JP2009298863A - Vehicle interior component produced by using new polyamide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an automobile interior component, as compared with the automobile interior components by using conventional nylon 6 and nylon 66, excellent in weatherability, having a low water absorption properties and excellent dimensional stability, excellent in chemical resistance and hydrolysis resistance, having a wider moldable temperature width than those of the automobile interior components obtained by using 1,9-nonane diamine singly as a diamine component, excellent in melt moldability, and having a further higher molecular weight and toughness. <P>SOLUTION: The automobile interior component is produced by using a polyamide resin of which the dicarboxylic acid component consists of oxalic acid, and the diamine component consists of the 1,9-nonane diamine and 2-methyl-1,8-octane, and having a (1:99) to (99:1) 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 vehicle interior part manufactured using a novel polyamide resin. Specifically, compared to conventional vehicle interior parts using nylon 6 and nylon 66, it has excellent weather resistance, low water absorption, excellent dimensional stability, excellent chemical resistance and hydrolysis resistance, and diamine component The present invention relates to a vehicle interior part having a wider moldable temperature range and excellent melt moldability than a vehicle interior part using 1,9-nonanediamine alone, and having a high molecular weight and toughness.

  Crystalline polyamides such as nylon 6 and nylon 66 are not only used for clothing, industrial materials, or general-purpose engineering plastics, but also for register blades, washers, Widely used as vehicle interior parts such as lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket.

  As vehicle interior parts, performance such as weather resistance, low water absorption, chemical resistance, dimensional stability, etc. is particularly required. For example, nylon 6 has low weather resistance and chemical resistance and high water absorption. When inferior in dimensional stability and placed under conditions of high temperature and high humidity, the rigidity reduction and dimensional change due to high water absorption are large, and it is not always satisfactory as a material for interior parts. Therefore, in order to use it as a material for vehicle interior parts, it is essential to use layered silicate together (for example, Patent Document 1).

  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 substance that cannot form a tough molded article is obtained. In addition, JP-A-5-506466 discloses 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 ( Patent Document 3). In this case as well, there is a problem that only a low molecular weight body that cannot be formed into a tough molded body is obtained.
In the prior literature, there was no specific disclosure of a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio.

  In this technical field, it is desired to develop a polyamide resin having excellent weather resistance, low water absorption and excellent dimensional stability, and manufacturing a vehicle interior part using the polyamide resin.

JP-A-2-208357 JP 2006-57033 A Special table 5-506466

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988)

  The present invention has been made based on the above circumstances, and the present invention is superior in weather resistance, low water absorption, and excellent in dimensional stability as compared with conventional vehicle interior parts using nylon 6 and nylon 66. Excellent in chemical resistance and hydrolysis resistance, has a wider moldable temperature range than vehicle interior parts using 1,9-nonanediamine alone as a diamine component, has excellent melt moldability, and has a high molecular weight and toughness. It is an object to provide parts.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that from oxalic acid diester as the oxalic acid source, 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component. It has been found that the above-mentioned problems can be solved by using the resulting polyamide resin for the vehicle interior parts, and the present invention has been completed.

Specifically, the present invention relates to the following aspects.
[Aspect 1]
The dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine Is a vehicle interior part manufactured using a polyamide resin having a ratio of 1:99 to 99: 1.

[Aspect 2]
Aspect 1 in which the relative viscosity (ηr) measured at 25 ° C. using a polyamide resin solution having a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent is 1.8 to 6.0. Vehicle interior parts described in 1.
[Aspect 3]
1% weight loss temperature in thermogravimetric analysis of the polyamide resin measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and differential scanning calorimetry measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. The vehicle interior part according to aspect 1 or 2, wherein the temperature difference from the melting point measured by the step is 50 ° C or higher.

[Aspect 4]
The vehicle interior part according to any one of aspects 1 to 3, wherein the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 95: 5.

  The vehicle interior parts of the present invention have superior weather resistance, low water absorption, excellent dimensional stability, chemical resistance and hydrolysis resistance compared to conventional vehicle interior parts using nylon 6 and nylon 66. It is excellent and has a wider moldable temperature range than a vehicle interior part using 1,9-nonanediamine alone as a diamine component, has excellent melt moldability, and can produce a tough part made of a polymer.

Hereinafter, the present invention will be described in detail.
[Polyamide resin]
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 molar ratio with 1,8-octanediamine is 1:99 to 99: 1.

  As the oxalic acid source as the dicarboxylic acid source of the polyamide resin used in the present invention, oxalic acid diester is used, and there is no particular limitation as long as it has reactivity with an amino group. Dimethyl oxalate, diethyl oxalate, oxalic acid Di-n- (or i-) propyl, oxalic acid diesters of aliphatic monohydric alcohols such as di-n- (or i-, or t-) butyl oxalate, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, diphenyl oxalate, etc. And oxalic acid diesters of aromatic alcohols.

  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.

  In the polyamide resin used in the present invention, oxalic acid is used as the dicarboxylic acid source, but other dicarboxylic acid components can be blended within a range that does not impair the effects of the present invention. Examples of 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 dicarboxylic acid aromatic dicarboxylic acids such as such alone or may be added any mixtures thereof during the polycondensation reaction. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The blending amount of the other dicarboxylic acid is not particularly limited as long as the effects of the present invention are not impaired. In general, it is preferably 5 mol% or less with respect to the total amount of the dicarboxylic acid.

  As the diamine component, 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used. The molar ratio of the 1,9-nonanediamine component to the 2-methyl-1,8-octanediamine component is 1:99 to 99: 1, preferably 5:95 to 95: 5. By copolymerizing a specific amount of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, a polyamide having a high molecular weight and a high melt viscosity can be obtained as compared with a conventional polyamide.

Furthermore, the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is preferably, for example, 5:95 to 40:60 or 60:40 to 95: 5, and 5: It is particularly preferred that it is 95-30: 70 or 70: 30-90: 10.
When the molar ratio is 5:95 to 40:60, particularly 5:95 to 30:70, the crystallinity is excellent, so that low water absorption and mechanical properties are excellent, and liquid and / or vapor (for example, , Alcohol) has low permeability, and more water absorption than the case where the molar content of 1,9-nonanediamine is higher than the molar content of 2-methyl-1,8-octanediamine. There is an advantage that it is low. On the other hand, when the molar ratio is 60:40 to 95: 5, particularly 70:30 to 90:10, there is an advantage that low water absorption and mechanical properties are more excellent and excellent transparency is imparted. .

  The polyamide resin used in the present invention uses 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component, but other diamine components are used as long as the effects of the present invention are not impaired. Can be blended. 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'-aromatic diamines diaminodiphenyl ether or the like, etc. alone, or can be added any mixture thereof during the polycondensation reaction.

  Although it will not specifically limit if it is a range which does not impair the effect of this invention as a compounding quantity of said other diamine component, It is preferable that it is 5 mol% or less with respect to the total amount of a diamine component.

[Production method of polyamide resin]
The polyamide resin used in the present invention can be produced by any method known as a method for producing polyamide. According to the study by the present inventors, it is preferable to polymerize the polyamide resin by subjecting diamine and oxalic acid diester to a polycondensation reaction 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).

  While stirring and / or nitrogen bubbling in the reactor charged with the above raw materials, the temperature is raised under normal pressure. 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 reached is 3-6 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.

  Next, the specific example of the manufacturing method of the polyamide resin used for this invention is demonstrated. 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 that is not lower than the melting point and lower than the boiling point of the oxalic acid diester and diamine, and the polyoxamide generated by the polycondensation reaction of the oxalic acid diester and 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 1:99 to 99: In the case of a polyoxamide resin using diamine 1 and dibutyl oxalate as raw materials, the mixing temperature is preferably 15 ° C to 240 ° C. Moreover, since the molar ratio of 1,9-nonanediamine and 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 and diamine is oxalic acid diester / diamine as described above, 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio), more preferably 0.98. -1.02 (molar ratio).

  Subsequently, 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 no thermal decomposition occurs. For example, a diamine and shu comprising 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 85:15. In the case of a polyoxamide resin using dibutyl acid 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.

[Characteristics of polyamide resin]
The molecular weight of the polyamide resin used in the present invention is 1.0 to 6.0 g, more preferably 2.0 to 5 relative viscosity ηr measured at 25 ° C. using a 1.0 g / dl 96% concentrated sulfuric acid solution. .5, particularly preferably having a molecular weight in the range of 2.5 to 4.5. When the molecular weight is low, the melt viscosity is low, and when the molecular weight is high, the melt viscosity is high and the moldability tends to be poor.

  The polyamide resin used in the present invention uses oxalic acid as the carboxylic 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. The relative viscosity can be increased, that is, the molecular weight can be increased as compared with the polyamide made of 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 polyamide composed of 1,9-nonanediamine, 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.

[Vehicle interior parts]
In the present specification, the term “vehicle interior part” means a part used for the interior of a vehicle. Vehicles include automobiles such as passenger cars, buses, trucks, special automobiles such as tractors, road rollers, snow vehicles, forklifts, wheel cranes, special purpose automobiles such as ambulances, fire trucks, television relay cars, and refrigerated cars. However, it is not limited to these.

Examples of the vehicle interior parts include, for example, a register blade, a washer lever, a window regulator handle, a knob of a window regulator handle, a passing light lever, a sun visor bracket, an instrument panel, a console box, a glove box, a steering wheel, Trim is mentioned.
Although the vehicle interior component of the present invention includes the above-described polyamide resin, the vehicle interior component can further include the following components as optional components in addition to the polyamide resin.

(1) Other polymer The dicarboxylic acid component used in the present invention 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- The polyamide resin having a molar ratio with methyl-1,8-octanediamine of 1:99 to 99: 1 can be partially substituted with other polymer components as long as the effects of the present invention are not impaired. Examples of other polymer components include other polyamides such as polyoxamide, aromatic polyamide, aliphatic polyamide, alicyclic polyamide, and polymers other than polyamide, such as thermoplastic polymers and elastomers.

Although it will not specifically limit if it is the range which does not impair the effect of this invention as said substitution ratio by said other polymer, Preferably it is less than 50 mass%, More preferably, it is 30 mass% or less.
In the following, when simply referred to as “polyamide” or “polyamide resin”, the dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, And it shall refer to the polyamide resin whose molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 1: 99-99: 1.

(2) Additive Further, the vehicle interior part of the present invention can contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, pigments, dyes, colorants, heat resistance agents, antioxidants, weathering agents, UV absorbers, light stabilizers, lubricants, crystal nucleating agents, crystallization accelerators, mold release agents, and charging agents. Examples thereof include stabilizers, plasticizers, stabilizers such as copper compounds, antistatic agents, flame retardants, glass fibers, lubricants, fillers, reinforcing fibers, reinforcing particles, and foaming agents.

  As the ultraviolet absorber, an ultraviolet absorber conventionally used in polyamide resins can be used. Examples of the ultraviolet absorber include benzophenone, benzotriazole, triazole, imidazole, oxazole, resorcinol, salicylate, cyanoacrylate, triazine, metal complex, and the like. Can be mentioned.

  Specifically, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-) Methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-tert) -Octylphenyl) benzotriazole, 2- (3,5-di-tert-butyl) 2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazole-2) -Yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2,2′-methylenebis [4-tert-butyl-6- (2H-benzotriazol-2-yl) phenol], 2-Ethylhexyl-3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxy Enyl] propionate, octyl-3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl-3- [3-tert-butyl- 5- (5-Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl)- 4-hydroxyphenyl] propionic acid.

Trade names of the above-mentioned ultraviolet absorbers include, for example, Tinuvin 327 (benzotriazole series manufactured by Ciba Specialty Chemicals Co., Ltd.), Tinuvin 234 (benzotriazole series manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanduvor VSU (Clariant Co., Ltd.) Succinic acid anilide type).
The ultraviolet absorber is usually used at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin.

  Examples of the light stabilizer include hindered amines. Specifically, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) -2,2-bis (3 5-di-tert-butyl-4-hydroxybenzyl) malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, bis (2,2,6,6-tetramethyl- 4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 4- [3- (3,5-di − ert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -2,2,6,6 -Tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1- Mixed esterified product of lidocaanol, mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3, 4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetra Mixed esterified products with oxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2- Hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, dimethyl succinate and 1- (2-hydro Xylethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [{6- (1,1,3,3 -Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6, 6-tetramethyl-4-piperidyl) imino}], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane polycondensate , N, N ′, 4,7-tetrakis [4 6-bis {N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1, 10-diamine, N, N ′, 4-tris [4,6-bis {N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino} -1,3,5- Triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6) , 6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6- Bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino}- , 3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine.

As a trade name of the light stabilizer, for example, Tinuvin 123 (Ciba Specialty Chemicals Co., Ltd., hindered amine series) Chimassorb 944 (Ciba Specialty Chemicals Co., Ltd., hindered amine series), Chimassorb 119 (Ciba Specialty Corp.) Chemicals Co., Ltd., hindered amine type).
The light stabilizer is usually used at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin.

  The method for adding the other polymer and the additive is not particularly limited as long as each of them can be dispersed in the polyamide resin, and the polyamide resin can be added to the polyamide resin at any time without impairing its effect. Can be added. For example, the other polymers and additives can be added immediately after the post polycondensation step of the polyamide resin.

(3) Layered silicate The vehicle interior parts of the present invention are low in water absorption and excellent in dimensional stability with only the above-mentioned polyamide resin, but in applications requiring lower water absorption and dimensional stability, the layered silicate is used. Can be added to the polyamide resin.
Moreover, the addition of the layered silicate can improve the rigidity, weather resistance and / or heat resistance of the vehicle interior part of the present invention, and the barrier property against liquid or vapor.
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, it is preferable that the said layered silicate is what is uniformly disperse | distributed in the said polyamide resin, each layer maintaining the interlayer distance of about 20 mm or more.

  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.

  The amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but preferably 0.05 to 10 mass with respect to 100 parts by mass of the polyamide resin. Parts, more preferably 0.05 to 8 parts by mass, particularly preferably 0.05 to 5 parts by mass. When the proportion of layered silicate is low, the effect of layered silicate is not exhibited, and when the proportion is high, the melt viscosity becomes extremely high and the molding processability tends to deteriorate or the impact resistance tends to decrease. .

  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 method for adding the layered silicate is not particularly limited as long as the layered silicate can be uniformly dispersed in the polyamide resin. For example, when the raw material of the layered silicate is a multilayered clay mineral, as disclosed in JP-A-62-74957, the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as, for example, 1,9-nonanediamine and 2-methyl-1,8-octanediamine are added to widen the space between the layers of the layered silicate in advance. Next, a polyamide raw material can be introduced between the layers, and the raw materials can be polymerized between the layers.

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

  The vehicle interior part of the present invention can be molded by, for example, extrusion molding, blow molding, compression molding, injection molding, or the like.

  Vehicle interior parts of the present invention include, for example, a register blade, a washer lever, a window regulator handle, a knob of a window regulator handle, a passing light lever, a sun visor bracket, an instrument panel, a console box, a glove box, a steering wheel, and a trim. It can be used for applications such as seat members such as seat rails, seat belt anchors, electric seat parts, seat heater parts, seat blowing parts, HVAC parts, steering switch parts, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples.

[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. After being melted by heating at 260 ° C. (resin temperature: 290 ° C. for PA66) for 5 minutes in a reduced pressure atmosphere of 500 to 700 Pa, the film was formed by pressing at 5 MPa for 1 minute. 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 (%) = 100 × (Y−X) / X (1)

(7) Chemical Resistance After immersing the polyamide hot press film obtained by the present invention in the chemicals listed below for 7 days at 23 ° C., changes in the residual mass (%) and appearance of the film were observed. Concentrated hydrochloric acid, 64% sulfuric acid, and glacial acetic acid were tested.

(8) Hydrolysis resistance A hot press film is prepared from the material for vehicle interior parts of the present invention, and the hot press film is placed in an autoclave, and water (pH = 7), 0.5 mol / l sulfuric acid (pH = 1). ) Or 1 mol / l sodium hydroxide aqueous solution (pH = 14), and the weight residual ratio (%) and appearance change after treatment at 121 ° C. for 60 minutes were examined.

(9) Mechanical properties [1] to [4] shown below are obtained by molding the following test pieces by injection molding at a resin temperature of 260 ° C. (resin temperature of 290 ° C. for PA66) and a mold temperature of 80 ° C. This was done. The data measured at 23 ° C. after the molding was shown in the table as dry, the moisture was adjusted at a humidity of 65% RH after molding, and the data measured at 23 ° C. was shown in the table.
[1] Tensile yield strength or tensile strength: Measured according to ASTM D638 using a Type I test piece described in ASTM D638.
[2] Flexural modulus: Measured according to ASTM D790 using a test piece with a test piece size of 3.2 mm × 12.7 mm × 127 mm. [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 The water absorption rate (%) was calculated according to the measurement method of (6) saturated water absorption rate, except that it was placed under conditions of 23 ° C. and humidity 65% RH.

(11) Weather resistance According to JIS-A-1415, it evaluated on the conditions of a black panel, temperature 83 degreeC, and no rain. Visual evaluation was performed after the test for 50 hours and 100 hours in accordance with the criteria of ○ (no cracks), Δ (slightly cracked), and × (with cracks).
Further, after the 50-hour weather resistance test, the tensile strength retention rate (%) of the sample was evaluated. The tensile strength retention rate (%) is calculated by dividing the tensile strength after the 50-hour weather resistance test by the tensile strength before the weather resistance test and multiplying by 100.

[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-92-0]
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 PA92-1 to PA92-6 and PA92-0.
Table 1 shows the characteristic data of commercially available products PA6 (Ube Industries, UBE nylon 1015B) and PA66 (Ube Industries, UBE nylon 2020B).

  From Table 1, the vehicle interior parts produced using the polyamide resin of the present invention have low water absorption compared to nylon 6 or nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. Excellent mechanical properties, wider moldable temperature range than polyamide resin (PA92-0) using 1,9-nonanediamine alone as diamine component, excellent melt moldability, and high molecular weight tough parts I understand.

[Examples 1 to 6]
To the pellets of PA92-1 to PA92-6 produced in Production Examples 1 to 6, Tinuvin 327 as an ultraviolet absorber and Tinuvin 123 as a light stabilizer were each added to 0.25 parts by mass with respect to 100 parts by mass of the polyamide resin. After adding a mass part and 0.25 mass part and knead | mixing at 260 degreeC using a biaxial kneader and manufacturing a pellet, the sample for a weather resistance test was created and used for the test. The results are shown in Table 2.

[Comparative Examples 1 and 2]
A sample for a weather resistance test was prepared and used for the test in the same manner as in Example 1 except that the above PA6 or PA66 was used as the resin. The results are shown in Table 2.

[Example 7: Manufacture of vehicle interior parts]
Samples of PA92-1 to PA92-6 prepared in Production Examples 1 to 6, samples containing the ultraviolet absorber and the light stabilizer produced in Examples 1 to 6, and PA6 and PA66 samples of Comparative Examples 1 and 2 Were used to produce sun visor brackets and instrumental panels by injection molding. The samples of PA92-1 to PA92-6 prepared in Production Examples 1 to 6 and the samples containing the ultraviolet absorber and the light stabilizer produced in Examples 1 to 6 were molded to be equal to or more than the PA6 sample and PA66 sample. Had sex.

  The vehicle interior parts of the present invention have superior weather resistance, low water absorption, excellent dimensional stability, chemical resistance and hydrolysis resistance compared to conventional vehicle interior parts using nylon 6 and nylon 66. Excellent, and has a wider moldable temperature range and excellent melt moldability than polyamide resin-based vehicle interior parts using 1,9-nonanediamine alone as a diamine component, and is a tough part with a high molecular weight, such as a register blade, Because it can be used widely as vehicle interior parts such as washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, instrument panel, console box, glove box, steering wheel, trim, etc. , Industrially useful.

Claims (4)

  The dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine Is a vehicle interior part manufactured using a polyamide resin having a ratio of 1:99 to 99: 1.   The relative viscosity (ηr) of the polyamide resin measured at 25 ° C. using a polyamide resin solution having a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent is 1.8 to 6.0. The vehicle interior part 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 differential scanning calorimetry measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. The vehicle interior part according to claim 1 or 2, wherein the temperature difference from the melting point measured by the above is 50 ° C or more.   The vehicle interior part according to any one of claims 1 to 3, wherein a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 95: 5.