate pressure in the case of performing the vacuum polymerization is less than 0.1 MPa to 13.3 Pa.

  A more specific example of the method for producing the polyamide resin used in the present invention will be described below. First, the raw oxalic acid diester is charged into the container. The container is not particularly limited as long as it can withstand the temperature and pressure of the polycondensation reaction to be performed later. Thereafter, the container is heated to a temperature at which it is mixed with the raw material diamine, and then the diamine is injected to start the polycondensation reaction. The temperature at which the raw materials are mixed is not particularly limited as long as it is a temperature not lower than the melting point and lower than the boiling point of the oxalic acid esters and diamines of the raw materials and the polyoxamide generated by the polycondensation reaction between the oxalic acid diester and the diamine is not thermally decomposed. For example, it consists of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is from 1:99 to In the case of a polyoxamide resin starting from 99: 1 diamine and dimethyl oxalate, the mixing temperature is preferably 15 ° C to 240 ° C. Further, when the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 90:10, it is liquid at room temperature or liquefied only by heating to about 40 ° C. It is more preferable because it is easy to handle. When the mixing temperature is equal to or higher than the boiling point of the alcohol produced by the condensation reaction, it is desirable to use a container equipped with a device for distilling and condensing the alcohol. In addition, when pressure polymerization is performed in the presence of an alcohol generated by a condensation reaction, a pressure vessel is used. The charging ratio of oxalic acid diester to diamine is oxalic acid diester / the above diamine, preferably 0.8 to 1.2 (molar ratio), more preferably 0.91 to 1.09 (molar ratio), and still more preferably 0. .98 to 1.02 (molar ratio).

  Next, the inside of the container is heated to a temperature not lower than the melting point of the polyoxamide resin and not higher than the temperature at which it does not decompose. For example, a diamine composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine and having a molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of 85:15 In the case of a polyoxamide resin using dibutyl oxalate as a raw material, the melting point is 235 ° C., so it is preferable to raise the temperature from 240 ° C. to 280 ° C. (pressure is 2 MPa to 4 MPa). While distilling off the produced alcohol, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. When the raw materials are mixed in a pressure vessel and subjected to pressure polymerization in the presence of an alcohol produced by a condensation reaction, the pressure is first released while the produced alcohol is distilled off. Thereafter, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 760 to 0.1 Torr. The temperature is preferably 240 to 280 ° C. The alcohol is cooled and liquefied by a water-cooled condenser and recovered.

(II) Other components In the present invention, various additives can be combined as necessary in addition to the above-mentioned polyamide resin, and these can be combined during or after the polyamide polycondensation reaction. .

  Various additives include fuel permeation improvers, fillers, reinforcing fibers, stabilizers such as copper compounds, colorants, UV absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization Accelerators, glass fibers, plasticizers, lubricants, heat-resistant agents and the like can be mentioned.

  Examples of the fuel permeation improver include layered silicate. The layered silicate can improve the mechanical strength and heat resistance of the fuel tank component of the present invention and improve the fuel permeation resistance. The layered silicate is preferably a flat plate having a side length of 0.002 to 1 μm and a thickness of 6 to 20 mm. Moreover, when the said layered silicate is disperse | distributed in a polyamide resin, it is preferable that each layer maintains the interlayer distance of about 18 mm or more, and is disperse | distributed uniformly.

  Here, “interlayer distance” refers to the distance between the centroids of the plate-like layered silicate, and “uniformly dispersed” means that each layer exists mainly in a random state, and the layered silicate 50% by mass or more, preferably 70% by mass or more is dispersed in a single layer without forming a multilayer.

  Examples of the raw material for the layered silicate include layered phyllosilicate minerals composed of magnesium silicate or aluminum silicate layers, that is, aluminum silicate phyllosilicate or magnesium silicate phyllosilicate. Specific examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, and halloysite. It may be what was done.

  Further, in order to disperse the layered silicate in the polyamide resin, a swelling agent is usually used. The swelling agent has a role of expanding the interlayer of the clay mineral and a role of giving the clay mineral a force for taking up the interlayer polymer. In the present invention, it is preferable to use 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the swelling agent.

  The layered silicate is preferably pulverized using a mixer, a ball mill, a vibration mill, a pin mill, a jet mill, a beating machine, or the like to have a desired shape and size in advance.

  The amount of the layered silicate is not particularly limited as long as the effect of improving mechanical strength, heat resistance and fuel permeability is obtained, but with respect to 100 parts by mass of the polyamide resin used in the present invention. The amount is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass. When the ratio of the layered silicate is lowered, the mechanical strength, heat resistance and fuel permeation resistance tend to be improved, and when the ratio is increased, the fluidity of the resin composition and the physical properties of the obtained molded product, particularly The impact strength tends to be low.

  Examples of the method for uniformly dispersing the layered silicate in the polyamide resin include the following methods. When the raw material of the layered silicate is a multilayered clay mineral, the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as 1,9-nonanediamine and 2-methyl-1,8-octanediamine is added thereto. And the space | interval of each layer of layered silicate is expanded previously. Next, a polyamide raw material can be introduced between the layers, and the raw materials can be polymerized between the layers.

  Alternatively, using a polymer compound as a swelling agent, the layers may be preliminarily spread to about 100 mm or more, melt-mixed with the polyamide resin, and each layer may be dispersed in the polyamide resin.

(III) Formation of Fuel Tank Parts The fuel tank parts of the present invention are molded using a conventionally known molding method according to the application, such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching. , Vibration welding method, die slide injection, die rotary injection and two-color injection injection welding method, ultrasonic welding method, spin welding method, hot plate welding method, hot wire welding method, laser welding method, high frequency induction heating welding method, etc. And can be applied to objects. In forming the fuel tank part, the temperature of the polyamide resin is preferably maintained at a temperature that does not change the quality of the polyamide resin.

[Physical property measurement, molding, evaluation method]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The evaluation shown in the table was performed by the following method.

[Physical property measurement, molding, evaluation method]
The characteristic value was measured by the following method.

(1) Relative viscosity (ηr)
ηr was measured at 25 ° C. with an Ostwald viscometer using a 96% sulfuric acid solution of polyamide (concentration: 1.0 g / dl).

(2) Melting point (Tm) and crystallization temperature (Tc)
Tm and Tc were measured under a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer. The temperature was raised from 30 ° C. to 270 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 270 ° C. for 3 minutes, and then lowered to −100 ° C. at a rate of 10 ° C./min (temperature fall first). Then, the temperature was raised to 270 ° C. at a rate of 10 ° C./min (called a temperature raised second run). From the obtained DSC chart, the exothermic peak temperature of the temperature decrease first run was Tc, and the endothermic peak temperature of the temperature increase second run was Tm.

(3) 1% weight loss temperature (Td)
Td was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation. The temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min under a nitrogen stream of 20 ml / min, and Td was measured.

(4) Melt viscosity Melt viscosity was measured by attaching a 25 mm cone plate to a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan Co., Ltd., at 250 ° C. in nitrogen and at a shear rate of 0.1 s ⁻¹ . Measured under conditions.

(5) Film formation A film was formed from the pellets using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. In a reduced pressure atmosphere of 500 to 700 Pa, the film was heated and melted at 260 ° C. (290 ° C. when PA66 was used, and 230 ° C. when PA12 was used) for 5 minutes, and then pressed at 5 MPa for 1 minute to form a film. Next, the reduced-pressure atmosphere was returned to normal pressure, and then cooled and crystallized at room temperature of 5 MPa for 1 minute to obtain a film.

(6) Saturated water absorption rate A film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass of about 0.05 g) formed under the conditions of (5) above is immersed in ion-exchanged water at 23 ° C., and every predetermined time. The film was taken out and the mass of the film was measured. When the rate of increase in the film mass lasts 3 times within the range of 0.2%, it is judged that the absorption of moisture into the polyamide resin film has reached saturation, and the mass (Xg) of the film before being immersed in water The saturated water absorption (%) was calculated from the mass (Yg) of the film when reaching saturation with the following equation (1).

  Saturated water absorption (%) = (Y−X) / X × 100 (1)

(7) Chemical Resistance After the polyamide hot press film obtained according to the present invention was immersed in the following chemicals for 7 days, changes in mass residual rate (%) and appearance of the film were observed. Tests were conducted on samples immersed in concentrated hydrochloric acid, 64% sulfuric acid, and glacial acetic acid at 23 ° C.

(8) Hydrolysis resistance The film molded under the condition (5) above is put in an autoclave, and in water, 0.5 mol / l sulfuric acid, 1 mol / l sodium hydroxide aqueous solution (that is, pH = 7, pH = 1, pH = 14), and the mass residual ratio (%) after treatment at 121 ° C. for 60 minutes was examined.

(9) Mechanical properties The measurement shown below is performed by injection molding of the following test piece at a resin temperature of 260 ° C. (290 ° C. when using PA66, 230 ° C. when using PA12) and a mold temperature of 80 ° C. It shape | molded and performed using this.

  [1] Tensile yield strength: Measured according to ASTM D638 using a Type I test piece described in ASTM D638.

  [2] Flexural modulus: Measured at 23 ° C. in accordance with ASTM D790 using a test piece with a test piece size of 3.2 mm × 12.7 mm × 127 mm. What was evaluated without humidity adjustment after molding was described in the table as dry, and what was evaluated after conditioning at 23 ° C. and 65% humidity after molding was shown in the table.

  [3] Izod impact strength: Measured at 23 ° C. in accordance with ASTM D256 using a test piece with a test piece size of 3.2 mm × 12.7 mm × 127 mm.

  [4] Deflection temperature under load (thermal deformation temperature): Measured at a load of 1.82 MPa in accordance with ASTM D648 using a test piece having a test piece size of 3.2 mm × 12.7 mm × 127 mm.

(10) Water absorption rate A film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass of about 0.05 g) formed under the condition (5) above is placed under conditions of 23 ° C. and 65% RH, and the film is taken every predetermined time. Was taken out and the mass of the film was measured. When the rate of increase in the film mass continues three times within the range of 0.2%, it is determined that the absorption of moisture into the polyamide resin film has reached saturation, and before the 23 ° C. and 65% RH conditions are satisfied. The water absorption rate (%) was calculated from the mass (Xg) of the film and the mass (Yg) of the film when saturation was reached by the following formula (2).

Water absorption (%) = (Y−X) / X × 100 (2)
(11) Amino end group concentration 1 g of polyamide resin was dissolved in a phenol / methanol mixed solution and titrated with 0.02N hydrochloric acid.

(12) E10 Fuel Permeability Coefficient According to JIS Z0208, a fuel permeation test was performed at a measurement ambient temperature of 60 ° C. using a test piece of φ75 mm and thickness 1 mm molded by injection molding. As a fuel, 10% ethanol was mixed with Fuel C in which isooctane and toluene were mixed at a volume ratio of 1: 1. Further, the fuel permeation measurement sample surface was placed with the permeation surface facing downward so that the fuel was always in contact.
E10 fuel permeability coefficient (g · mm / m ² · day · atom) = [permeation weight (g) × film thickness (mm)] / [permeation area (mm ² ) × days (day) × pressure (atom)]

(13) Initial Adhesive Strength A test piece (Type I test piece described in ASTM D638) in which the component 1 and the component 2 were joined by the following method was produced. That is, a metal piece having the shape of part 2 described later was inserted into a mold, and part 1 was molded using polyethylene modified with maleic anhydride. Next, the component 1 was sufficiently cooled and then inserted into a mold, and a test piece was obtained by molding into the shape of the component 2 using a resin to be evaluated. Using this test piece, measure the maximum tensile strength until peeling from the interface between parts 1 and 2 or breaking at a part other than the interface (base material failure) at a tensile speed of 50 mm / min. It was.

(14) Adhesive strength after immersion in fuel A test piece molded in the same procedure as the evaluation of initial adhesive strength was placed in an autoclave, and Fuel C + ethanol 10% mixed fuel was sealed until the test piece was completely immersed. The autoclave was left in a 60 ° C. hot water tank for 350 hours. Thereafter, the maximum tensile strength of the test piece taken out was measured in the same manner as described above, and was taken as the adhesive strength after immersion in fuel.

[Production Example 1: Production of PA92-1]
Oxalic acid in a pressure vessel with a volume of 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with a diaphragm pump, nitrogen gas inlet, pressure relief port, pressure regulator and polymer outlet The operation of charging 28.40 kg (140.4 mol) of dibutyl, pressurizing the inside of the pressure vessel to 0.5 MPa with nitrogen gas having a purity of 99.9999%, and then releasing nitrogen gas to normal pressure is performed 5 After repeated nitrogen substitution, the system was heated while stirring under a sealing pressure. After adjusting the temperature of dibutyl oxalate to 100 ° C. over about 30 minutes, 18.89 kg (119.3 mol) of 1,9-nonanediamine and 3.34 kg (21.1 mol) of 2-methyl-1,8-octanediamine were obtained. ) (Molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 85:15) into a reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. The temperature was raised simultaneously with the supply. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. over 1 hour. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was brought to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. for 4.5 hours. . Thereafter, stirring was stopped, the inside of the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes, then released to an internal pressure of 0.5 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer. The obtained polyamide was a white tough polymer, and ηr = 3.20.

[Production Example 2: Production of PA92-2]
A mixture of 17.62 kg (111.3 mol) of 1,9-nonanediamine and 4.45 kg (28.1 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 80:20). The obtained polyamide was a white tough polymer and had ηr = 3.10.

[Production Example 3: Production of PA92-3]
A mixture of 11.11 kg (70.2 mol) of 1,9-nonanediamine and 11.11 kg (70.2 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 50:50). The obtained polymer was a white tough polymer, and ηr = 3.35.

[Production Example 4: Production of PA92-4]
A mixture of 6.67 kg (42.1 mol) of 1,9-nonanediamine and 15.56 kg (98.3 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by reacting in the same manner as in Production Example 1 except that the octanediamine molar ratio was 30:70). The obtained polyamide was a white tough polymer, and ηr = 3.55.

[Production Example 5: Production of PA92-5]
A mixture of 1.33 kg (8.4 mol) of 1,9-nonanediamine and 20.88 kg (131.9 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 6:94). The obtained polymer was a white tough polymer, and ηr = 3.53.

[Production Example 6: Production of PA92-6]
A mixture of 1.33 kg (8.4 mol) of 1,9-nonanediamine and 20.88 kg (131.9 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -The octanediamine molar ratio was 6:94), and the reaction was carried out in the same manner as in Production Example 1 except that the internal pressure by extracting butanol was maintained at 0.25 MPa to obtain polyamide. The obtained polymer was a white tough polymer, and ηr = 4.00.

[Production Example 7: Production of PA-1]
Using only 22.25 kg (140.4 mol) of 1,9-nonanediamine as a diamine raw material, a reaction was carried out in the same manner as in Production Example 1 to obtain a polyamide. The obtained polymer was a yellowish white polymer, and ηr = 2.78.

  Table 1 shows the characteristic data of polyamides prepared in Production Examples 1 to 7 and commercially available PA6 (Ube Industries, UBE nylon 1015B), PA66 (Ube Industries, UBE nylon 2020B) and PA12 (Ube Industries, UBESTA3020U). Shown in

  Various evaluation shown in Table 2 was performed using PA92-1-6 prepared above and said PA6.

[Example 1]
When PA92-6 was used and a nozzle for connecting a hose was molded as a fuel tank part by injection molding, there was no generation of bubbles, surface protrusions, silver, cracks, etc., and it was possible to mold without problems.

  The fuel tank component of the present invention has excellent fuel permeation resistance and low water absorption, but can be made to have a high molecular weight by melt polymerization, and has a wide range of moldable temperature estimated from the difference between the melting point and the thermal decomposition temperature. Since it is excellent in moldability and excellent in chemical resistance and hydrolysis resistance, it can be suitably used as various bubbles, various connection nozzles, various separators and the like.

Claims (5)

  The dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the moles of 1,9-nonanediamine and 2-methyl-1,8-octanediamine A fuel tank component comprising a polyamide resin having a ratio of 1:99 to 99: 1 and attached to the fuel tank.   The relative viscosity (ηr) of the polyamide resin when measured at 25 ° C. using a polyamide resin solution with a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent is 1.8 to 6.0. The fuel tank component according to 1.   1% weight loss temperature in thermogravimetric analysis of the polyamide resin measured at a heating rate of 10 ° C./min in a nitrogen atmosphere and by differential scanning calorimetry measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. The fuel tank component according to claim 1 or 2, wherein a temperature difference from the measured melting point is 50 ° C or more.   The fuel tank component according to any one of claims 1 to 3, wherein the diamine component has a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine of 5:95 to 95: 5. . The fuel tank component according to claim 1, wherein the polyamide resin has an amino end group concentration of 1.5 × 10 ⁻⁵ eq / g to 1.0 × 10 ⁻⁴ eq / g.