JP5584966B2 - Heat-resistant agent-containing resin composition and molded product formed from the heat-resistant agent-containing resin composition - Google Patents

Description

  The present invention relates to a heat-resistant agent-containing resin composition using a novel polyamide resin. Specifically, it contains a polyamide resin whose dicarboxylic acid component is oxalic acid and a heat-resistant agent, has low water absorption, excellent chemical resistance and hydrolysis resistance, a wide moldable temperature range, excellent moldability, and heat resistance. The present invention relates to a heat-resistant agent-containing resin composition that is also excellent in properties.

  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. Among these, improvement of the heat resistance of the polyamide resin is demanded depending on applications such as various automobile members and electric / electronic members. 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.

  A resin composition containing a polyamide resin and a heat-resistant agent is conventionally known. For example, in Patent Document 1, an extrusion resin composition comprising 100 parts by weight of a polyamide resin, 0.01 to 2.0 parts by weight of a heavy metal deactivator and 0 to 3.0 parts by weight of a heat-resistant agent is applied to a copper wire. A covered electric wire is disclosed. However, this technique has a problem that heat resistance, low water absorption, chemical resistance, and hydrolysis resistance cannot be satisfied at a satisfactory level.

  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 problematic, 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 whose diamine component is 1,9-nonanediamine (hereinafter abbreviated as PA92), L. Franco et al. Discloses a production method and its 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. 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 form a tough molded body is obtained.

The present inventors use oxalic acid as a dicarboxylic acid component, and a polyamide resin using 1,9-nonanediamine and 2-methyl-1,8-octanediamine in a specific ratio as a diamine component has low water absorption, It was disclosed that it is a polyamide resin (PA92C) having a wide melt molding temperature range and excellent properties (Patent Document 4).
However, this polyamide resin uses oxalic acid as the dicarboxylic acid component, and has a specific ratio of three diamines of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine as the diamine component. It is not the polyoxamide resin used in 1.

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988) JP-A-7-268211 JP 2006-57033 A Japanese National Patent Publication No. 5-506466 WO2008 / 072754

  The inventors of the present invention are that the dicarboxylic acid component is oxalic acid, the dicarboxylic acid component is oxalic acid, and the diamine component is a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine (hereinafter referred to as “C9 diamine mixture”). ) And 1,6-hexanediamine (hereinafter also referred to as “C6 diamine”), and a molar ratio of the C9 diamine mixture to the C6 diamine is 1:99 to 99: 1 (hereinafter referred to as “polyamide resin”). In the same manner as the polyamide resin (PA92C) previously disclosed in Patent Document 3 by the present inventors, while being excellent in mechanical properties and chemical resistance, With a molecular weight, the difference between the melting point and the thermal decomposition temperature is sufficiently large and excellent in melt moldability, and without impairing the low water absorption seen in linear polyoxamide resins. Not only is a polyamide resin composition superior in hydrolysis resistance compared to conventional polyamides, but this novel polyamide resin (PA92 / 62T) has a higher melting point and flexural elasticity than PA92C. It has excellent mechanical properties such as rate and deflection temperature under load, and is advantageous in terms of cost, but has a feature that the decrease in melting temperature range is within an allowable range and low water absorption is not substantially lost. The present invention has been completed. However, there is a demand for improvement in heat resistance particularly in applications such as various automobile members and electric / electronic members.

  The problem to be solved by the present invention is a low water absorption, a wide range of moldable temperature estimated from the difference between the melting point and the thermal decomposition temperature, excellent in melt moldability, excellent in chemical resistance and hydrolysis resistance, Furthermore, it is providing the resin composition which is excellent in heat resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the dicarboxylic acid component is oxalic acid, and the diamine component is a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. (Hereinafter referred to as “C9 diamine mixture”) and 1,6-hexanediamine (hereinafter referred to as “C6 diamine”), and the molar ratio of C9 diamine mixture to C6 diamine is 1:99 to 99: 1. By using a combination of a polyamide resin and a heat-resistant agent (hereinafter also referred to as “PA92 / 62T”), the moldable temperature range estimated by the difference between the melting point and the thermal decomposition temperature is, for example, 50 ° C. or more while having low water absorption. Resin composition that is excellent in melt moldability, and can be as wide as 60 ° C. or more, excellent in chemical resistance and hydrolysis resistance, and also in heat resistance Heading can be obtained, and have completed the present invention. That is, the present invention is as follows.

[1] A heat-resin-containing resin composition comprising a polyamide resin and a heat-resistant agent,
The dicarboxylic acid component of the polyamide resin is composed of oxalic acid, the diamine component is composed of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine, and C9 diamine (1,9-nonanediamine). And 2-methyl-1,8-octanediamine) and 1,6-hexanediamine in 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 heat-resin-containing resin composition 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 heat-resisting agent-containing resin composition 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] In any one of [1] to [3] above, the diamine component has a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine of 5:95 to 95: 5. The heat-resistant agent containing resin composition of description.

  [5] The heat resistance according to any one of [1] to [4], wherein the heat-resistant agent is blended within a range of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the polyamide resin. Agent-containing resin composition.

  [6] A molded product formed from the heat-resistant agent-containing resin composition according to any one of [1] to [5].

  The heat-resisting agent-containing resin composition of the present invention has a low water-absorbing property, but has a wide moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature, and is excellent in melt moldability, excellent in chemical resistance and hydrolysis resistance. Furthermore, because it is also excellent in heat resistance, it is widely used as a molding material for industrial materials, industrial materials, household products, etc., especially for various automotive parts, electrical / electronic parts, etc. that require heat resistance. Can do.

  The heat-resistant agent-containing resin composition of the present invention is a combination of a specific polyamide resin and a heat-resistant agent, and has a wide moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature, and is excellent in melt moldability. In addition, the heat-resistant agent-containing resin composition of the present invention has the advantages of low water absorption, excellent chemical resistance, hydrolysis resistance, and excellent heat resistance, so that it does not easily deteriorate even after long-term use. Have.

(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, the diamine component is 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine and a polyamide having a molar ratio of C9 diamine (1,9-nonanediamine and 2-methyl-1,8-octanediamine) to 1,6-hexanediamine of 1:99 to 99: 1 Resin.

  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 above 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.

  The molar ratio of the 1,9-nonanediamine component to the 2-methyl-1,8-octanediamine component in the C9 diamine mixture used in the polyamide resin of the present invention is generally 1:99 to 99: 1, preferably 5:95 to 95: 5, more preferably 5:95 to 40:60 or 60:40 to 95: 5, especially 5:95 to 30:70 or 70:30 to 90:10. By copolymerizing 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine in the above specific amounts, the moldable temperature range is wide, the melt moldability is excellent, and the water absorption is low. Polyamide having excellent properties, chemical resistance, hydrolysis resistance, transparency and the like can be obtained.

  In the polyamide resin of the present invention, as the diamine component, the C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octanediamine) mixed with 1,6-hexanediamine is used. The molar ratio of C9 diamine mixture to 1,6-hexanediamine is 1:99 to 99: 1. By mixing 1,6-hexanediamine in a molar ratio of 1/99 or more with respect to the C9 diamine mixture, the above excellent effect of the polyamide resin (PA92C) comprising oxalic acid as the dicarboxylic acid component and C9 diamine mixture as the diamine component Can be maintained (particularly without impairing melt moldability and low water absorption), the melting point of the polyamide resin can be increased, and particularly the mechanical properties can be improved. The molar ratio of the C9 diamine mixture to 1,6-hexanediamine is preferably 5.1: 94.9 to 99: 1, more preferably 10:90 to 99: 1, and even more preferably 20:80 to 99: 1. It is. In particular, it is preferably 30:70 to 98: 2, and more preferably 30:70 to 90:10 (further 30:70 to 70:30). In this polyamide resin, the change to the melting point appears clearly by copolymerizing 1,6-hexanediamine in a molar ratio of 1/99 or more with respect to the C9 diamine mixture, and the melting point of the resin rises. If 6-hexanediamine is within a molar ratio of 99/1, an acceptable melt moldability can be obtained. If the molar ratio of 1,6-hexanediamine is within 80/20, the melting point of the polyamide resin will be 300 ° C. or lower, and polymerization and molding (melt moldability) will be easier, and within 70/30. It is more preferable because the melting point becomes 280 ° C. or lower and the melt moldability becomes easier.

(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. 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 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. Other diamine components other than 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 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, isophoronediamine and other alicyclic diamines, 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 is composed of oxalic acid, the diamine component is composed of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine, and C9 diamine (1, 9-nonanediamine, 2-methyl-1,8-octanediamine) and 1,6-hexanediamine in a molar ratio of 1:99 to 99: 1 as polyamides other than polyamide, polyoxamide, aromatic polyamide, aliphatic Examples thereof include polyamides such as polyamide and alicyclic polyamide, and thermoplastic polymers other than polyamide. 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, 2-methyl-1,8-octanediamine and 1,6-hexanediamine, and C9 diamine ( 1,9-nonanediamine, 2-methyl-1,8-octanediamine) and 1,6-hexanediamine have a molar ratio of 1:99 to 99: 1. % Or more is preferable.

(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 oxalic acid by copolymerizing 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine as the diamine component. It is possible to increase the relative viscosity, that is, to increase the molecular weight, as compared with a polyamide comprising 1,9-nonanediamine. 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.

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 not lower than the boiling 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, a mixture of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,6-hexanediamine, and C9 diamine (1,9-nonanediamine and 2-methyl-1,8-octanediamine) In the case of a polyoxamide resin using diamine and dibutyl oxalate as raw materials in a molar ratio of a mixture of 1,6-hexanediamine of 1:99 to 99: 1, the mixing temperature is preferably 15 ° C to 300 ° C. When the molar ratio of C9 diamine (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6-hexanediamine is about 5:95 to 90:10, it is liquid at room temperature. Or it is more preferable because it is easy to handle because it liquefies only by heating to about 50 ° C. 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, 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio), more preferably 0.98 to 1. 0.02 (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, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine, and C9 diamine (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) ) And 1,6-hexanediamine molar ratio is 50:50, and diamine and dibutyl oxalate having a molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of 50:50 are used as raw materials. In the case of the polyoxamide resin, the melting point is 261 ° C., so it is preferable to raise the temperature from 270 ° C. to 300 ° 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 270 to 300 ° C. The alcohol is cooled and liquefied by a water-cooled condenser and recovered.

(II) Heat-resistant agent As the heat-resistant agent, any one that can be used as a heat-resistance improving agent for polyamide can be used, and organic or inorganic heat-resistant agents can be used depending on the purpose.

  Examples of the organic heat-resistant agent of the heat-resistant agent used in the present invention include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and benzotriazole-based materials. Specifically, 3,9-bis [2- [3- (t-Butyl-4-hydroxy-5-methylphenyl) propoxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5.5) undecane, triethylene glycol- Bis [3- (3t-butyl-5-methyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5 di-t-butyl-4hydroxyphenyl) propionate], N, N′-hexamethylenebis (3 5 di-t-butyl 4-hydroxy-hydroxynnamamide), tris (2,4 di-t-butylphenyl) phosphite, trisnoni Phenyl phosphite, pentaerythritol tetrakis (3-lauryl thiopropionate), 2- (3,5-di-t-butyl 2-hydroxyphenyl) 5 chlorobenzotriazole, 2- [2-hydroxy-3,5-bis (Α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, dimethyl succinate 1 (2-hydroxyethyl) 4hydroxy 2,2,6,6 tetramethylpyrimidine polycondensate and the like.

  One type of inorganic heat-resistant agent used in the present invention is a metal compound (salt) belonging to a Group I transition series element. For example, a halide, sulfate, acetate, salicylic acid of this metal. Salts, nicotinates or stearates are mentioned. Further, alkali metal halide salts may be used alone or in combination with metal compounds (salts) belonging to the above Group I transition series elements. Specific examples thereof are potassium iodide, sodium iodide or potassium bromide. Furthermore, it is more effective when a nitrogen-containing compound such as melamine, benguanamine, dimethylolurea or cyanuric acid is used in combination.

  It is preferable that the compounding quantity of the heat-resistant agent used by this invention exists in the range of 0.01-3.0 mass parts with respect to 100 mass parts of polyamide resins used by this invention, More preferably, 0.01-2. It is in the range of 0 parts by mass. When the blending amount is 0.01 parts by mass or more, the effect of improving the heat resistance is particularly good. When the blending amount is 3.0 parts by mass or less, the heat-resistant agent-containing resin composition and the colored product formed therefrom are colored. The effect of adding a heat-resistant agent can be sufficiently obtained while avoiding the occurrence of cracks and bumps.

(III) Other components In the present invention, various additives can be combined as needed in addition to the polyamide resin and the heat-resistant agent, and these may be combined during or after the polyamide polycondensation reaction. it can.

  Various additives include fillers, reinforcing fibers, stabilizers such as copper compounds, colorants, UV absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, glass fibers, plastics Agents, lubricants and the like.

(IV) Molding process from heat-resistant agent-containing resin composition to molded product The present invention also provides a molded product formed from the above-described heat-resistant agent-containing resin composition of the present invention. As the molding method from the heat-resisting agent-containing resin composition to the molded product, all known molding processing methods applicable to polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching can be used, By these molding methods, it can be processed into molded products such as films, sheets, molded articles, and fibers.

  More specifically, for example, predetermined amounts of polyamide resin, heat-resistant agent and various additives to be used as needed are mixed using a low-speed rotary mixer such as a V-type blender or tumbler or a high-speed rotary mixer such as a Henschel mixer. After mixing in advance, a method of directly molding a molded product using an injection molding machine or an extrusion molding machine can be applied.

(V) Use of molded product The molded product obtained according to the present invention includes various extruded products, various injection molded products, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded products have been conventionally used. As a molded product, it can be used for a wide range of applications such as automobile parts, computers and related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, It can be suitably used for various automotive parts, electrical / electronic parts and the like that are required to have high performance.

  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 300 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 300 ° 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 300 ° C. at a rate of 10 ° C./min (called a temperature rising 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 25mm cone plate to a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan Co., Ltd. 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 melted by heating at 290 ° C. (260 ° C. for PA6, 290 ° C. for PA66, 230 ° C. for PA12) 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 increase rate of the film mass is continued three times in the range of 0.2%, it is determined 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 saturation was reached by 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 following test specimens were measured by injection molding of the following test pieces at a resin temperature of 290 ° C. (260 ° C. for PA6, 290 ° C. for PA66, 230 ° C. for 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 (%) was calculated from the mass (Xg) of the film and the mass (Yg) of the film when saturation was reached by the following formula (1).

  Water absorption rate (%) = (Y−X) / X × 100 (1)

(11) Presence or absence of cracks The test piece for measuring the deflection temperature under load was left in an oven at 140 ° C, taken out after 0 to 20 days, and visually observed for occurrence of cracks when bent at 90 °.

(12) Tensile Strength Retention Rate The Type I test piece described in ASTM D638 was left in an oven at 140 ° C., taken out after 14 days, and the breaking strength was measured. The test piece which was not heat-processed was measured and the fracture strength retention was computed from the following (2) formula.

  Tensile strength retention rate (%) = [(breaking strength of heat-treated sample) / (breaking strength of untreated sample)] × 100 (2)

[Production Example 1: PA92 / 62T-1]
Oxalic acid in a pressure vessel with an internal volume of about 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected to the diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator and polymer outlet The operation of charging 28.230 kg (139.56 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 times. After repeated nitrogen substitution, the system was heated while stirring under a sealing pressure. After the temperature of dibutyl oxalate was raised to 100 ° C. over about 30 minutes, 1.241 kg (7.84 mol) of 1,9-nonanediamine and 19.639 kg (124.04 mol) of 2-methyl-1,8-octanediamine were obtained. And a mixture of 0.893 kg (7.68 mol) of 1,6-hexanediamine (molar ratio of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine is 5.62: 88.88: 5.50) was supplied into the reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes, and at the same time the temperature was raised. 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 0.75 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 = 3.13.

[Production Example 2: PA92 / 62T-2]
28.462 kg (140.71 mol) of dibutyl oxalate was charged, 16.448 kg (103.88 mol) of 1,9-nonanediamine, 2.903 kg (18.34 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 2.150 kg (18.50 mol) (mixture ratio of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine is 73.83: 13.13. 03: 13.14) was reacted in the same manner as in Production Example 1 to obtain polyamide. The obtained polyamide was a white tough polymer with ηr = 2.97.

[Production Example 3: PA92 / 62T-3]
30.238 kg (149.49 mol) of dibutyl oxalate was charged, 4.486 kg (28.33 mol) of 1,9-nonanediamine, 4.486 kg (28.33 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 10.79 kg (92.85 mol) (1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine molar ratio of 18.95: 18. 95: 62.10) was supplied into the reaction vessel with a diaphragm pump at a flow rate of 1.49 liters / minute over about 17 minutes, and at the same time the temperature was raised. 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 270 ° C. over 1.5 hours. Meanwhile, the internal pressure was adjusted to 1.00 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 270 ° 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 changed to 285 ° C. over about 1 hour, and the reaction was carried out at 285 ° C. for 1.5 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 = 2.88.

[Production Example 4: PA92 / 62T-4]
29.864 kg (147.64 mol) of dibutyl oxalate was charged, and 5.598 kg (35.36 mol) of 1,9-nonanediamine, 5.598 kg (35.36 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 8.941 kg (76.92 mol) of a mixture (the molar ratio of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine was 23.95: 23. 95: 52.10) was supplied to the reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute over about 17 minutes, and at the same time the temperature was raised. 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 250 ° C. over 1 hour. Meanwhile, the internal pressure was adjusted to 1.00 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 250 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 liters / minute, and the temperature of the polycondensate was increased to 270 ° C. over about 1 hour and reacted at 270 ° C. for 2 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 with ηr = 2.83.

[Production Example 5: PA92 / 62T-5]
29.107 kg (143.89 mol) of dibutyl oxalate was charged, 5.641 kg (35.63 mol) of 1,9-nonanediamine, 10.028 kg (63.34 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 5.223 kg (44.93 mol) (1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,6-hexanediamine molar ratio 24.76: 44. 02: 31.22) was supplied into the reaction vessel over about 17 minutes at a flow rate of 1.49 liters / minute by means of a diaphragm pump, and the temperature was raised. 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 250 ° C. over 1 hour. Meanwhile, the internal pressure was adjusted to 0.75 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 240 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 liters / minute, and the temperature of the polycondensate was adjusted to 265 ° C. over about 1 hour, and the reaction was carried out at 265 ° C. for 3 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 with ηr = 3.11.

[Reference Production Example 1: PA92C]
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 was charged with 28.40 kg (140.4 mol) of dibutyl oxalate. Was supplied into the reaction vessel over about 17 minutes at a flow rate of 1.49 liters / minute by means of a diaphragm pump, and at the same time the temperature was raised. 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 = 3.35.

[Comparative Production Example 1: Production of PA92]
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.

  Polyamide PA92 / 62T-1 to PA92 / 62T-5, PA92C, PA92, and nylon 6 (manufactured by Ube Industries, UBE nylon 1015B: PA6) produced in Production Examples 1-5, Reference Production Example 1 and Comparative Production Example 1. For nylon 66 (Ube Industries, UBE nylon 2020B: PA66) and nylon 12 (Ube Industries, UBESTA3020U: PA12), relative viscosity, melting point, crystallization temperature, 1% weight loss temperature, melt viscosity, saturated water absorption, resistance to water Chemical properties, hydrolysis resistance, mechanical properties in dry and wet conditions were measured. The results are shown in Table 1.

[Examples 1 to 7, Comparative Examples 1 and 2, Reference Example]
The composition shown in Table 2 was melt kneaded at a cylinder setting temperature of 290 ° C. (260 ° C. for PA 6 and 230 ° C. for PA 12) at a rotational speed of 150 rpm in a biaxial kneader PCM-45 manufactured by Ikekai Tekko Co., Ltd. Using the test piece obtained by injection molding at a resin temperature of 290 ° C. (260 ° C. for PA6, 230 ° C. for PA12) and a mold temperature of 80 ° C., the evaluation shown in Table 2 was performed by the method described above. .

In addition, the used heat-resistant agent is as follows corresponding to the code | symbol in a table | surface.
a: 3,9-bis [2- (3- (t-butyl-4-hydroxy-5-methylphenyl) propoxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro ( 5,5) Undecane b: Triethylene glycol-bis [3- (3t-butyl-5methyl 4-hydroxyphenyl) propionate]

  Although the heat-resistant resin composition of the present invention has low water absorption, it has a wide moldable temperature range estimated from the difference between the melting point and the thermal decomposition temperature, and is excellent in melt moldability, excellent in chemical resistance and hydrolysis resistance, Furthermore, since it is excellent also in heat resistance, it can be used suitably as molding materials, such as industrial material, industrial material, and household goods. Molded articles formed from the heat-resisting agent-containing resin composition of the present invention include, for example, various extrusion molded articles, various injection molded articles, molded articles such as sheets, films, pipes, tubes, monofilaments, fibers, etc., automobile members, optical devices. Can be used for a wide range of applications such as parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, especially various automotive parts, electrical / electronic parts that require heat resistance It can use suitably for uses, such as.

Claims (5)

A heat-resin-containing resin composition comprising a polyamide resin and a heat-resistant agent,
The dicarboxylic acid component of the polyamide resin is composed of oxalic acid,
The diamine component is from a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine (hereinafter referred to as “C9 diamine mixture”) and 1,6-hexanediamine (hereinafter referred to as “C6 diamine”). Become
The molar ratio of the C9 diamine mixture and C6 diamine 1: 99 to 99: Ri 1 der,
The molar ratio of the 2-methyl-1,8-octane diamine and the 1,9 is 5:95 to 95: 5 der Ru, heat-containing resin composition.   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. 1. The heat-resisting agent-containing resin composition 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 heat-resisting agent-containing resin composition according to claim 1 or 2, wherein the temperature difference from the measured melting point is 50 ° C or more. The heat-resistant agent-containing resin composition according to any one of claims 1 to 3 , wherein the heat-resistant agent is blended within a range of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the polyamide resin. object. A molded product formed from the heat-resistant agent-containing resin composition according to any one of claims 1 to 4 .