JP6724368B2 - Molded article and polyamide resin composition - Google Patents

Description

The present invention relates to a molded product obtained by molding a polyamide resin composition and a polyamide resin composition suitably used for the molded product.

Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, and are therefore preferably used for automobiles and electric/electronic component applications. Among various applications, heat resistant aging resistance and calcium chloride resistance are required for automobile underhood parts such as radiator tanks and canisters. Conventionally, in these applications, a polyamide resin composition in which glass fibers are composited has been often used, but in recent years, higher heat aging resistance and calcium chloride resistance have been demanded. Further, when a large amount of glass fibers are combined, there is a problem that the surface appearance is impaired.

Conventionally, as a technique for improving the calcium chloride resistance of a polyamide resin, for example, a polyamide resin composition obtained by blending polyamide 6 or 66 with a higher polyamide selected from polyamides 11, 12, 610 and 612 (see, for example, Patent Document 1). )It has been known. However, there is a problem that the heat aging resistance is insufficient.

On the other hand, as a technique for improving the heat aging resistance of a polyamide resin, for example, a polyamide resin composition in which a copper compound and a halogen compound are mixed with a polyamide resin (for example, see Patent Document 2) is known. However, the polyamide resin composition of Patent Document 2 is insufficient in heat aging resistance against the recent increase in use environment temperature. Moreover, the effect on the calcium chloride resistance and the fuel barrier property was small.

In response to this, various technological improvements have been attempted as techniques for improving the heat aging resistance at high temperatures. For example, a polyamide resin composition containing a polyamide resin, a polyhydric alcohol having a number average molecular weight of less than 2000, a co-stabilizer such as a copper stabilizer or a hindered phenol, and a polymer reinforcement (see, for example, Patent Document 3). ), a polyamide resin, polyethyleneimine, a lubricant, a copper-containing stabilizer, a filler, and nigrosine have been proposed (see, for example, Patent Document 4).

JP-A-57-212252 JP, 2006-273945, A Special table 2011-599991 gazette Japanese Patent Publication No. 2008-530290

However, the molded article obtained from the polyamide resin composition of Patent Document 3 has excellent heat aging resistance in the temperature range of 150°C to 230°C, but heat aging in the temperature range of less than 150°C and 240°C or more. There was a problem that it was inferior in sex. Further, the polyamide resin composition of Patent Document 4 also has excellent heat aging resistance in the temperature range of 160°C to 180°C, but has a problem of poor heat aging resistance in the temperature range of less than 150°C. .. The temperature of the environment under which automobile underhood parts are used tends to increase year by year, but since the temperature is not always high, materials that also have heat aging resistance at low temperatures are required. Moreover, the effect on the calcium chloride resistance was small. Further, the polyamide resin compositions of Patent Documents 3 and 4 have problems in surface appearance such as (i) bleeding out of a polyhydric alcohol or the like to the surface layer of a molded product and coloring due to liberation of copper ions.

The present invention has been made in view of these problems of the prior art, and an object thereof is to provide a molded product excellent in heat aging resistance, calcium chloride resistance and surface appearance.

上記一般式（１）中、Ｘ^１〜Ｘ^６はそれぞれ同一でも異なってもよく、ＯＨ、ＮＨ_２、ＣＨ_３またはＯＲを表す。ただし、ＯＨとＮＨ_２とＯＲの数の和は３以上である。また、Ｒはアミノ基、エポキシ基またはカルボジイミド基を有する有機基を表し、ｎは０〜２０の範囲を表す。
［４］大気下、１３０℃にて１００時間熱処理した際、成形品表面から０．２ｍｍまでの深さにおけるポリアミド樹脂組成物中のカルボキシル基濃度の増加が４×１０^−５ｍｏｌ／ｇ以下である［１］〜［３］のいずれかに記載の成形品。
［５］（Ａ）ポリアミド樹脂１００重量部に対して、（Ｂ）水酸基および／またはアミノ基と、エポキシ基および／またはカルボジイミド基とを有し、１分子中の水酸基およびアミノ基の数の和が、１分子中のエポキシ基およびカルボジイミド基の数の和よりも多い化合物０．１〜２０重量部を配合してなり、前記（Ｂ）化合物が、（ｂ）水酸基および／またはアミノ基含有化合物と、（ｂ’）エポキシ基および／またはカルボジイミド基含有化合物との反応物であり、水酸基またはアミノ基と、エポキシ基またはカルボジイミド基との反応率が１０〜９０％であり、かつ、（ｂ’）エポキシ基および／またはカルボジイミド基含有化合物の分子量が８００以上１００００以下であるポリアミド樹脂組成物であって、ポリアミド樹脂組成物を射出成形して得られる厚さ６．４ｍｍの棒状試験片を、大気下、１５０℃にて１０００時間熱処理した後、フーリエ変換赤外分光分析によって得られる棒状試験片表面におけるカルボキシル基のピーク強度Ｙと、棒状試験片表面から０．２８ｍｍの深さにおけるカルボキシル基のピーク強度Ｚとの比（Ｙ／Ｚ）が５．０以下となるポリアミド樹脂組成物。
［６］前記棒状試験片を大気下、１５０℃にて１０００時間熱処理した際、フーリエ変換赤外分光分析によって得られる棒状試験片表面におけるポリアミド樹脂組成物中の（Ｂ）化合物の濃度Ｖと、棒状試験片表面から０．２８ｍｍの深さにおけるポリアミド樹脂組成物中の（Ｂ）化合物の濃度Ｗとの比（Ｖ／Ｗ）が１．２〜５．０となる［５］記載のポリアミド樹脂組成物。
［７］（ｂ）水酸基および／またはアミノ基含有化合物と、（ｂ’）分子量が８００以上１０００以下であるエポキシ基および／またはカルボジイミド基含有化合物を、あらかじめ反応率１０〜９０％で反応させ作製した（Ｂ）化合物を（Ａ）ポリアミド樹脂とともに溶融混練する［５］または［６］に記載のポリアミド樹脂組成物の製造方法。 In order to solve the above problems, the present invention mainly has the following configurations.
[1] A molded product having a thickness of 0.56 mm or more obtained by molding a polyamide resin composition, which is obtained by Fourier transform infrared spectroscopy after heat treatment at 150° C. for 1000 hours in the air a peak intensity Y of the carboxyl groups on the surface, the ratio of the peak intensity Z of the carboxyl group (Y / Z) of 5.0 I der less at a depth of 0.28mm from the surface of the molded article, the polyamide resin composition Has (B) a hydroxyl group and/or an amino group and an epoxy group and/or a carbodiimide group with respect to 100 parts by weight of the (A) polyamide resin, and the sum of the number of hydroxyl groups and amino groups in one molecule is 0.1 to 20 parts by weight of a compound, which is more than the sum of the numbers of epoxy groups and carbodiimide groups in one molecule, is blended, and the (B) compound is (b) a hydroxyl group- and/or amino group-containing compound. And (b′) an epoxy group- and/or carbodiimide group-containing compound, the reaction rate of the hydroxyl group or amino group with the epoxy group or carbodiimide group is 10 to 90%, and (b′) ) A molded article in which the epoxy group and/or carbodiimide group-containing compound has a molecular weight of 800 or more and 10000 or less .
[2] When heat-treated at 150° C. for 1000 hours in the air, the concentration V of the (B) compound in the polyamide resin composition on the surface of the molded product obtained by Fourier transform infrared spectroscopy and the value of 0. The molded article according to [ 1 ], wherein the ratio (V/W) of the (B) compound concentration W in the polyamide resin composition at a depth of 28 mm is 1.2 to 5.0.
[ 3 ] The molded article according to [1] or [2], wherein the compound (B) is a compound having a structure represented by the following general formula (1) and/or a condensate thereof.

In the above general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH _2, and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0-20.
[ 4 ] When heat-treated at 130° C. for 100 hours in the atmosphere, the increase in the carboxyl group concentration in the polyamide resin composition at a depth of 0.2 mm from the surface of the molded product is 4×10 ⁻⁵ mol/g or less. The molded product according to any one of [1] to [3] .
[5] (A) 100 parts by weight of the polyamide resin, (B) having a hydroxyl group and/or an amino group and an epoxy group and/or a carbodiimide group, the sum of the number of hydroxyl groups and amino groups in one molecule but Ri name by blending 0.1 to 20 parts by weight the compound and less than the sum of the number of epoxy groups and carbodiimide groups in one molecule, (B) the compound, (b) hydroxyl and / or amino group-containing A reaction product of a compound with (b') an epoxy group and/or a carbodiimide group-containing compound, wherein the reaction rate of the hydroxyl group or amino group with the epoxy group or carbodiimide group is 10 to 90%, and (b ') A polyamide resin composition having a molecular weight of the epoxy group and/or carbodiimide group-containing compound of 800 or more and 10000 or less, wherein a rod-shaped test piece having a thickness of 6.4 mm obtained by injection molding of the polyamide resin composition, After heat treatment at 150° C. for 1000 hours in air, the peak intensity Y of the carboxyl group on the surface of the rod-shaped test piece obtained by Fourier transform infrared spectroscopy and the carboxyl group at a depth of 0.28 mm from the surface of the rod-shaped test piece A polyamide resin composition having a ratio (Y/Z) to the peak strength Z of 5.0 or less.
[6] When the rod-shaped test piece is heat-treated at 150° C. for 1000 hours in the air, the concentration V of the (B) compound in the polyamide resin composition on the surface of the rod-shaped test piece obtained by Fourier transform infrared spectroscopy, and [ 5 ] The polyamide resin according to [ 5 ], which has a ratio (V/W) of 1.2 to 5.0 with the concentration W of the (B) compound in the polyamide resin composition at a depth of 0.28 mm from the surface of the rod-shaped test piece. Composition.
[7] (b) Hydroxyl group and/or amino group-containing compound and (b') epoxy group and/or carbodiimide group-containing compound having a molecular weight of 800 or more and 1000 or less are preliminarily reacted at a reaction rate of 10 to 90% to prepare. The method for producing a polyamide resin composition according to [5] or [6], wherein the compound (B) is melt-kneaded with the polyamide resin (A).

In the above general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH _2, and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0-20.
[6] When heat-treated at 130° C. for 100 hours in the air, the increase in the carboxyl group concentration in the polyamide resin composition at a depth of 0.2 mm or less from the surface of the molded product is 4×10 ⁻⁵ mol/g or less. The molded article according to any one of [1] to [5].
[7] (A) 100 parts by weight of the polyamide resin, (B) a hydroxyl group and/or an amino group, and an epoxy group and / or a carbodiimide group, the sum of the number of hydroxyl groups and amino groups in one molecule Is a polyamide resin composition in which 0.1 to 20 parts by weight of a compound, which is more than the sum of the numbers of epoxy groups and carbodiimide groups in one molecule, is blended, and is obtained by injection molding the polyamide resin composition. A bar-shaped test piece having a thickness of 6.4 mm was heat-treated at 150° C. for 1000 hours in the atmosphere, and then the peak intensity Y of the carboxyl group on the surface of the bar-shaped test piece obtained by Fourier transform infrared spectroscopy and the surface of the bar-shaped test piece were obtained. To 0.28 mm, the polyamide resin composition has a ratio (Y/Z) to the peak intensity Z of the carboxyl group of 5.0 or less.
[8] When the rod-shaped test piece is heat-treated at 150° C. for 1000 hours in the air, the concentration V of the (B) compound in the polyamide resin composition on the surface of the rod-shaped test piece obtained by Fourier transform infrared spectroscopy, and [7] The polyamide resin according to [7], wherein the ratio (V/W) to the concentration W of the (B) compound in the polyamide resin composition at a depth of 0.28 mm from the surface of the rod-shaped test piece is 1.2 to 5.0. Composition.

The molded article of the present invention is excellent in heat aging resistance, calcium chloride resistance and surface appearance.

The FT-IR spectrum of the surface of the molded product obtained by Example 3 and having a thickness of 6.4 mm after heat treatment at 150° C. for 1000 hours. The FT-IR spectrum of the cross section of the molded product obtained by Example 3 and having a thickness of 6.4 mm after heat treatment at 150° C. for 1000 hours. The graph which plotted the peak intensity of the standardized carboxyl group in the FT-IR spectrum of FIG. 1 and FIG. 2 with respect to the distance from the molded product surface. The graph which plotted the peak intensity of the aliphatic ether group of the standardized (B) compound in the FT-IR spectrum of FIG. 1 and FIG. 2 with respect to the distance from the molded article surface. ¹ H-NMR spectrum of a dry blend product of dipentaerythritol and bisphenol A type epoxy resin. ¹ H-NMR spectrum of a melt-kneaded reaction product of a polyhydric alcohol and an epoxy compound obtained in Reference Example 9.

Hereinafter, embodiments of the present invention will be described in detail. The molded product of the embodiment of the present invention is a molded product having a thickness of 0.56 mm or more obtained by molding a polyamide resin composition, and is subjected to heat treatment at 150° C. for 1000 hours in the air, and then Fourier transform infrared Ratio (Y/Z) of the peak intensity Y of the carboxyl group on the surface of the molded article obtained by the spectroscopic analysis and the peak intensity Z of the carboxyl group at a depth of 0.28 mm from the surface of the molded article (hereinafter, "peak of the carboxyl group" In some cases, it is described as “strength ratio”) is 5.0 or less. Here, the peak intensity of the carboxyl group after heat treatment at 150° C. for 1000 hours is an index showing the degree of embrittlement due to oxidative deterioration of the polyamide resin, as described later. Generally, when a molded product obtained by molding a polyamide resin composition is heated under atmospheric pressure, the peak intensity ratio of the carboxyl group changes due to oxidative deterioration of the polyamide resin, but when the heating time elapses to some extent The peak intensity ratio is almost constant. Further, according to the study by the present inventors, a molded product having a peak intensity ratio of carboxyl groups of 5.0 or less under the conditions of heat treatment temperature of 150° C. and heat treatment time of 1000 hours was found to have heat aging resistance, calcium chloride resistance and surface. It has been experimentally confirmed that the appearance is excellent. Therefore, in the embodiment of the present invention, the heat treatment condition at 150° C. for 1000 hours is selected as the condition that the peak intensity ratio of the carboxyl groups is constant. Further, the oxidative deterioration of the polyamide resin is likely to occur in the surface layer of the molded product, and the peak intensity of the carboxyl group is almost constant inside the molded product. Therefore, in the embodiment of the present invention, a depth of 0.28 mm from the surface of the molded article is selected as the inside of the molded article in which the peak intensity of the carboxyl group is constant, and the peak intensity of the carboxyl group at that depth is used as a reference. To do. Therefore, the thickness of the molded product according to the embodiment of the present invention is 0.56 mm or more.

When the peak intensity ratio of the carboxyl groups becomes 5.0 or less after heat treating a molded product having a thickness of 0.56 mm or more at 150° C. in the atmosphere, the molded product has heat aging resistance and chlorination resistance. Excellent calcium content and surface appearance. The cause of this is not clear, but the decrease in heat aging resistance is due to the fact that the molded product obtained by molding the polyamide resin composition is heated in the atmosphere, and the polyamide resin on the surface of the molded product in contact with oxygen is oxidatively deteriorated. However, it is considered that this is due to the low molecular weight and embrittlement. It is considered that the embrittlement of the surface of the molded product promotes the generation of cracks and also reduces the calcium chloride resistance. In addition, cracks due to embrittlement of the surface of the molded product and surface defects such as floating of the fibrous filler also occur. At this time, the carboxyl groups increase on the surface of the molded product as the molecular weight of the polyamide resin decreases. On the other hand, at a depth of 0.28 mm or more from the surface of the molded product, since it is not in contact with oxygen and oxidative deterioration is unlikely to occur, it is difficult to reduce the molecular weight of the polyamide resin and increase the number of carboxyl groups. In the embodiment of the present invention, the peak intensity ratio of the carboxyl groups of 5.0 or less indicates that the oxidative deterioration of the polyamide resin on the surface of the molded product is small and suppresses the embrittlement due to the low molecular weight. It has excellent heat aging resistance, calcium chloride resistance and surface appearance. When the peak intensity ratio of the carboxyl group is more than 5.0, the surface of the molded product becomes brittle due to the low molecular weight, and the heat aging resistance, calcium chloride resistance and surface appearance are deteriorated. The peak intensity ratio of the carboxyl group is preferably 4.3 or less, more preferably 3.5 or less, further preferably 2.0 or less, and the closer to 1.0, the more preferable.

The peak intensity of the carboxyl group on the surface of the molded product is the macro infrared attenuated total reflection method (macro infrared ATR method) of a Fourier transform infrared spectrophotometer for the surface of the molded product that has been heat-treated at 150° C. for 1000 hours in the air. ) Can be used for measurement. The peak intensity of the C=O stretching vibration of the carboxyl group in the obtained FT-IR spectrum was determined, and the value normalized by the peak intensity of the C=O stretching vibration of the amide bond was used as the peak of the carboxyl group on the surface of the molded product. Strength.

The peak intensity of the carboxyl group at a depth of 0.28 mm from the surface of the molded product is the microscopic infrared ATR method of a Fourier transform infrared spectrophotometer for the cross section of the molded product that has been heat-treated at 150° C. for 1000 hours in the air. It can be determined by measuring with. The peak intensity of the C=O stretching vibration of the carboxyl group in the obtained FT-IR spectrum was determined, and the value normalized by the peak intensity of the C=O stretching vibration of the amide bond was 0.28 mm from the surface of the molded product. It is the peak intensity of the carboxyl group at the depth.

As an example, FIG. 1 shows the FT-IR spectrum of the surface of the molded product obtained by heat-treating the molded product having a thickness of 6.4 mm obtained in Example 3 at 150° C. for 1000 hours in the atmosphere. The FT-IR spectrum of the cross section of the molded product in the depth direction is shown in FIG. From the spectra of FIGS. 1 and 2, a peak intensity of C═O stretching vibration of a carboxyl group near 1720 cm ^{−1 is} normalized by a peak intensity of C═O stretching vibration of an amide bond near 1632 cm ^−1. .. FIG. 3 shows a plot of normalized peak intensity with respect to the distance from the surface of the molded product. From FIG. 3, the peak intensity ratio of the carboxyl groups can be calculated by dividing the peak intensity on the surface of the molded product by the peak intensity at a depth of 0.28 mm from the surface of the molded product.

A molded product having a peak intensity ratio of carboxyl groups of 5.0 or less can be obtained, for example, by molding the polyamide resin composition described below.

The molded article of the embodiment of the present invention has (B) a hydroxyl group and/or an amino group and an epoxy group and/or a carbodiimide group, which will be described later, and the sum of the numbers of the hydroxyl group and the amino group in one molecule is one molecule. When obtained by molding a polyamide resin composition containing a compound (hereinafter, sometimes referred to as “(B) compound”) that is more than the sum of the number of epoxy groups and carbodiimide groups in When the molded article was treated at 150° C. for 1000 hours in the atmosphere, the concentration V of the (B) compound in the polyamide resin composition on the surface of the molded article obtained by Fourier transform infrared spectroscopy and the surface of the molded article The ratio (V/W) to the concentration W of the (B) compound in the polyamide resin composition at a depth of 0.28 mm (hereinafter sometimes referred to as “concentration ratio of (B) compound”) is 1. It is preferably 2 to 5.0. Here, the concentration ratio of the (B) compound after heat treatment at 150° C. for 1000 hours is, as described later, a molding of the (B) compound that suppresses embrittlement due to oxidative deterioration of the polyamide resin, which is easily affected by oxygen. It is an index showing the degree of concentration on the product surface. Generally, when such a molded product is heated under atmospheric pressure, the peak intensity ratio of the carboxyl groups changes due to the oxidation deterioration of the polyamide resin, and the concentration ratio of the (B) compound also tends to change. After some time, the concentration ratio of the compound (B) becomes almost constant. Therefore, in the embodiment of the present invention, the heat treatment condition at 150° C. for 1000 hours is selected as the condition that the concentration ratio of the compound (B) is constant. In addition, the oxidative deterioration of the polyamide resin is likely to occur in the surface layer of the molded product, and the compound (B) tends to move to the surface of the molded product, but the concentration of the compound (B) is almost constant inside the molded product. Therefore, in the embodiment of the present invention, a depth of 0.28 mm from the surface of the molded product is selected as the inside of the molded product which is less likely to be affected by the movement of the compound (B) to the surface of the molded product, and at the depth ( B) Based on compound concentration.

When the concentration ratio of the (B) compound is 1.2 or more, the (A) polyamide resin can be distributed at a high concentration on the surface of the molded article in which the (A) polyamide resin is prone to oxidative deterioration. By the reaction of the (B) compound with the (B) compound, it is possible to effectively suppress the lowering of the molecular weight of the (A) polyamide resin, and the heat aging resistance is further improved. Furthermore, since the (B) compound having a branched structure and the (A) polyamide resin react with each other to form a crosslinked layer on the surface of the molded article, it is possible to further suppress the occurrence of cracks and to improve the calcium chloride resistance. improves. The concentration ratio of the compound (B) is preferably 1.5 or more, more preferably 2.0 or more. On the other hand, when the concentration ratio of the (B) compound is 5.0 or less, excessive distribution of the (B) compound on the surface of the molded article can be suppressed, and decomposition of the polyamide resin by the (B) compound is suppressed. It As a result, the heat aging resistance is further improved. Further, a crosslinked layer can be appropriately formed on the surface of the molded product, and the calcium chloride resistance is further improved. Further, bleeding out of the compound (B) to the surface of the molded product can be suppressed, and the surface appearance is further improved. The concentration ratio of the compound (B) is preferably 4.5 or less, more preferably 4.0 or less.

The concentration V of the (B) compound in the polyamide resin composition on the surface of the molded product is the macro-infrared ATR method of the Fourier transform infrared spectrophotometer for the surface of the molded product which is heat-treated at 150° C. for 1000 hours in the atmosphere. It can be determined by measuring with. The peak intensity derived from the (B) compound in the obtained FT-IR spectrum was determined and normalized by the peak intensity of the C=O stretching vibration of the amide bond, and the value is the concentration V of the (B) compound on the surface of the molded article. And

The concentration W of the compound (B) in the polyamide resin composition at a depth of 0.28 mm from the surface of the molded product was measured by Fourier transform red with respect to the cross section of the molded product which was heat-treated at 150° C. for 1000 hours in the air. It can be determined by measurement using the microscopic infrared ATR method of an external spectrophotometer. The peak intensity derived from the (B) compound in the obtained FT-IR spectrum was determined, and the value normalized by the peak intensity of C=O stretching vibration of the amide bond was measured at a depth of 0.28 mm from the surface of the molded product. (B) The concentration W of the compound.

As an example, FIG. 1 shows the FT-IR spectrum of the surface of the molded product obtained by heat-treating the molded product having a thickness of 6.4 mm obtained in Example 3 at 150° C. for 1000 hours in the atmosphere. The FT-IR spectrum of the cross section of the molded product in the depth direction is shown in FIG. From the spectra of FIG. 1 and FIG. 2, the peak intensity of the C—O stretching vibration of the aliphatic ether group of the compound (B) near 1005 cm ^{−1 is} the peak intensity of the C═O stretching vibration of the amide bond near 1632 cm ^−1. Calculate the value standardized by. FIG. 4 shows a plot of the normalized peak intensity with respect to the distance from the surface of the molded product. From FIG. 4, the concentration ratio of the compound (B) can be calculated by dividing the peak intensity on the surface of the molded product by the peak intensity at a depth of 0.28 mm from the surface of the molded product.

The molded product in which the concentration ratio of the compound (B) is 1.2 to 5.0 can be obtained, for example, by molding the polyamide resin composition described below.

When a molded product having a thickness of 0.56 mm or more according to an embodiment of the present invention is heat-treated at 130° C. for 100 hours in the air, a carboxyl group in a polyamide resin composition having a depth of 0.2 mm from the surface of the molded product. It is preferable that the increase in concentration is 4×10 ⁻⁵ mol/g or less. Generally, when a molded product obtained by molding a polyamide resin composition is heated under atmospheric pressure, the concentration of carboxyl groups tends to increase due to oxidative deterioration of the polyamide resin. Further, the oxidative deterioration of the polyamide resin is likely to occur on the surface layer of the molded product, and the carboxyl group concentration becomes almost constant inside the molded product. Therefore, in the embodiment of the present invention, as an index showing the degree of susceptibility to oxidative deterioration of the polyamide resin, the heat treatment condition of 100° C. for 100 hours and the surface of the molded product which easily causes oxidative deterioration of the polyamide resin are 0. A depth of up to 0.2 mm is selected, and attention is paid to changes in the concentration of carboxyl groups in such a range.

When the increase in the carboxyl group concentration when heat-treated at 130° C. for 100 hours is 4×10 ⁻⁵ mol/g or less, the heat aging resistance and calcium chloride resistance of the molded product are further improved. The cause of this is not clear, but the decrease in heat aging resistance is due to the fact that the molded product obtained by molding the polyamide resin composition is heated in the atmosphere to heat (A) the polyamide resin on the surface of the molded product which is in contact with oxygen. Is considered to be due to oxidative deterioration, lower molecular weight and embrittlement. However, if the increase in the concentration of the carboxyl terminal group in the polyamide resin composition after the heat treatment is suppressed, the lowering of the molecular weight of the (A) polyamide resin can be further suppressed, and the heat aging resistance and the calcium chloride resistance are more improved. improves. When the polyamide resin composition contains the (B) compound, the carboxyl terminal group of the (A) polyamide resin, which increases when the (A) polyamide resin has a low molecular weight, reacts with the (B) compound to form a carboxyl group. It is possible to further suppress the increase in the terminal group concentration after the heat treatment. The increase in the carboxyl group concentration when heat-treated at 130° C. for 100 hours is more preferably 1.4×10 ⁻⁵ mol/g or less, further preferably 0.5×10 ⁻⁵ mol/g or less.

Regarding the carboxyl terminal group concentration of the polyamide resin composition, a polyamide resin composition having a depth of up to 0.2 mm from the surface of a molded product that has been heat-treated at 130° C. in the atmosphere for 100 hours is cut using a milling machine, It can be measured by a known method such as a neutralization titration method.

Next, the polyamide resin composition used in the molded article of the embodiment of the present invention and the polyamide resin composition of the embodiment of the present invention will be described. The polyamide resin composition used in the molded article of the embodiment of the present invention and the polyamide resin composition of the embodiment of the present invention include at least (A) a polyamide resin, (B) a hydroxyl group and/or an amino group, and an epoxy group. And/or a carbodiimide group and the number of hydroxyl groups and amino groups in one molecule is greater than the sum of the number of epoxy groups and carbodiimide groups in one molecule ((B) compound). It is preferable that Hereinafter, each component will be described.

In the polyamide resin composition of the embodiment of the present invention, it is considered that the (A) polyamide resin has a carboxyl terminal group that undergoes a dehydration condensation reaction with a hydroxyl group and/or an amino group in the (B) compound described below. Furthermore, in the polyamide resin composition of the embodiment of the present invention, the amino terminal group and the carboxyl terminal group of the (A) polyamide resin are the same as the hydroxyl group and/or amino group, the epoxy group and/or the carbodiimide group in the (B) compound. It is considered to react. Therefore, the polyamide resin (A) is considered to have excellent compatibility with the compound (B).

The (A) polyamide resin used in the embodiment of the present invention is a polyamide containing (i) an amino acid, (ii) a lactam or (iii) a diamine and a dicarboxylic acid as main raw materials. Typical examples of the raw material of the (A) polyamide resin include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethyl Hexamethylenediamine, 5-methylnonamethylenediamine, aliphatic diamines such as 2-methyloctamethylenediamine, aromatic diamines such as metaxylylenediamine and paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1 , 4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, Aliphatic diamines such as 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine and aminoethylpiperazine, aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. Acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Alicyclic dicarboxylic acids such as aromatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. .. In the embodiment of the present invention, as a raw material of the (A) polyamide resin, two or more kinds of polyamide homopolymers or polyamide copolymers derived from these raw materials may be blended.

Specific examples of the polyamide resin include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410). , Polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (Nylon 106), polydecamethylene sebacamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polycaproamide/polyhexamethylene azide Pamide copolymer (nylon 6/66), polycaproamide/polyhexamethylene terephthalamide copolymer (nylon 6/6T), polyhexamethylene adipamide/polyhexamethylene terephthalamide copolymer (nylon 66/6T), polyhexamethylene Adipamide/polyhexamethylene isophthalamide copolymer (nylon 66/6I), polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (nylon 6T/6I), polyhexamethylene terephthalamide/polyundecane amide copolymer (nylon 6T/ 11), polyhexamethylene terephthalamide/polydodecane amide copolymer (nylon 6T/12), polyhexamethylene adipamide/polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (nylon 66/6T/6I), polyhexa Methylene adipamide/polyhexamethylene isophthalamide/polycaproamide copolymer (nylon 66/6I/6), polyxylylene adipamide (nylon XD6), polyxylylene sebacamide (nylon XD10), polyhexamethylene terephthalate Amide/polypentamethylene terephthalamide copolymer (nylon 6T/5T), polyhexamethylene terephthalamide/poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T/M5T), polypentamethylene terephthalamide/polydecamethylene terephthalamide copolymer (Nylon 5T/10T), polynonamethylene terephthalamide (nylon 9T), polydecamethylene tere Examples include phthalamide (nylon 10T) and polydodecamethylene terephthalamide (nylon 12T). Further, specific examples of the polyamide resin also include a mixture of these and a copolymer. Here, “/” indicates a copolymer. The same applies hereinafter.

A particularly preferred polyamide resin is a polyamide resin having a melting point of 240°C to 330°C. A polyamide resin having a melting point of 240°C to 330°C has excellent heat resistance and strength. The polyamide resin having a melting point of 240° C. or higher can be melt-kneaded under a high resin pressure under high temperature conditions, and the reactivity with the (B) compound described later can be increased. Therefore, the dispersibility of the (B) compound in the polyamide resin composition can be further enhanced, and the heat aging resistance and calcium chloride resistance can be further improved. The melting point of the polyamide resin is more preferably 250°C or higher. On the other hand, by using a polyamide resin having a melting point of 330° C. or lower, the melt-kneading temperature can be appropriately suppressed and the decomposition of the polyamide resin can be suppressed. Therefore, the heat aging resistance can be further improved. Here, the melting point of the polyamide resin in the embodiment of the present invention is measured by using a differential scanning calorimeter after the polyamide resin is cooled from the molten state to 30° C. at a temperature decreasing rate of 20° C./min. , The temperature of the endothermic peak that appears when the temperature is raised to the melting point +40° C. at a temperature rising rate of 20° C./min. However, when two or more endothermic peaks are detected, the temperature of the endothermic peak with the highest peak intensity is taken as the melting point.

Examples of the polyamide resin having a melting point of 240° C. to 330° C. include nylon 66, nylon 46, nylon 410, nylon 56, nylon 6T/66, nylon 6T/6I, nylon 6T/12, nylon 6T/5T, nylon 6T. /M5T, nylon 6T/6 and other copolymers having hexamethyleterephthalamide units, polyhexamethylene adipamide/polyhexamethylene isophthalamide/polycaproamide copolymer (nylon 66/6I/6), nylon 5T/ Examples thereof include 10T, nylon 9T, nylon 10T, nylon 12T and the like.

It is also practically preferable to blend two or more of these polyamide resins in accordance with the required properties such as heat aging resistance, calcium chloride resistance and surface appearance. It is preferable to mix nylon 6, nylon 11 and/or nylon 12 with a polyamide resin having a melting point of 240° C. to 330° C., which can further improve the heat aging resistance of the molded product. In this case, the total blending amount of nylon 6, nylon 11 and nylon 12 is preferably 5 to 55 parts by weight with respect to 100 parts by weight of the polyamide resin having a melting point of 240°C to 330°C.

The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity (ηr) measured at 25° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g/ml is in the range of 1.5 to 5.0. Preferably. When the relative viscosity is 1.5 or more, the mechanical strength and heat aging resistance of the obtained molded product can be further improved. The relative viscosity is more preferably 2.0 or more. On the other hand, when the relative viscosity is 5.0 or less, the moldability can be improved.

The polyamide resin composition of the embodiment of the present invention has (B) a hydroxyl group and/or an amino group and an epoxy group and/or a carbodiimide group, and the sum of the number of hydroxyl groups and amino groups in one molecule is 1 It contains more compounds than the sum of the number of epoxy groups and carbodiimide groups in the molecule. The hydroxyl group and/or amino group-containing compound has an effect of improving molding processability such as fluidity and heat aging resistance at 150 to 230°C, but is less than 150°C, probably due to low compatibility with the (A) polyamide resin. Also, there is a problem that the heat aging resistance at 240° C. or higher is insufficient. In addition, the hydroxyl group- and/or amino group-containing compound has a problem that the surface appearance is deteriorated by bleeding out on the surface layer of the molded article, and the hydroxyl group and/or amino group-containing compound has a hydroxyl group and/or amino group of (A) polyamide resin There is also a problem that the hydrolysis of the amide bond is accelerated and the resistance to calcium chloride is poor. Further, there is a problem that the compound containing a hydroxyl group and/or an amino group plasticizes the (A) polyamide resin, and the mechanical strength of the obtained molded article is lowered. On the other hand, in the embodiment of the present invention, in the compound (B), the hydroxyl group and/or amino group is considered to undergo a dehydration condensation reaction with the carboxyl terminal group of the polyamide resin (A), and the hydroxyl group, amino group, Since the epoxy group and/or the carbodiimide group are considered to react with the amino terminal group and the carboxyl terminal group of the (A) polyamide resin, the compatibility with the (A) polyamide resin is excellent and fine dispersion in the polyamide resin composition is achieved. A phase can be formed, and the heat aging resistance below 150° C. and above 240° C. can be improved. Further, it is possible to suppress the bleed-out of the compound (B) to the surface layer of the molded product and improve the surface appearance. Furthermore, since the epoxy group and the carbodiimide group are more reactive than the hydroxyl group and the amino group with the terminal group of the (A) polyamide resin, the sum of the numbers of the hydroxyl group and the amino group in one molecule of the (B) compound is shown. Is more than the sum of the number of epoxy groups and carbodiimide groups, moderately forming a crosslinked structure to suppress the decrease in the degree of polymerization due to hydrolysis of an amide bond, and to prevent brittleness due to the formation of an excessive crosslinked structure. It is considered that it can be suppressed and the calcium chloride resistance can be improved. A compound having a hydroxyl group and an epoxy group and/or a carbodiimide group is more preferable.

In the embodiment of the present invention, examples of the (B) compound include a reaction product of a (b) hydroxyl group- and/or amino group-containing compound and (b') epoxy group- and/or carbodiimide group-containing compound described later. .. The compound (B) may be a low molecular weight compound, a polymer, or a condensate. The structure of the compound (B) can be specified by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.).

In the embodiment of the present invention, the branching degree of the compound (B) is not particularly limited, but is preferably 0.05 to 0.70. The degree of branching is a numerical value that represents the degree of branching in the compound. A linear compound has a degree of branching of 0, and a fully branched dendrimer has a degree of branching of 1. The larger this value, the more the crosslinked structure can be introduced into the polyamide resin composition, and the more the mechanical properties of the molded product can be improved. By setting the degree of branching to 0.05 or more, a crosslinked structure in the polyamide resin composition is sufficiently formed, and heat aging resistance and calcium chloride resistance can be further improved. The branching degree is more preferably 0.10 or more. On the other hand, by setting the degree of branching to 0.70 or less, the crosslinked structure in the polyamide resin composition is appropriately suppressed, the dispersibility of the (B) compound in the polyamide resin composition is further increased, and heat aging resistance and chlorination resistance are improved. The calcium nature can be improved more. The degree of branching is more preferably 0.35 or less. The degree of branching is defined by the following equation (2).
Branching degree=(D+T)/(D+T+L) (2)
In the above formula (2), D represents the number of dendritic units, L represents the number of linear units, and T represents the number of terminal units. The above D, T, and L can be calculated from the integrated value of the peak shift measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom which is a methyl group, and L is a primary or secondary carbon atom, Derived from those excluding T.

Examples of the (B) compound having a degree of branching in the above range include, for example, a reaction product of a preferable (b) hydroxyl group- and/or amino group-containing compound and (b') epoxy group- and/or carbodiimide group-containing compound described below. Is mentioned.

The hydroxyl value of the compound (B) used in the embodiment of the present invention is preferably 100 to 2000 mgKOH/g. By setting the hydroxyl value of the compound (B) to 100 mgKOH/g or more, it becomes easy to secure a sufficient amount of reaction between the (A) polyamide resin and the compound (B), and thus heat aging resistance and calcium chloride resistance It is possible to further improve the sex. The hydroxyl value of the compound (B) is more preferably 300 mgKOH/g or more. On the other hand, by setting the hydroxyl value of the (B) compound to 2000 mgKOH/g or less, the reactivity between the (A) polyamide resin and the (B) compound is appropriately increased, and heat aging resistance and calcium chloride resistance are further improved. be able to. Further, by setting the hydroxyl value of the compound (B) to 2000 mgKOH/g or less, gelation due to excessive reaction can be suppressed. The hydroxyl value of the compound (B) is more preferably 1800 mgKOH/g or less. Here, the hydroxyl value of the (B) compound can be determined by acetylating the (B) compound with a mixed solution of acetic anhydride and pyridine anhydride and titrating the mixture with an ethanolic potassium hydroxide solution.

The amine value of the (B) compound used in the embodiment of the present invention is preferably 100 to 2000 mgKOH/g. By setting the amine value of the (B) compound to 100 mgKOH/g or more, it becomes easy to secure a sufficient reaction amount between the (A) polyamide resin and the (B) compound, so that the heat aging resistance and calcium chloride resistance are high. It is possible to further improve the sex. The amine value of the compound (B) is more preferably 200 mgKOH/g or more. On the other hand, when the amine value of the (B) compound is 2000 mgKOH/g or less, the reactivity between the (A) polyamide resin and the (B) compound is moderately increased, and thus the heat aging resistance and the calcium chloride resistance are further improved. Can be made. Further, by setting the amine value of the compound (B) to 2000 mgKOH/g or less, gelation of the polyamide resin composition due to excess reaction can be suppressed. The amine value of the compound (B) is more preferably 1600 mgKOH/g or less. Here, the amine value of the compound (B) can be determined by dissolving the compound (B) in ethanol and performing neutralization titration with an ethanolic hydrochloric acid solution.

Examples of the (B) compound having a hydroxyl value or amine value in the above range include, for example, a preferred (b) hydroxyl group- and/or amino group-containing compound and (b') epoxy group- and/or carbodiimide group-containing compound described below. Examples include reactants.

The compound (B) used in the embodiment of the present invention is preferably a solid at 25°C or a liquid having a viscosity of 200 mPa·s or more at 25°C. In that case, it becomes easy to obtain a desired viscosity during melt-kneading, the compatibility with the (A) polyamide resin can be further improved, and the heat aging resistance and calcium chloride resistance can be further improved.

The number of hydroxyl groups or amino groups in one molecule of the compound (B) used in the embodiment of the present invention is preferably 3 or more. When the number of hydroxyl groups or amino groups in one molecule is 3 or more, the compatibility with the (A) polyamide resin is excellent, and the heat aging resistance and calcium chloride resistance can be further improved. The number of hydroxyl groups or the number of amino groups in one molecule is preferably 4 or more, and more preferably 6 or more.

In the case of a low molecular weight compound, the number of hydroxyl groups or amino groups in one molecule of the compound (B) can be determined by a conventional analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). It can be specified and calculated. In the case of a polymer, the number average molecular weight and the hydroxyl value or amine value of the compound (B) can be calculated and can be calculated by the following formula (3).
Number of hydroxyl groups or amino groups = (number average molecular weight x hydroxyl value or amine value)/56110 (3)
The number of epoxy groups or carbodiimide groups in one molecule of the compound (B) used in the embodiment of the present invention is preferably 2 or more. When the number of epoxy groups or carbodiimide groups in one molecule is 2 or more, the compatibility with the (A) polyamide resin is excellent, and heat aging resistance and calcium chloride resistance can be further improved. The number of epoxy groups or the number of carbodiimide groups in one molecule is preferably 4 or more, and more preferably 6 or more, respectively.

In the case of a low molecular weight compound, the number of epoxy groups or carbodiimide groups in one molecule of the compound (B) can be determined by a usual analytical method (for example, a combination of NMR, FT-IR, GC-MS, etc.). Can be specified and calculated. In the case of a polymer, it can be calculated by a value obtained by dividing the number average molecular weight of the compound (B) by the epoxy equivalent or the carbodiimide equivalent.

Examples of the (B) compound having the number of hydroxyl groups, the number of amino groups, the number of epoxy groups and the number of carbodiimide groups in the above ranges include, for example, preferred (b) hydroxyl group- and/or amino group-containing compounds and (b′) epoxy groups and/or Examples thereof include a reaction product with a carbodiimide group-containing compound.

The (b) hydroxyl group- and/or amino group-containing compound used in the embodiment of the present invention is preferably an aliphatic compound having 3 or more hydroxyl groups or 3 or more amino groups in one molecule. By having three or more hydroxyl groups or three or more amino groups in one molecule, it becomes easy to adjust the number of hydroxyl groups or amino groups of the compound (B) to a preferable range. The number of hydroxyl groups or the number of amino groups in one molecule is more preferably 4 or more, still more preferably 6 or more. Further, the aliphatic compound has a lower steric hindrance than the aromatic compound or the alicyclic compound, and the compatibility of the (B) compound and the (A) polyamide resin is excellent, and therefore, the heat aging resistance of the obtained molded article and the It is considered that the calcium chloride resistance can be further improved.

(B) The number of hydroxyl groups or amino groups in one molecule of a compound containing a hydroxyl group and/or an amino group is, in the case of a low molecular weight compound, an ordinary analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). ), the structural formula of the compound can be specified and calculated. In the case of a polymer, the number average molecular weight of the (b) hydroxyl group- and/or amino group-containing compound and the hydroxyl value or amine value can be calculated and calculated according to the above formula (3).

The molecular weight of the (b) hydroxyl group- and/or amino group-containing compound used in the embodiment of the present invention is not particularly limited, but is preferably in the range of 50 to 10,000. When the molecular weight of the compound (b) containing a hydroxyl group and/or an amino group is 50 or more, the compound (B) is less likely to volatilize during melt-kneading, resulting in excellent workability. The molecular weight of the compound (b) containing a hydroxyl group and/or an amino group is preferably 150 or more, more preferably 200 or more. On the other hand, when the molecular weight of the (b) hydroxyl group- and/or amino group-containing compound is 10,000 or less, the compatibility between the (B) compound and the (A) polyamide resin becomes higher, so that the effect of the present invention becomes more remarkable. Played. The molecular weight of the compound (b) containing a hydroxyl group and/or an amino group is preferably 6000 or less, more preferably 4000 or less, still more preferably 800 or less.

The molecular weight of the compound (b) containing a hydroxyl group and/or an amino group can be calculated by specifying the structural formula of the compound by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). In addition, the weight average molecular weight is used as the molecular weight for the molecular weight when the hydroxyl group- and/or amino group-containing compound is a condensate. The weight average molecular weight (Mw) can be calculated using gel permeation chromatography (GPC). Specifically, a solvent in which the compound is dissolved, such as hexafluoroisopropanol, is used as a mobile phase, polymethylmethacrylate (PMMA) is used as a standard substance, and the column is matched with the solvent. For example, when hexafluoroisopropanol is used, Shimadzu is used. The weight average molecular weight can be measured using "SHODEX GPC HFIP-806M" and/or "SHODEX GPC HFIP-LG" manufactured by GL Corp. using a differential refractometer as a detector.

The degree of branching of the (b) hydroxyl group- and/or amino group-containing compound used in the embodiment of the present invention is not particularly limited, but is preferably 0.05 to 0.70. Thereby, it becomes easy to make the branching degree of the compound (B) within a preferable range. The branching degree is more preferably 0.10 or more and 0.35 or less. The branching degree is defined by the above equation (2).

Among the (b) hydroxyl group- and/or amino group-containing compounds used in the embodiment of the present invention, the hydroxyl group-containing compound preferably has a hydroxyl value of 100 to 2000 mgKOH/g. By setting the hydroxyl value to such a range, it becomes easy to adjust the hydroxyl value of the obtained compound (B) to the above-mentioned preferable range. The hydroxyl value of the hydroxyl group-containing compound is more preferably 300 mgKOH/g or more and 1800 mgKOH/g or less. The hydroxyl value can be determined by acetylating a hydroxyl group-containing compound with a mixed solution of acetic anhydride and anhydrous pyridine and titrating the mixture with an ethanolic potassium hydroxide solution.

Specific examples of the hydroxyl group-containing compound include 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,6-hexanetetrol, glycerin, Diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, ditrimethylolpropane, tritrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, glucose, mannitol, sucrose, 1,3,5 -Trihydroxybenzene, 1,2,4-trihydroxybenzene, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, triethanolamine, trimethylolethane, trimethylolpropane, 2-methylpropanetriol, trishydroxymethylaminomethane, Examples thereof include 2-methyl-1,2,4-butanetriol. Further, the hydroxyl group-containing compound may also include a hydroxyl group-containing compound having a repeating structural unit, for example, ester bond, amide bond, ether bond, methylene bond, vinyl bond, imine bond, siloxane bond, urethane bond, thioether bond, Examples thereof include a hydroxyl group-containing compound having a repeating structural unit having a silicon-silicon bond, a carbonate bond, a sulfonyl bond and an imide bond. The hydroxyl group-containing compound may contain a repeating structural unit containing two or more of these bonds. The hydroxyl group-containing compound having a repeating structural unit is more preferably a hydroxyl group-containing compound having a repeating structural unit having an ester bond, a carbonate bond, an ether bond and/or an amide bond.

The hydroxyl group-containing compound having a repeating structural unit having an ester bond is, for example, a compound having one or more hydroxyl groups, in which a carbon atom adjacent to a carboxyl group is a saturated carbon atom and all hydrogen atoms on the carbon atom are substituted. And a monocarboxylic acid having two or more hydroxyl groups is reacted. The hydroxyl group-containing compound having a repeating structural unit having an ether bond can be obtained, for example, by ring-opening polymerization of a compound having one or more hydroxyl groups and a cyclic ether compound having one or more hydroxyl groups. The hydroxyl group-containing compound having a repeating structural unit having an ester bond and an amide bond can be obtained, for example, by a polycondensation reaction between aminodiol and a cyclic acid anhydride. The hydroxyl group-containing compound having a repeating structural unit having an ether bond containing an amino group can be obtained by, for example, intermolecular condensation of trialkanolamine. The hydroxyl group-containing compound composed of a repeating structural unit having a carbonate bond can be obtained, for example, by a polycondensation reaction of an aryl carbonate derivative of trisphenol.

Among the hydroxyl group-containing compounds, pentaerythritol, dipentaerythritol, and tripentaerythritol are preferable.

Among the (b) hydroxyl group- and/or amino group-containing compounds used in the embodiment of the present invention, the amine value of the amino group-containing compound is preferably 100 to 2000 mgKOH/g. By setting the amine value in such a range, it becomes easy to set the amine value of the compound (B) in a preferable range. The amine value of the amino group-containing compound is more preferably 200 mgKOH/g or more and 1600 mgKOH/g or less. The amine value can be determined by dissolving the amino group-containing compound in ethanol and performing neutralization titration with an ethanolic hydrochloric acid solution.

Specific examples of the amino group-containing compound have three amino groups such as 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane and 1,2,4-triaminobutane. Compounds and amino groups such as 1,1,2,3-tetraaminopropane, 1,2,3-triamino-2-methylaminopropane, 1,2,3,4-tetraaminobutane and their isomers are Individual compounds, compounds having five amino groups such as 3,6,9-triazaundecane-1,11-diamine, 3,6,9,12-tetraazatetradecane-1,14-diamine, 1 ,1,2,2,3,3-hexaaminopropane, 1,1,2,3,3-pentaamino-2methylaminopropane, 1,1,2,2,3,4-hexaaminobutane and these Examples thereof include compounds having 6 amino groups such as isomers of, and polyethyleneimine obtained by polymerizing ethyleneimine. As the amino group-containing compound, for example, (i) a compound obtained by introducing an alkylene oxide unit into the above-mentioned compound having an amino group, (ii) three compounds in one molecule such as trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples thereof also include compounds obtained by reacting the above-mentioned compound having a hydroxyl group and/or a compound in which the hydroxyl group is methyl esterified with alkylene oxide, and further aminating the terminal group.

The (b) hydroxyl group- and/or amino group-containing compound used in the embodiment of the present invention may have other reactive functional groups in addition to the hydroxyl group and/or amino group. Examples of other functional groups include aldehyde groups, sulfo groups, isocyanate groups, oxazoline groups, oxazine groups, ester groups, amide groups, silanol groups, silyl ether groups, and the like.

The (b') epoxy group- and/or carbodiimide group-containing compound used in the embodiment of the present invention preferably has two or more epoxy groups and/or carbodiimide groups in one molecule. Thereby, it becomes easy to set the number of epoxy groups and/or carbodiimide groups of the compound (B) within a preferable range. The number of epoxy groups or carbodiimide groups of the compound (B), the epoxy group and/or the carbodiimide group-containing compound (b') is more preferably 4 or more, still more preferably 6 or more. The epoxy group and/or carbodiimide group-containing compound (b') may be a low molecular weight compound or a polymer.

(B′) The number of epoxy groups or carbodiimide groups in one molecule of the epoxy group- and/or carbodiimide group-containing compound is the number of epoxy compounds or carbodiimide groups in the case of a low molecular weight compound, which is determined by a usual analysis method (for example, NMR, FT-IR, GC-MS). (Combination of etc.), the structural formula of the compound can be specified and calculated. In the case of a polymer, the value can be calculated by dividing the number average molecular weight of the compound (b') containing an epoxy group and/or a carbodiimide group by the epoxy equivalent or the carbodiimide equivalent.

Specific examples of the epoxy group-containing compound include epichlorohydrin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl group-containing vinyl-based compound. Examples include coalescence and the like. You may use 2 or more types of these.

Examples of the glycidyl ether type epoxy resin include those produced from epichlorohydrin and bisphenol A, those produced from epichlorohydrin and bisphenol F, and phenol novolac type epoxy resins obtained by reacting novolac resin with epichlorohydrin. , Orthocresol novolac type epoxy resin, so-called brominated epoxy resin derived from epichlorohydrin and tetrabromobisphenol A, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether and the like.

As the glycidyl ester type epoxy resin, an epoxy resin produced from epichlorohydrin and phthalic acid, tetrahydrophthalic acid, p-oxybenzoic acid or dimer acid, trimesic acid triglycidyl ester, trimellitic acid triglycidyl ester, pyro An example is meritic acid tetraglycidyl ester.

Examples of the glycidylamine type epoxy resin include an epoxy resin produced from epichlorohydrin and aniline, diaminodiphenylmethane, p-aminophenol, metaxylylenediamine or 1,3-bis(aminomethyl)cyclohexane, tetraglycidylaminodiphenylmethane. , Triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, tetraglycidyl metaxylenediamine, tetraglycidyl bisaminomethylcyclohexane, triglycidyl cyanurate, triglycidyl isocyanurate and the like.

Examples of the alicyclic epoxy resin include compounds having a cyclohexene oxide group, a tricyclodecene oxide group and a cyclopentene oxide group. Examples of the heterocyclic epoxy resin include an epoxy resin produced from epichlorohydrin and hydantoin or isocyanuric acid.

Examples of the glycidyl group-containing vinyl polymer include those obtained by radical polymerization of raw material monomers that form the glycidyl group-containing vinyl unit. Specific examples of the raw material monomer forming the glycidyl group-containing vinyl unit include glycidyl (meth)acrylate, glycidyl ester of unsaturated monocarboxylic acid such as glycidyl p-styrylcarboxylate, unsaturated acid such as maleic acid and itaconic acid. Examples thereof include monoglycidyl ester or polyglycidyl ester of polycarboxylic acid, unsaturated glycidyl ether such as allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-4-glycidyl ether.

Commercially available epoxy group-containing compounds include polyglycidyl ether compounds that are low-molecular polyfunctional epoxy compounds (for example, "SR-TMP" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., "Denacol" manufactured by Nagase Chemtex Co., Ltd.). (Registered trademark) EX-521"), a polyfunctional epoxy compound containing polyethylene as a main component (for example, ""Bond Fast" (registered trademark) E" manufactured by Sumitomo Chemical Co., Ltd.), and an acrylic-based main component. Functional epoxy compounds (for example, "Reseda" (registered trademark) GP-301 manufactured by Toagosei Co., Ltd., "ARUFON" (registered trademark) UG-4000 manufactured by Toagosei Co., Ltd., Mitsubishi Rayon Co., Ltd.) ""Metablene" (registered trademark) KP-7653" or the like), a polyfunctional epoxy compound containing an acrylic-styrene copolymer as a main component (for example, ""Joncryl" (registered trademark)-ADR-4368" manufactured by BASF), "ARUFON" (registered trademark) UG-4040 manufactured by Toagosei Co., Ltd.), and a polyfunctional epoxy compound containing a silicone-acrylic copolymer as a main component (for example, "Metablene" (registered trademark) S-2200). , Etc.), a polyfunctional epoxy compound containing polyethylene glycol as a main component (for example, “Epiol” (registered trademark) “E-1000” manufactured by NOF CORPORATION), and a bisphenol A type epoxy resin (for example, Mitsubishi Chemical ( "JER" (registered trademark) "1004" manufactured by K.K.), novolac phenol type modified epoxy resin (for example, "EPPN" (registered trademark) "201" manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of the carbodiimide group-containing compound include dicarbodiimides such as N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, and poly(1,6-hexadiene). Methylenecarbodiimide), poly(4,4′-methylenebiscyclohexylcarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(4,4′-dicyclohexylmethanecarbodiimide) , Poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(naphthalenecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide) ), poly(tolylcarbodiimide), poly(diisopropylcarbodiimide), poly(methyl-diisopropylphenylenecarbodiimide), poly(1,3,5-triisopropylbenzene) polycarbodiimide, poly(1,3,5-triisopropylbenzene) Examples thereof include polycarbodiimides such as polycarbodiimide, poly(1,5-diisopropylbenzene)polycarbodiimide, poly(triethylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide).

Examples of commercially available carbodiimide group-containing compounds include "Carbodilite" (registered trademark) manufactured by Nisshinbo Holdings Inc. and "Stavaxol (registered trademark)" manufactured by Rhein Chemie.

The molecular weight of the (b') epoxy group- and/or carbodiimide group-containing compound of the embodiment of the present invention is not particularly limited, but is preferably in the range of 800 to 10,000. When the molecular weight of the epoxy group- and/or carbodiimide group-containing compound (b') is 800 or more, the compound (B) is less likely to volatilize during melt-kneading, and is excellent in processability. Further, since the viscosity at the time of melt-kneading can be increased, the compatibility between the (A) polyamide resin and the (B) compound becomes higher, and the peak intensity ratio of the carboxyl group and the concentration ratio of the (B) compound are The desired range described above can be easily obtained, and the heat aging resistance, calcium chloride resistance and surface appearance are further improved. The molecular weight of the compound (b') containing an epoxy group and/or a carbodiimide group is more preferably 1,000 or more, still more preferably 2,000 or more. By setting the molecular weight of the (b') epoxy group and/or carbodiimide group-containing compound to 2000 or more, bleeding-out of the (B) compound to the surface layer of the molded article can be further suppressed and the surface appearance can be further improved even during wet heat treatment. Can be improved. On the other hand, when the molecular weight of the (b′) epoxy group- and/or carbodiimide group-containing compound is 10,000 or less, the viscosity of the resulting (B) compound during melt-kneading can be appropriately suppressed, resulting in excellent processability. .. Further, the compatibility between the polyamide resin (A) and the compound (B) can be kept high. The molecular weight of the (b') epoxy group- and/or carbodiimide group-containing compound is more preferably 8,000 or less.

(B′) The molecular weight of the epoxy group and/or carbodiimide group-containing compound can be calculated by specifying the structural formula of the compound by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). it can. Further, the weight average molecular weight is used as the molecular weight for the molecular weight when the epoxy group- and/or carbodiimide group-containing compound is a condensate. The weight average molecular weight (Mw) can be calculated using gel permeation chromatography (GPC). Specifically, a solvent in which the compound is dissolved, such as hexafluoroisopropanol, is used as a mobile phase, polymethylmethacrylate (PMMA) is used as a standard substance, and the column is matched with the solvent. For example, when hexafluoroisopropanol is used, Shimadzu is used. The weight average molecular weight can be measured using "SHODEX GPC HFIP-806M" and/or "SHODEX GPC HFIP-LG" manufactured by GL Corp. using a differential refractometer as a detector.

The (b') epoxy group- and/or carbodiimide group-containing compound used in the embodiment of the present invention is preferably a solid at 25°C or a liquid having a viscosity of 200 mPa·s or higher at 25°C. In that case, the viscosity of the obtained compound (B) during melt-kneading can be easily adjusted to a desired range, the compatibility between the (A) polyamide resin and the (B) compound becomes higher, and heat aging resistance and resistance The calcium chloride property is further improved.

The value obtained by dividing the molecular weight by the number of functional groups in one molecule, which is an index showing the functional group concentration of the (b′) epoxy group and/or carbodiimide group-containing compound in the embodiment of the present invention, is 50 to 3,000. It is preferable. Here, the number of functional groups refers to the total number of epoxy groups and carbodiimide groups. The smaller this value is, the higher the functional group concentration is, but by setting it to 50 or more, gelation due to excessive reaction between the obtained (B) compound and (A) polyamide resin can be suppressed, and heat aging can be suppressed. And calcium chloride resistance can be further improved. The value obtained by dividing the molecular weight of the compound (b') containing an epoxy group and/or a carbodiimide group by the number of functional groups in one molecule is more preferably 100 or more, still more preferably 1100 or more. (B') The value obtained by dividing the molecular weight of the epoxy group- and/or carbodiimide group-containing compound by the number of functional groups in one molecule is 1100 or more, so that the surface layer of the molded article (B) is Bleed out of the compound can be further suppressed and the surface appearance can be further improved. On the other hand, the value obtained by dividing the molecular weight of the (b′) epoxy group- and/or carbodiimide group-containing compound by the number of functional groups in one molecule is 3000 or less to obtain the (B) compound and the (A) polyamide resin. It is possible to sufficiently secure the reaction with and to further improve the heat aging resistance and the calcium chloride resistance. From this viewpoint, the value obtained by dividing the molecular weight of the (b′) epoxy group- and/or carbodiimide group-containing compound by the number of functional groups in one molecule is more preferably 2000 or less, more preferably 1000 or less, and 300 or less. More preferable.

In the embodiment of the present invention, the compound (B) is preferably a compound having a structure represented by the following general formula (1) and/or a condensate thereof.

In the above general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH _2, and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0-20.

R in the general formula (1) represents an organic group having an amino group, an organic group having an epoxy group, or an organic group having a carbodiimide group. Examples of the organic group having an amino group include an alkylamino group and a cycloalkylamino group which may have a substituent, and examples of the substituent include an alkylene oxide group and an aryl group. Examples of the organic group having an epoxy group include an epoxy group, a glycidyl group, a glycidyl ether type epoxy group, a glycidyl ester type epoxy group, a glycidyl amine type epoxy group, an epoxy group or a hydrocarbon group substituted with a glycidyl group, an epoxy group. Alternatively, a heterocyclic group substituted with a glycidyl group and the like can be mentioned. Examples of the organic group having a carbodiimide group include an alkylcarbodiimide group, a cycloalkylcarbodiimide group, and an arylalkylcarbodiimide group.

N in General formula (1) represents the range of 0-20. When n is 20 or less, plasticization of the (A) polyamide resin is suppressed, and heat aging resistance and calcium chloride resistance can be further improved. n is more preferably 4 or less, and the heat aging resistance and the calcium chloride resistance can be further improved. On the other hand, n is more preferably 1 or more, and the molecular mobility of the (B) compound can be increased, and the compatibility with the (A) polyamide resin can be further improved.

The sum of the numbers of OH, NH ₂ and OR in the general formula (1) is 3 or more. Thereby, the compatibility with the (A) polyamide resin is excellent, and the heat aging resistance and calcium chloride resistance of the obtained molded product can be further improved. Here, the sum of the numbers of OH, NH _2, and OR determines the structural formula of a compound by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.) in the case of a low-molecular compound. , Can be calculated.

In the case of the condensate, the number of OH or NH ₂ is calculated by calculating the number average molecular weight of the compound having the structure represented by the general formula (1) and/or its condensate and the hydroxyl value or amine value, ).

In the case of a condensate, the number of ORs should be calculated by dividing the number average molecular weight of the compound having the structure represented by the general formula (1) and/or its condensate by the amine equivalent, the epoxy equivalent or the carbodiimide equivalent. You can The number average molecular weight of the compound having the structure represented by the general formula (1) and/or its condensate can be calculated by using a gel permeation chromatograph (GPC). Specifically, it can be calculated by the following method. A solvent in which the compound having the structure represented by the general formula (1) and/or a condensate thereof is dissolved, such as hexafluoroisopropanol, is used as a mobile phase, and polymethylmethacrylate (PMMA) is used as a standard substance. The column is matched with the solvent, and for example, in the case of using hexafluoroisopropanol, "Shodex GPC HFIP-806M" and/or "Shodex GPC HFIP-LG" manufactured by Shimadzu GC Co., Ltd. is used as a detector. The number average molecular weight can be measured using a differential refractometer.

In the embodiment of the present invention, the compounding amount of the (B) compound in the polyamide resin composition is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (A) polyamide resin. When the compounding amount of the compound (B) is 0.1 part by weight or more, the heat aging resistance and the calcium chloride resistance can be further improved. Moreover, the peak intensity ratio of the carboxyl group and the concentration ratio of the compound (B) can be easily adjusted to the desired range described above. The compounding amount of the compound (B) is more preferably 0.5 part by weight or more, further preferably 2 parts by weight or more. On the other hand, by adjusting the compounding amount of the (B) compound to 20 parts by weight or less, the dispersibility of the (B) compound in the polyamide resin composition is further improved, and the bleed-out of the (B) compound to the surface layer of the molded article is improved. It can be suppressed and the surface appearance can be further improved. Further, it is possible to suppress plasticization and decomposition of the polyamide resin, and further improve heat aging resistance and calcium chloride resistance. Moreover, the peak intensity ratio of the carboxyl group and the concentration ratio of the compound (B) can be easily adjusted to the desired range described above. The compounding amount of the compound (B) is more preferably 7.5 parts by weight or less, further preferably 6 parts by weight or less.

The method for producing the (B) compound used in the embodiment of the present invention is not particularly limited. A method of dry blending and melt-kneading at a temperature higher than the melting points of both components is preferable.

It is also preferable to add a catalyst in order to promote the reaction between the hydroxyl group and/or amino group and the epoxy group and/or carbodiimide group. The addition amount of the catalyst is not particularly limited, and 0 to 1 part by weight is added to 100 parts by weight of the total of the (b) hydroxyl group- and/or amino group-containing compound and the (b') epoxy group and/or carbodiimide group-containing compound. It is preferably 0.01 to 0.3 part by weight.

Examples of the catalyst that promotes the reaction between the hydroxyl group and the epoxy group include phosphines, imidazoles, amines, and diazabicyclos. Specific examples of the phosphines include triphenylphosphine (TPP) and the like. Specific examples of the imidazoles include 2-heptadecylimidazole (HDI), 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole and the like. Specific examples of amines include N-hexadecylmorpholine (HDM), triethylenediamine, benzyldimethylamine (BDMA), tributylamine, diethylamine, triethylamine, 1,8-diazabicyclo(5,4,0)-undecene-7. (DBU), 1,5-diazabicyclo(4,3,0)-nonene-5(DBN), trisdimethylaminomethylphenol, tetramethylethylenediamine, N,N-dimethylcyclohexylamine, 1,4-diazabicyclo-(2 , 2,2)-octane (DABCO) and the like.

Examples of the catalyst that promotes the reaction between the hydroxyl group and the carbodiimide group include trialkyl lead alkoxide, borofluoric acid, zinc chloride, sodium alkoxide, and the like.

(B) Hydroxyl group and/or amino group-containing compound and (b') epoxy group and/or carbodiimide group-containing compound are melt-kneaded to give (b) a hydroxyl group and/or a hydroxyl group in the amino-containing compound and/or The amino group reacts with the epoxy group and/or carbodiimide group in the (b′) epoxy group and/or carbodiimide group-containing compound. When (b) is a hydroxyl group-containing compound, a dehydration condensation reaction also occurs between the hydroxyl group-containing compounds. Thus, the compound (B) having a multi-branched structure can be obtained.

When the compound (B) is prepared by reacting the compound (b) having a hydroxyl group and/or an amino group with the compound (b') containing an epoxy group and/or a carbodiimide group, the compounding ratio of these compounds is not particularly limited. B) The compound such that the sum of the number of hydroxyl groups and amino groups in one molecule of the compound is larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the (B) compound and/or its condensate. Is preferably blended. The epoxy group and the carbodiimide group are more excellent in reactivity with the terminal group of the (A) polyamide resin than the hydroxyl group and the amino group. Therefore, by making the sum of the number of hydroxyl groups and amino groups in one molecule of the (B) compound larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the (B) compound, excess crosslinking can occur. Embrittlement due to the formation of the structure can be suppressed, and the heat aging resistance and calcium chloride resistance can be further improved.

Further, the weight ratio ((b)/(b')) of the (b) hydroxyl group and/or amino group-containing compound to the (b') epoxy group- and/or carbodiimide group-containing compound to be reacted is 0.3 or more and less than 10,000. Is preferred. (A) the reactivity of the polyamide resin with the (b') epoxy group and/or carbodiimide group-containing compound, and (b) the hydroxyl group and/or amino group containing compound and (b') the epoxy group and/or carbodiimide group containing compound The reactivity is higher than that of the (A) polyamide resin and the (b) hydroxyl group- and/or amino group-containing compound. Therefore, when the weight ratio ((b)/(b')) is 0.3 or more, generation of gel due to excessive reaction is suppressed, and heat aging resistance and calcium chloride resistance are further improved.

When the compound (B) is prepared by reacting the compound (b) having a hydroxyl group and/or an amino group with the compound (b') containing an epoxy group and/or a carbodiimide group, a hydroxyl group or an amino group and an epoxy group or a carbodiimide group are prepared. The reaction rate of is preferably 1 to 95%. When the reaction rate is 1% or more, the branching degree of the (B) compound can be increased, the self-cohesive force can be reduced, the reactivity with the (A) polyamide resin can be increased, and heat aging resistance and chlorination resistance can be increased. Calcium is further improved. The reaction rate is more preferably 10% or more, further preferably 20% or more. On the other hand, when the reaction rate is 95% or less, the epoxy group or the carbodiimide group can be appropriately left and the reactivity with the (A) polyamide resin can be increased. The reaction rate is more preferably 90% or less, further preferably 70% or less.

The reaction rate between the hydroxyl group and/or amino group and the epoxy group and/or carbodiimide group is determined by dissolving the compound (B) in a solvent (for example, deuterated dimethyl sulfoxide, deuterated hexafluoroisopropanol). In the case of a carbodiimide group, a decrease amount before and after the reaction with (b) a hydroxyl group- and/or amino group-containing compound is determined for the epoxy ring-derived peak by a ¹ H-NMR measurement, and in the case of a carbodiimide group, a carbodiimide group by a ¹³ C-NMR measurement. The origin peak can be calculated by determining the amount of decrease before and after the reaction with the compound (b) having a hydroxyl group and/or an amino group. The reaction rate can be calculated by the following formula (4).
Reaction rate (%)={1-(e/d)}×100 (4)
In the above formula (4), d represents a peak area of a compound obtained by dry blending the compound (b) having a hydroxyl group and/or an amino group and the compound (b') having an epoxy group and/or a carbodiimide group, and e is (B ) Represents the peak area of the compound.

As an example, FIG. 5 shows the ¹ H-NMR spectrum of a dry blend of dipentaerythritol and a bisphenol A type epoxy resin (“jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation) at a weight ratio of 3:1. .. Further, the ¹ H-NMR spectrum of the (B-7) compound and/or its condensate obtained in Reference Example 9 described later is shown in FIG. 6. Deuterated dimethyl sulfoxide was used as a solvent, the sample amount was 0.035 g, and the solvent amount was 0.70 ml. Reference numeral 1 indicates a solvent peak.

From the ¹ H-NMR spectrum shown in FIG. 5, the total of epoxy ring-derived peak areas appearing in the vicinity of 2.60 ppm and 2.80 ppm was obtained, and similarly, the total of peak areas shown in FIG. 6 was obtained, and the reaction rate calculation formula ( The reaction rate is calculated from 4). At this time, the peak area is normalized by the area of the peak of the benzene ring of the epoxy resin that does not contribute to the reaction.

The polyamide resin composition used for the molded article of the embodiment of the present invention and the polyamide resin composition of the embodiment of the present invention may further contain a copper compound. It is considered that the copper compound, in addition to coordinating to the amide group of the (A) polyamide resin, also coordinates with the hydroxyl group and hydroxide ion of the (B) compound. Therefore, it is considered that the copper compound has an effect of increasing the compatibility between the (A) polyamide resin and the (B) compound.

The polyamide resin composition of the embodiment of the present invention may further contain a potassium compound. Potassium compounds suppress the liberation and precipitation of copper. Therefore, it is considered that the potassium compound has an effect of promoting the reaction of the copper compound with the (B) compound and the (A) polyamide resin.

Examples of the copper compound include copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper borofluoride, copper citrate, copper hydroxide, copper nitrate, copper sulfate, and copper oxalate. And so on. You may contain 2 or more types of these as a copper compound. Among these copper compounds, those commercially available are preferable, and copper halide is preferable. Examples of the copper halide include copper iodide, cuprous bromide, cupric bromide, cuprous chloride and the like. Copper iodide is more preferable as the copper halide.

Examples of the potassium compound include potassium iodide, potassium bromide, potassium chloride, potassium fluoride, potassium acetate, potassium hydroxide, potassium carbonate, potassium nitrate and the like. You may contain 2 or more types of these as a potassium compound. Among these potassium compounds, potassium iodide is preferable. By including the potassium compound, the surface appearance, weather resistance and mold corrosion resistance of the molded product can be further improved.

In the embodiment of the present invention, the content (weight basis) of the copper element in the polyamide resin composition is preferably 25 to 200 ppm. When the content of the copper element is 25 ppm or more, the compatibility between the (A) polyamide resin and the (B) compound is further improved, and the heat aging resistance of the molded product can be further improved. The content (weight basis) of the copper element in the polyamide resin composition is preferably 80 ppm or more. On the other hand, by setting the content of the copper element to be 200 ppm or less, it is possible to suppress the coloring due to the precipitation and liberation of the copper compound and further improve the surface appearance of the molded product. Further, by setting the content of the copper element to 200 ppm or less, it is possible to suppress the decrease in the hydrogen bonding force of the amide group due to the excessive coordination bond between the polyamide resin and copper, and further improve the heat aging resistance of the molded product. be able to. The content (weight basis) of the copper element in the polyamide resin composition is preferably 190 ppm or less. The content of the copper element in the polyamide resin composition can be adjusted to the above-mentioned desired range by appropriately adjusting the blending amount of the copper compound.

The content of copper element in the polyamide resin composition can be determined by the following method. First, pellets of the polyamide resin composition are dried under reduced pressure. The pellets are ashed in an electric furnace at 550° C. for 24 hours, concentrated sulfuric acid is added to the ashed product, and the mixture is heated and wet-decomposed to dilute the decomposition liquid. The copper content can be determined by subjecting the diluted solution to atomic absorption analysis (calibration curve method).

The ratio Cu/K of the content of the copper element to the content of the potassium element in the polyamide resin composition is preferably 0.21 to 0.43. Cu/K is an index showing the degree of suppression of copper precipitation and release, and the smaller this value is, the more suppressed copper precipitation and release is, and the copper compound, (B) compound and (A) polyamide resin. The reaction with can be promoted. By setting Cu/K to 0.43 or less, the precipitation and liberation of copper can be suppressed and the surface appearance of the molded product can be further improved. Further, by adjusting the Cu/K to 0.43 or less, the compatibility of the polyamide resin composition is also improved, so that the heat aging resistance of the molded product can be improved. On the other hand, by setting Cu/K to 0.21 or more, the dispersibility of a compound containing potassium is improved, and even deliquescent potassium iodide is unlikely to form lumps, which has the effect of suppressing the precipitation and release of copper. As a result, the reaction of the copper compound with the (B) compound and the (A) polyamide resin is sufficiently promoted, and the heat aging resistance of the molded product is further improved. The potassium element content in the polyamide resin composition can be determined by the same method as the above copper content.

The polyamide resin composition used for the molded article of the embodiment of the present invention and the polyamide resin composition of the embodiment of the present invention may further contain a filler. As the filler, either an organic filler or an inorganic filler may be used, and a fibrous filler or a non-fibrous filler may be used. A fibrous filler is preferable as the filler.

Examples of the fibrous filler include glass fiber, PAN (polyacrylonitrile)-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber and brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, Ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whiskers, zinc oxide whiskers, calcium carbonate whiskers, wollastonite whiskers, borate aluminum whiskers, silicon nitride whiskers Fibrous or whisker-like fillers such as. As the fibrous filler, glass fiber and carbon fiber are particularly preferable.

The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, long fiber type or short fiber type chopped strands, milled fiber, etc. can be selected and used. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like. Furthermore, the cross section of the glass fiber is not limited to a circular shape, a flat gourd shape, an eyebrow shape, an oval shape, an elliptical shape, a rectangular shape, or the like. From the viewpoint of reducing the warp peculiar to the molded product that is likely to occur in the glass fiber-containing polyamide resin composition, flat fibers having a major axis/minor axis ratio of 1.5 or more are preferred, and 2.0 or more are more preferred. Those of 10 or less are preferable, and those of 6.0 or less are more preferable. If the ratio of major axis/minor axis is less than 1.5, the effect of flattening the cross section is small, and if it exceeds 10, it is difficult to manufacture the glass fiber itself.

As the non-fibrous filler, for example, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, non-swelling silicates such as calcium silicate, Li-type fluorine. Swelling layered silicate represented by swelling mica of teniolite, Na-type fluoro-teniolite, Na-type tetrasilicon-fluorine mica, Li-type tetra-silicon-fluorine mica, silicon oxide, magnesium oxide, alumina, silica, diatomaceous earth, zirconium oxide, oxidation Metal oxides such as titanium, iron oxide, zinc oxide, calcium oxide, tin oxide, antimony oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite, hydrotalcite and other metal carbonates, calcium sulfate, barium sulfate Such as metal sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, metal hydroxide such as basic magnesium carbonate, smectite clay mineral such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite Examples thereof include various clay minerals such as vermiculite, halloysite, kanemite, kenyaite, zirconium phosphate and titanium phosphate, glass beads, glass flakes, ceramic beads, boron nitride, aluminum nitride, silicon carbide, calcium phosphate, carbon black and graphite. In the swellable layered silicate, the exchangeable cations existing between the layers may be exchanged with organic onium ions, and examples of the organic onium ions include ammonium ion, phosphonium ion, sulfonium ion and the like. Moreover, you may contain 2 or more types of these fillers.

The surface of the filler is a known coupling agent (eg, silane coupling agent, titanate coupling agent, etc.) or known sizing agent (eg, carboxylic acid type, epoxy type, urethane type, etc.). And the like, and can further improve the mechanical strength and surface appearance of the molded product. The sizing agent is preferably an epoxy sizing agent. As the method of treating the filler, for example, in the case of treatment with a coupling agent, a method of preliminarily surface-treating the filler with a coupling agent according to a conventional method and then melt-kneading with a polyamide resin is preferably used. An integrable blending method in which a coupling agent is added may be used when the filler and the polyamide resin are melt-kneaded without performing the surface treatment. The treating amount of the coupling agent is preferably 0.05 parts by weight or more, and more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the filler. On the other hand, the treatment amount of the coupling agent is preferably 10 parts by weight or less, and more preferably 3 parts by weight or less with respect to 100 parts by weight of the filler.

In the embodiment of the present invention, the content of the filler in the polyamide resin composition is preferably 1 to 150 parts by weight with respect to 100 parts by weight of the (A) polyamide resin. When the content of the filler is 1 part by weight or more, the mechanical strength and heat aging resistance of the molded product can be further improved. The content of the filler is more preferably 10 parts by weight or more, further preferably 20 parts by weight or more. On the other hand, when the content of the filler is 150 parts by weight or less, the float of the filler on the surface of the molded product is suppressed, and a molded product having a better surface appearance can be obtained. The content of the filler is more preferably 80 parts by weight or less, further preferably 70 parts by weight or less.

Further, in the embodiment of the present invention, the polyamide resin composition may contain a resin other than the polyamide resin and various additives depending on the purpose, as long as the effects of the present invention are not impaired.

Specific examples of resins other than polyamide resins include polyester resins, polyolefin resins, modified polyphenylene ether resins, polysulfone resins, polyketone resins, polyetherimide resins, polyarylate resins, polyethersulfone resins, polyetherketone resins, polythioethers. Examples thereof include a ketone resin, a polyether ether ketone resin, a polyimide resin, a polyamideimide resin, and a tetrafluoropolyethylene resin. When these resins are blended, the content thereof is preferably 30 parts by weight or less, and more preferably 20 parts by weight or less with respect to 100 parts by weight of the (A) polyamide resin in order to fully utilize the characteristics of the polyamide resin.

Further, specific examples of various additives include heat stabilizers other than copper compounds, isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, coupling agents such as epoxy compounds, and polyalkylene oxide oligomers. -Based compounds, thioether-based compounds, plasticizers such as ester-based compounds, crystal nucleating agents such as polyetheretherketone, montanic acid waxes, metallic soaps such as lithium stearate and aluminum stearate, ethylenediamine/stearic acid/sebacic acid Examples thereof include a condensate, a release agent such as a silicone compound, a lubricant, an anti-UV agent, a colorant, a flame retardant, an impact resistance improver, and a foaming agent. When these additives are contained, the content thereof is preferably 10 parts by weight or less, and more preferably 1 part by weight or less, relative to 100 parts by weight of the (A) polyamide resin in order to fully utilize the characteristics of the polyamide resin.

Examples of heat stabilizers other than copper compounds include phenol compounds, sulfur compounds and amine compounds. Two or more of these may be used as the heat stabilizer other than the copper compound.

As the phenolic compound, a hindered phenolic compound is preferably used, and N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis[methylene-3-(3 ',5'-Di-t-butyl-4'-hydroxyphenyl)propionate]methane and the like are preferably used.

Examples of sulfur compounds include organic thioacid compounds, mercaptobenzimidazole compounds, dithiocarbamic acid compounds, and thiourea compounds. Among these sulfur compounds, mercaptobenzimidazole compounds and organic thioacid compounds are preferable. In particular, a thioether compound having a thioether structure receives oxygen from an oxidized substance and reduces it, and thus can be suitably used as a heat stabilizer. Specific examples of the thioether compound include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate). ) And pentaerythritol tetrakis (3-lauryl thiopropionate) are preferable, and pentaerythritol tetrakis (3-dodecyl thiopropionate) and pentaerythritol tetrakis (3-lauryl thiopropionate) are more preferable. The molecular weight of the sulfur compound is usually 200 or more, preferably 500 or more, and the upper limit thereof is usually 3,000.

The amine compound is preferably a compound having a diphenylamine skeleton, a compound having a phenylnaphthylamine skeleton and a compound having a dinaphthylamine skeleton, more preferably a compound having a diphenylamine skeleton and a compound having a phenylnaphthylamine skeleton. Among these amine compounds, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, N,N′-di-2-naphthyl-p-phenylenediamine and N,N′-diphenyl-p-phenylenediamine are available. More preferred are N,N′-di-2-naphthyl-p-phenylenediamine and 4,4′-bis(α,α-dimethylbenzyl)diphenylamine.

As the combination of the sulfur compound or the amine compound, a combination of pentaerythritol tetrakis(3-laurylthiopropionate) and 4,4′-bis(α,α-dimethylbenzyl)diphenylamine is more preferable.

The polyamide resin composition of the embodiment of the present invention is a rod-shaped test obtained by Fourier transform infrared spectroscopy when a rod-shaped test piece having a thickness of 6.4 mm is injection-molded and heat-treated at 150° C. for 1000 hours in the atmosphere. The ratio (Y/Z) of the peak intensity Y of the carboxyl group on one surface to the peak intensity Z of the carboxyl group at a depth of 0.28 mm from the surface of the rod-shaped test piece is preferably 5.0 or less. When the rod-shaped test piece was heat-treated at 150° C. for 1000 hours in the atmosphere, the concentration V of the (B) compound in the polyamide resin composition on the surface of the rod-shaped test piece obtained by Fourier transform infrared spectroscopy and the bar-shaped The ratio (V/W) to the concentration W of the (B) compound in the polyamide resin composition at a depth of 0.28 mm from the surface of the test piece is preferably 1.2 to 5.0. The method for measuring the peak intensity ratio of the carboxyl group and the concentration ratio of the compound (B) is as described for the molded article of the embodiment of the present invention.

In the embodiment of the present invention, the method for producing the polyamide resin composition is not particularly limited, but production in a molten state, production in a solution state, or the like can be used, and in terms of reactivity improvement, in a molten state. Manufacturing can be preferably used. For production in a melted state, melt kneading with an extruder or melt kneading with a kneader can be used, but from the viewpoint of productivity, melt kneading with an extruder that allows continuous production is preferable. For melt-kneading with an extruder, one or more extruders such as a single-screw extruder, a twin-screw extruder, a four-screw extruder or a multi-screw extruder, or a twin-screw single-screw extruder can be used. From the viewpoints of improving reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder is preferable, and a method of melt-kneading using a twin-screw extruder is most preferable.

In the embodiment of the present invention, as a method for producing a polyamide resin composition, a (B) compound prepared in advance from (b) a hydroxyl group- and/or amino group-containing compound and (b') an epoxy group and/or a carbodiimide group-containing compound Examples of the method include melt-kneading (A) with a polyamide resin.

In the case of melt-kneading using a twin-screw extruder, there is no particular limitation on the method of supplying the raw material to the twin-screw extruder. When the compound (B) is fed to the twin-screw extruder, the compound (B) easily accelerates the decomposition of the polyamide resin in a temperature range higher than the melting point of the polyamide resin. It is preferable to supply it from the downstream side and shorten the kneading time of the (A) polyamide resin and the (B) compound. Here, the side of the twin-screw extruder to which the raw material is supplied is defined as upstream, and the side where the molten resin is discharged is defined as downstream.

It is considered that the copper compound plays a role of protecting the amide group by coordinating with the amide group of the (A) polyamide resin, and also plays a role of a compatibilizing agent for the (A) polyamide resin and the (B) compound. Therefore, when the copper compound is blended, it is preferable to supply it to the twin-screw extruder together with the (A) polyamide resin to sufficiently react the (A) polyamide resin and the copper compound.

The ratio (L/D) of the total screw length L and the screw diameter D of the twin-screw extruder is preferably 25 or more, and more preferably more than 30. When L/D is 25 or more, it becomes easy to supply the compound (B) after sufficiently kneading the polyamide resin (A) and the copper compound as necessary. In addition, when the copper compound is blended, it becomes easy to supply the compound (B) after sufficiently kneading the polyamide resin (A) and the copper compound. As a result, the decomposition of the (A) polyamide resin can be suppressed. Further, it is considered that the compatibility of the (A) polyamide resin and the (B) compound is further improved, and the heat aging resistance and calcium chloride resistance of the molded product can be further improved.

In the embodiment of the present invention, it is preferable that at least (A) a polyamide resin and, if necessary, a copper compound are supplied to a twin-screw extruder from an upstream side of 1/2 of the screw length and melt-kneaded. It is more preferable to supply from the upstream end. The screw length referred to here is the length from the upstream end of the screw segment at the position (feed port) where the (A) polyamide resin at the screw root is supplied to the screw tip. The upstream end of the screw segment refers to the position of the screw piece located at the most upstream end of the screw segment connected to the extruder.

The compound (B) is preferably melt-kneaded by being supplied to the twin-screw extruder from the downstream side of half the screw length. By supplying the compound (B) from the downstream side of 1/2 of the screw length, it is possible to supply the compound (B) after the polyamide resin (A) and the copper compound have been sufficiently kneaded if necessary. It will be easier. As a result, the reaction rate of the (B) compound can be increased while suppressing the increase in the viscosity of the (A) polyamide resin, and the degree of branching can be increased to reduce the self-cohesive force. It is considered that the compatibility of the compound (B) increases. As a result, the heat aging resistance and calcium chloride resistance of the molded product can be further improved.

When a polyamide resin composition is produced using a twin-screw extruder, it is preferable to use a twin-screw extruder having a plurality of full flight zones and a plurality of kneading zones from the viewpoint of improving kneading properties and reactivity. .. The full flight zone is composed of one or more full flights, and the kneading zone is composed of one or more kneading discs.

Further, among the resin pressures in a plurality of kneading zones, the maximum resin pressure is Pkmax (MPa), and among the resin pressures in a plurality of full flight zones, the minimum resin pressure is Pfmin (MPa). ,
Pkmax≧Pfmin+0.3
It is preferable to melt-knead under the following conditions,
Pkmax≧Pfmin+0.5
It is more preferable to melt-knead under the following conditions. The resin pressure in the kneading zone and the full flight zone refers to the resin pressure indicated by the resin pressure gauge installed in each zone.

The kneading zone is excellent in kneading property and reactivity of the molten resin as compared with the full flight zone. By filling the kneading zone with the molten resin, the kneadability and reactivity are dramatically improved. The value of the resin pressure is one index indicating the filled state of the molten resin, and the higher the resin pressure, the more the index shows that the molten resin is filled. That is, in the case of using a twin-screw extruder, the reaction can be effectively promoted by increasing the resin pressure in the kneading zone within a predetermined range from the resin pressure in the full flight zone. It is considered that the compatibility between the resin and the compound (B) is increased, and the heat aging resistance and calcium chloride resistance of the molded product can be further improved.

The method for increasing the resin pressure in the kneading zone is not particularly limited, for example, between the kneading zone or on the downstream side of the kneading zone, a reverse screw zone having an effect of pushing back the molten resin to the upstream side, or the molten resin. A method of introducing a seal ring zone or the like having an effect of accumulating can be preferably used. The reverse screw zone and the seal ring zone are formed of one or more reverse screws and one or more seal rings, and it is possible to combine them.

When the total length of the kneading zone on the upstream side of the compound (B) supply position is Ln1, Ln1/L is preferably 0.02 or more, and more preferably 0.03 or more. On the other hand, Ln1/L is preferably 0.40 or less, more preferably 0.20 or less. By setting Ln1/L to 0.02 or more, the reactivity of the (A) polyamide resin can be increased, and by setting it to 0.40 or less, shearing heat generation is appropriately suppressed and thermal deterioration of the resin is suppressed. be able to. The melting temperature of the (A) polyamide resin is not particularly limited, but it is preferably 340° C. or lower in order to suppress the decrease in the molecular weight due to the heat deterioration of the (A) polyamide resin.

When the total length of the kneading zone on the downstream side of the (B) compound supply position is Ln2, Ln2/L is preferably 0.02 to 0.30. By setting Ln2/L to 0.02 or more, the reactivity of the compound (B) can be further enhanced. Ln2/L is more preferably 0.04 or more. On the other hand, by setting Ln2/L to 0.30 or less, the decomposition of the (A) polyamide resin can be further suppressed. Ln2/L is more preferably 0.16 or less.

In the embodiment of the present invention, as a more preferable method for producing the polyamide resin composition, a high-concentration preliminary mixture is prepared by melt-kneading the (A) polyamide resin and the (B) compound with a twin-screw extruder, and preparing the high-concentration preliminary mixture. A method of melt-kneading the mixture with the (A) polyamide resin using a twin-screw extruder can be mentioned. (A) 10 to 250 parts by weight of the compound (B) is melt-kneaded with 100 parts by weight of the polyamide resin to prepare a high-concentration premix, and the high-concentration premix is further biaxially mixed with the (A) polyamide resin. It is more preferable to melt-knead with an extruder. The heat aging resistance and calcium chloride resistance of the obtained molded article can be dramatically improved as compared with the case where a high-concentration premix is not produced. The reason for this is not clear, but it is considered that the compatibility between the respective components is further improved by performing the melt-kneading twice. Further, when the high-concentration premix is prepared, the compounding amount of the (B) compound becomes large relative to the (A) polyamide resin. In order to suppress deterioration of retention stability, during melt kneading in a twin-screw extruder, the (B) compound is supplied from the downstream side of the polyamide resin supply position, and the (A) polyamide resin and (B) compound kneading time Is preferably shortened. The (A) polyamide resin used in the high-concentration premix and the (A) polyamide resin further blended in the high-concentration premix may be the same or different. The polyamide resin (A) used in the high-concentration premix is preferably nylon 6, nylon 11 and/or nylon 12 from the viewpoint of further improving the heat aging resistance of the molded product.

The polyamide resin composition thus obtained can be molded by a known method, and various molded products such as sheets, films and fibers can be obtained from the polyamide resin composition. Examples of the molding method include injection molding, injection compression molding, extrusion molding, compression molding, blow molding, and press molding.

The molded product of the embodiment of the present invention has a thickness of 0.56 mm or more. Here, the thickness of the molded product refers to the thickness of the thinnest part of the molded product. However, if the molded product is provided with a drain hole or the like, such a part is excluded.

A molded article obtained from the polyamide resin composition of the embodiment of the present invention utilizes its excellent characteristics, and is used for automobile engine peripheral parts, automobile underhood parts, automobile gear parts, automobile interior parts, automobile exterior parts, intake and exhaust system parts. It can be used for various purposes such as engine cooling water system parts, automobile electrical parts, electric/electronic parts, building materials, various containers, daily necessities, household goods and sanitary goods. Specifically, engine covers, air intake pipes, timing belt covers, intake manifolds, filler caps, throttle bodies, cooling fan and other automotive engine peripheral parts, cooling fans, radiator tank tops and bases, cylinder head covers, oil pans, Automotive underhood parts such as canisters, brake piping, fuel piping tubes, waste gas system parts, gears, actuators, bearing retainers, bearing cages, chain guides, chain tensioners and other automotive gear parts, shift lever brackets, steering lock brackets, Key cylinder, door inner handle, door handle cowl, interior mirror bracket, air conditioner switch, instrument panel, console box, glove box, steering wheel, trim and other automotive interior parts, front fender, rear fender, fuel lid, door panel, cylinder head cover , Door mirror stay, Tailgate panel, License garnish, Roof rail, Engine mount bracket, Rear garnish, Rear spoiler, Trunk lid, Rocker molding, Mall, Lamp housing, Front grille, Mudguard, Side bumper and other automotive exterior parts, Air intake manifold , Intercooler inlet, turbocharger, exhaust pipe cover, inner bush, bearing retainer, engine mount, engine head cover, resonator, and intake/exhaust system parts such as throttle body, chain cover, thermostat housing, outlet pipe, radiator tank, oil generator, And engine cooling water system parts such as delivery pipes, connectors and wire harness connectors, motor parts, lamp sockets, sensor in-vehicle switches, automotive electrical parts such as combination switches, and electrical/electronic parts such as generators, electric motors, transformers. , Current transformers, voltage regulators, rectifiers, resistors, inverters, relays, power contacts, switches, circuit breakers, switches, knife switches, other pole rods, motor cases, laptop housings and internal parts, CRT display housings And internal parts, printer housings and internal parts, mobile terminals such as mobile phones, mobile computers, handheld mobiles, etc. Housing and internal parts, IC and LED compatible housings, condenser seat plates, fuse holders, various gears, various cases, cabinets and other electrical parts, connectors, SMT compatible connectors, card connectors, jacks, coils, coil bobbins, sensors, LED lamps , Sockets, resistors, relays, relay cases, reflectors, small switches, power supplies, coil bobbins, capacitors, variable capacitor cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones , Headphone, small motor, magnetic head base, power module, Si power module or SiC power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, transformer member, parabolic antenna, computer related parts, etc. To be Among them, the molded article of the embodiment of the present invention is particularly preferably used for automobile underhood parts because it has excellent heat aging resistance, calcium chloride resistance and surface appearance.

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. The characteristic evaluation was performed according to the following methods.

[Melting point of polyamide resin]
About 5 mg of the polyamide resin was collected, and the melting point of the (A) polyamide resin was measured under the following conditions using a robot DSC (differential scanning calorimeter) RDC220 manufactured by Seiko Instruments under a nitrogen atmosphere. After the polyamide resin is heated to the melting point +40° C. to be in a molten state, the temperature is lowered to 30° C. at a temperature lowering rate of 20° C./min, the temperature is maintained at 30° C. for 3 minutes, and then the melting point is raised at a temperature rising rate of 20° C./min. The temperature (melting point) of the endothermic peak observed when the temperature was raised to +40°C was determined.

[Relative viscosity of polyamide resin]
The relative viscosity (ηr) was measured in a 98% concentrated sulfuric acid having a polyamide resin concentration of 0.01 g/ml at 25° C. using an Ostwald viscometer.

[Weight average molecular weight and number average molecular weight]
2.5 mg of the compound (B), the compound (b) containing a hydroxyl group and/or an amino group, and the compound (b') containing an epoxy group and/or a carbodiimide group (2.5 mg) are each added to hexafluoroisopropanol (0.005N-sodium trifluoroacetate added). The solution obtained by dissolving in 4 ml and filtering with a 0.45 μm filter was used for measurement. The measurement conditions are shown below.
Device: Gel permeation chromatography (GPC) (Waters)
Detector: Differential refractometer Waters410 (manufactured by Waters)
Column: Shodex GPC HFIP-806M (2 pieces) + HFIP-LG (Shimadzu GL Co., Ltd.)
Flow rate: 0.5 ml/min
Sample injection volume: 0.1 ml
Temperature: 30°C
Molecular weight calibration: polymethylmethacrylate.

[Hydroxyl value]
0.5 g of (b) hydroxyl group-containing compound and (B) compound were sampled and added to a 250 ml Erlenmeyer flask, respectively, and then 20.00 ml of a solution in which acetic anhydride and anhydrous pyridine were adjusted and mixed at 1:10 (mass ratio). It was collected, placed in the Erlenmeyer flask, equipped with a reflux condenser, refluxed for 20 minutes under stirring in an oil bath whose temperature was controlled at 100° C., and then cooled to room temperature. Further, 20 ml of acetone and 20 ml of distilled water were added to the Erlenmeyer flask through a condenser. A phenolphthalein indicator was added to this and titrated with a 0.5 mol/L ethanolic potassium hydroxide solution. In addition, the hydroxyl value was calculated by the following formula (5) by subtracting the measurement result of a blank (excluding the sample) which was separately measured.
Hydroxyl value [mgKOH/g]=[((B−C)×f×28.05)/S]+E (5)
However, B: amount of 0.5 mol/L ethanolic potassium hydroxide solution used for titration [ml], C: amount of 0.5 mol/L ethanolic potassium hydroxide solution used for blank titration [ml] ], f: factor of 0.5 mol/L ethanolic potassium hydroxide solution, S: mass of sample [g], E: acid value.

[Amine value]
0.5 to 1.5 g of (b) the amino group-containing compound and (B) compound were precisely weighed and dissolved in 50 ml of ethanol. Using a potentiometric titrator equipped with a pH electrode (AT-200 manufactured by Kyoto Electronics Manufacturing Co., Ltd.), this solution was subjected to neutralization titration with an ethanolic hydrochloric acid solution having a concentration of 0.1 mol/L. Using the inflection point of the pH curve as the titration end point, the amine value was calculated by the following formula (6).
Amine value [mgKOH/g]=(56.1×V×0.1×f)/W (6)
However, W: Weighed amount of sample [g], V: Titration amount at the end point of titration [ml], f: Factor of 0.1 mol/L ethanolic hydrochloric acid solution.
[Reaction rate of (B) compound]
(B) Compound (0.035 g) was dissolved in deuterated dimethylsulfoxide (0.7 ml), and ¹ H-NMR measurement was carried out for an epoxy group, and ¹³ C-NMR measurement was carried out for a carbodiimide group. Each analysis condition is as follows.
(1) ¹ H-NMR
Apparatus: JEOL Ltd. nuclear magnetic resonance apparatus (JNM-AL400)
Solvent: Deuterated dimethyl sulfoxide Observation frequency: OBFRQ399.65MHz, OBSET124.00KHz, OBFIN10500.00Hz
Accumulation frequency: 256 times (2) ¹³ C-NMR
Apparatus: JEOL Ltd. nuclear magnetic resonance apparatus (JNM-AL400)
Solvent: Deuterated dimethyl sulfoxide Observation frequency: OBFRQ100.40MHz, OBSET125.00KHz, OBFIN10500.00Hz
Total number of times: 512 times.

The area of the epoxy ring-derived peak was determined from the obtained ¹ H-NMR spectrum. Further, the area of the peak derived from the carbodiimide group was determined from the obtained ¹³ C-NMR spectrum. The peak area was calculated by using the analysis software attached to the NMR apparatus and integrating the area of the portion surrounded by the baseline and the peak. The reaction area is defined as the peak area of the compound obtained by dry-blending the (b) hydroxyl group and/or amino group-containing compound and the (b') epoxy group and/or carbodiimide group-containing compound, and the peak area of the (B) compound as e. Was calculated by the following formula (4).
Reaction rate (%)={1-(e/d)}×100 (4)

As an example, the ¹ H-NMR spectrum of a dry blend of dipentaerythritol and bisphenol A type epoxy resin "Mitsubishi Chemical Corporation "jER" (registered trademark) 1004 at a weight ratio of 3:1 is shown in FIG. shown. also from ¹ H-NMR spectrum shows a ¹ H-NMR spectrum of the obtained in reference example 9 (B-7) compound. Figure 5 shown in FIG. 6, the epoxy ring appearing in the vicinity of 2.60ppm and 2.80ppm The total of the peak areas derived was calculated, and the total of the peak areas shown in Fig. 2 was calculated in the same manner, and the reaction rate was calculated from the reaction rate calculation formula (4), where the peak area is the benzene of the epoxy resin that does not contribute to the reaction. Normalized by the area of the ring peak.

[Branching degree]
The compound (B) and the compound (b) having a hydroxyl group and/or an amino group were subjected to ¹³ C-NMR analysis under the following conditions, and then the degree of branching (DB) was calculated by the following formula (2).
Branching degree=(D+T)/(D+T+L) (2)
In the above formula (2), D represents the number of dendritic units, L represents the number of linear units, and T represents the number of terminal units. The above D, T, and L were calculated from the peak areas measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom which is a methyl group, and L is a primary or secondary carbon atom, Derived from those excluding T. The peak area was calculated by using the analysis software attached to the NMR apparatus and integrating the area of the portion surrounded by the baseline and the peak. The measurement conditions are as follows.
(1) ¹³ C-NMR
Apparatus: JEOL Ltd. nuclear magnetic resonance apparatus (JNM-AL400)
Solvent: Deuterated dimethyl sulfoxide measurement sample amount/solvent amount: 0.035 g/0.70 ml
Observation frequency: OBFRQ100.40MHz, OBSET125.00KHz, OBFIN10500.00Hz
Total number of times: 512 times.

[Number of hydroxyl groups and amino groups, and number of epoxy groups and carbodiimide groups]
The number of hydroxyl groups or amino groups was calculated by the following formula (3) by calculating the number average molecular weight and hydroxyl value or amine value of the compound (B) and the compound (b) containing a hydroxyl group and/or an amino group.
Number of OH or NH ₂ =(number average molecular weight x hydroxyl value or amine value)/56110 (3)

Further, the number of epoxy groups or carbodiimide groups was calculated by dividing the number average molecular weight of the compound (B), (b') epoxy group and/or carbodiimide group-containing compound by the epoxy equivalent or carbodiimide equivalent.

The number average molecular weight, hydroxyl value and amine value were measured by the above-mentioned methods. Epoxy equivalent is the compound (B), (b') epoxy group and/or carbodiimide group-containing compound 400 mg is dissolved in hexafluoroisopropanol 30 ml, then acetic acid 20 ml, tetraethylammonium bromide/acetic acid solution (=50 g/200 ml) Was added, and 0.1N perchloric acid was used as a titrant and crystal violet was used as an indicator, and it was calculated by the following formula (7) from the titration amount when the color of the solution changed from purple to blue-green.
Epoxy equivalent [g/eq]=W/((F−G)×0.1×f×0.001) (7)
However, F: the amount of 0.1N perchloric acid used for the titration [ml], G: the amount of 0.1N perchloric acid used for the titration of the blank [ml], f: 0.1N perchlorine Acid factor, W: mass of sample [g]

The carbodiimide equivalent was calculated by the following method. 100 parts by weight of the compound (B), the epoxy group- and/or carbodiimide group-containing compound (b') and 30 parts by weight of potassium ferrocyanide (manufactured by Tokyo Chemical Industry Co., Ltd.) as an internal standard substance are dry-blended at about 200°C. Heat pressing was performed for 1 minute to prepare a sheet. Then, the infrared absorption spectrum of the sheet was measured by a transmission method using an infrared spectrophotometer (IR Prestige-21/AIM8800, manufactured by Shimadzu Corporation). The measurement conditions were a resolution of 4 cm ⁻¹ and an integration count of 32 times. In the infrared absorption spectrum by the transmission method, since the absorbance is inversely proportional to the sheet thickness, it is necessary to standardize the peak intensity of the carbodiimide group using the internal standard peak. A value obtained by dividing the absorbance of the carbodiimide group-derived peak appearing at around 2140 cm ^{−1 by} the absorbance of the CN group absorption peak of potassium ferrocyanide that appears near 2100 cm ⁻¹ was calculated. In order to calculate the carbodiimide equivalent from this value, the carbodiimide equivalent was previously subjected to IR measurement using a known sample, and a calibration curve was prepared using the ratio of the absorbance of the carbodiimide group-derived peak and the absorbance of the internal standard peak, ( The carbodiimide equivalent was calculated by substituting the absorbance ratio of the compound B), the compound containing (b') epoxy group and/or carbodiimide group into the calibration curve. In addition, as a sample having a known carbodiimide equivalent, aliphatic polycarbodiimide (manufactured by Nisshinbo, “carbodilite” (registered trademark) LA-1, carbodiimide equivalent 247 g/mol), aromatic polycarbodiimide (manufactured by Rhein Chemie, “STABAXOL” (registered trademark) ) P, carbodiimide equivalent of 360 g/mol) was used.

[Peak intensity ratio of carboxyl group]
The 6.4 mm-thick rod-shaped test piece obtained by each Example and the comparative example was heat-processed at 150 degreeC for 1000 hours in air|atmosphere. On the surface of the rod-shaped test piece after the heat treatment, the peak intensity Y of the carboxyl group was measured under the following conditions using the macro infrared ATR method of a Fourier transform infrared spectrophotometer (Varian 7000FT-IR manufactured by Agilent Technologies, Inc.) did.
Light source: Special ceramics Detector: DTGS
Resolution: 4 cm ^-1
Cumulative number of times: 128 times IRE: Ge
Incident angle: 45 degrees Attachment: One-time reflection ATR attachment (thunder dome).

The peak intensity of the C=O stretching vibration of the carboxyl group in the obtained FT-IR spectrum was determined, and the value normalized by the peak intensity of the C=O stretching vibration of the amide bond was used as the peak of the carboxyl group on the surface of the molded product. It was calculated as intensity Y.

In addition, the cross section of the bar-shaped test piece after the heat treatment was cut in the depth direction with a band saw and mirror-finished with a diamond cutter, and a microscope of a Fourier transform infrared spectrophotometer (Spot-light manufactured by Perkin Elmer Co., Ltd.) was used. Using the infrared ATR method, the peak intensity of the carboxyl group at each arbitrary depth was measured while scanning in the depth direction from the surface of the rod-shaped test piece under the following conditions.
Light source: Special ceramics Detector: MCT
Resolution: 4 cm ^-1
Number of integration: 128 times/point Measurement mode: ATR method Measurement area per point: 80 μm×80 μm.

The peak intensity of C=O stretching vibration of the carboxyl group was obtained from the obtained FT-IR spectrum at each depth, and the peak intensity of the C=O stretching vibration of the amide bond was standardized to obtain the peak intensity at each depth. The peak intensity of the carboxyl group was calculated. The peak intensity ratio of the carboxyl groups was calculated by dividing the peak intensity Y by the peak intensity Z of the carboxyl groups at a depth of 0.28 mm from the surface of the molded product.

As an example, the FT-IR spectrum of the surface of the molded product after heat-treating the bar-shaped test piece (molded product) having a thickness of 6.4 mm obtained in Example 3 at 150° C. for 1000 hours in the atmosphere is shown in FIG. Show. The FT-IR spectrum of the cross section of the molded product in the depth direction is shown in FIG. From the spectra of FIGS. 1 and 2, the peak intensity of the C═O stretching vibration of the carboxyl group near 1720 cm ⁻¹ was normalized by the peak intensity of the C═O stretching vibration of the amide bond near 1632 cm ^−1. It was FIG. 3 shows a plot of normalized peak intensity with respect to the distance from the surface of the molded product. From FIG. 3, the peak intensity Y on the surface of the molded product was divided by the peak intensity Z at a depth of 0.28 mm from the surface of the molded product to calculate the peak intensity ratio (Y/Z) of the carboxyl groups.

[(B) Compound Concentration Ratio]
The 6.4 mm-thick rod-shaped test piece obtained by each Example and the comparative example was heat-processed at 150 degreeC for 1000 hours in air|atmosphere. Regarding the surface of the rod-shaped test piece after the heat treatment, a polyamide resin composition on the surface of the rod-shaped test piece was used under the following conditions by using a macro infrared ATR method of a Fourier transform infrared spectrophotometer (Varian 7000FT-IR manufactured by Agilent Technologies). The concentration V of the compound (B) in the product was measured.
Light source: Special ceramics Detector: DTGS
Resolution: 4 cm ^-1
Cumulative number of times: 128 times IRE: Ge
Incident angle: 45 degrees Attachment: One-time reflection ATR attachment (thunder dome).

The peak intensity derived from the (B) compound in the obtained FT-IR spectrum was determined, and normalized by the peak intensity of the C=O stretching vibration of the amide bond, and the value is the concentration V of the (B) compound on the surface of the molded article. And

In addition, the cross section of the bar-shaped test piece after the heat treatment was cut in the depth direction with a band saw and mirror-finished with a diamond cutter, and a microscope of a Fourier transform infrared spectrophotometer (Spot-light manufactured by Perkin Elmer Co., Ltd.) was used. Using the infrared ATR method, the concentration of the compound (B) in the polyamide resin composition at each arbitrary depth was measured while scanning in the depth direction from the surface of the rod-shaped test piece under the following conditions.
Light source: Special ceramics Detector: MCT
Resolution: 4 cm ^-1
Number of integration: 128 times/point Measurement mode: ATR method Measurement area per point: 80 μm×80 μm.

The peak intensity derived from the (B) compound was obtained from the obtained FT-IR spectrum at each depth, and normalized by the peak intensity of the C=O stretching vibration of the amide bond to obtain (B) at each depth. The concentration of compound was calculated. The concentration ratio of the (B) compound was obtained by dividing the concentration V of the (B) compound by the concentration W of the (B) compound at a depth of 0.28 mm from the surface of the molded product.

As an example, the FT-IR spectrum of the surface of the molded product after heat-treating the bar-shaped test piece (molded product) having a thickness of 6.4 mm obtained in Example 3 at 150° C. for 1000 hours in the atmosphere is shown in FIG. Shown in. The FT-IR spectrum of the cross section of the molded product in the depth direction is shown in FIG. From the spectra of FIG. 1 and FIG. 2, the peak intensity of the C—O stretching vibration of the aliphatic ether group of the compound (B) near 1005 cm ^{−1 is} the peak intensity of the C═O stretching vibration of the amide bond near 1632 cm ^−1. The value standardized by was calculated. FIG. 4 shows a plot of the normalized peak intensity with respect to the distance from the surface of the molded product. From FIG. 4, the peak intensity on the surface of the molded product was divided by the peak intensity at a depth of 0.28 mm from the surface of the molded product to calculate the concentration ratio (V/W) of the compound (B).

[Increase in carboxyl group concentration after heat treatment]
A 3.2 mm-thick ASTM No. 1 dumbbell test piece obtained in each Example and Comparative Example was fixed to the stage of a milling machine (Type: H-0-1) manufactured by Toyokuni Koki, and the scale was vertically operated. The ASTM No. 1 dumbbell test piece was moved up and down using an attached handle (1 scale: 0.02 mm) to cut the polyamide resin composition to a depth of 0.2 mm from the surface of the ASTM No. 1 dumbbell test piece. About 0.50 g of the cut polyamide resin composition was precisely weighed in a 50 ml Erlenmeyer flask, 20 ml of benzyl alcohol was added, and the mixture was dissolved using an aluminum block heater whose temperature was adjusted to 195°C. A phenolphthalein indicator was added to this solution, and the carboxyl group in the polyamide resin composition was calculated from the formula (8) using the amount of 0.02 mol/L ethanolic potassium hydroxide solution.
Carboxyl group concentration [mol/g]=((E−F)×f×0.001×0.02)/G (8)
(However, E: amount of 0.02 mol/L ethanolic potassium hydroxide solution used for titration [ml], F: amount of 0.02 mol/L ethanolic potassium hydroxide solution used for blank titration [ ml], f: factor of 0.02 mol/L ethanolic potassium hydroxide solution, G: mass of sample (excluding glass fiber) [g])

Then, the ASTM No. 1 dumbbell test piece obtained in each Example and Comparative Example was heat-treated at 130° C. for 100 hours in the atmosphere, and then the carboxyl group concentration of the surface layer was measured in the same manner. The amount of increase in concentration was calculated.

[Heat aging resistance]
A 3.2 mm-thick ASTM No. 1 dumbbell test piece obtained in each of the examples and comparative examples was tested according to ASTM D638 using a tensile tester Tensilon UTA2.5T (manufactured by Orientec Co., Ltd.) and a crosshead speed of 10 mm/min. The tensile test was performed under the conditions of and the tensile strength was measured. The measurement was performed 3 times, and the average value was calculated as the tensile strength before the heat aging resistance test treatment. Then, ASTM No. 1 dumbbell test piece is heat-treated at 135° C. in an atmospheric gear oven for 3000 hours, or 190° C. in an atmospheric gear oven for 2000 hours, or at 240° C. in an atmospheric gear oven for 2000 hours (heat aging). The test piece after the treatment was subjected to the same tensile test, and the average value of the three measured values of the tensile strength was calculated as the tensile strength after the heat aging resistance test treatment. The ratio (percentage) of the tensile strength after the treatment to the tensile strength before the heat aging resistance test treatment was calculated as the tensile strength retention rate. The higher the tensile strength retention rate, the better the heat aging resistance.

[Calcium chloride resistance]
The 80 mm×80 mm×3 mm thick square plate (film gate) obtained in each Example and Comparative Example was subjected to a moisture absorption treatment for 24 hours in a constant temperature and humidity bath adjusted to 60° C. and 95% RH, and then The cycle was repeated.
(1) Humidification treatment is carried out for 1 hour in a constant temperature and constant humidity tank adjusted to 85° C. and 95% RH.
(2) Gauze containing about 43% by weight of a saturated calcium chloride aqueous solution is applied to a square plate and heat-treated in the atmosphere at 100° C. for 1 hour.
(3) The gauze is removed, the square plate is left at room temperature for 1 hour, and the presence or absence of cracks is evaluated by visual observation of the surface.
(1) to (3) were defined as one cycle, and the number of cycles until cracks were generated was measured. The greater the number of cycles, the better the calcium chloride resistance.

[Surface appearance]
The 80 mm×80 mm×3 mm thick square plate (film gate) obtained in each Example and Comparative Example was heat-treated in the atmosphere at 150° C. for 5000 hours, and then the state of the square plate surface was visually observed, and the following criteria were used. evaluated.
A: No crack was observed on the surface of the molded product, and no bleeding was observed.
B: Cracks were observed on the surface of the molded product, and no bleeding was observed.
C: A crack is recognized on the surface of the molded product, and a bleeding product is also recognized.
In addition, the bleeding material refers to a material which is raised on the surface of a molded product, and is (b) a compound containing a hydroxyl group and/or an amino group, and (B) when the compound is solid at room temperature, it is like a dusting cloth, When the compound b) having a hydroxyl group and/or an amino group and the compound (B) are liquid at room temperature, they become viscous liquids.

[Hot water resistance]
The pellets obtained in Examples 2 to 3 and 14 to 15 were dried under reduced pressure at 80° C. for 12 hours, and an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) was used to obtain a cylinder temperature: (A). A No. 1 dumbbell ASTM 1 test piece having a thickness of 3.2 mm was prepared by injection molding under the conditions of the polyamide resin melting point +15°C and the mold temperature: 80°C. A tensile test was performed on this test piece with a tensile tester Tensilon UTA2.5T (manufactured by Orientec Co., Ltd.) at a crosshead speed of 10 mm/min according to ASTM D638. The measurement was performed 3 times, and the average value was calculated as the tensile strength before the hot water resistance test treatment. Next, the ASTM No. 1 dumbbell test piece was placed in a pressure-resistant autoclave, ion-exchanged water was added so that the test piece was sufficiently immersed, and the pressure-resistant autoclave was placed in a gear oven at 90°C for 6 hours to undergo a hot water resistance test treatment, and a test after treatment. The pieces were dried under reduced pressure at 80° C. for 12 hours. A similar tensile test was performed on the dried test piece, and the average value of three measurements was calculated as the tensile strength after the hot water resistance test treatment. The ratio (percentage) of the tensile strength after the hot water resistance test treatment to the tensile strength before the hot water resistance test treatment was calculated as the tensile strength retention rate. The higher the tensile strength retention rate, the better the hot water resistance.

[Moisture and heat resistance]
Pellets obtained in Examples 10 to 12, 14, and 16 and Comparative Examples 3 to 5 were dried under reduced pressure at 80° C. for 12 hours, and an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) was used. Cylinder temperature: (A) melting point of polyamide resin +15°C, mold temperature: 80°C, injection/cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 100 MPa, injection speed: 100 mm/second A 80 mm×80 mm×3 mm square plate (film gate) was injection molded. The obtained square plate was subjected to wet heat treatment at 80° C. and 95% RH for 1 hour, the state of the square plate surface after the treatment was visually observed, and evaluated according to the following criteria.
A: No bleeding is observed on the surface of the molded product.
B: Bleeds are recognized on the surface of the molded product.
The bleeding material is as described in the above [Surface appearance].

Reference Example 1 ((A-2) Nylon 10T)
An excess of 10T salt, which is an equimolar salt of decamethylenediamine and terephthalic acid, and 0.5 mol% of decamethylenediamine based on the total amount of decamethylenediamine were added. Further, 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials in total. This was placed in a pressure vessel, sealed, and purged with nitrogen. After heating was started and the internal pressure of the can reached 2.0 MPa, the internal pressure of the can was 2.0 MPa and the internal temperature of 240° C. was maintained for 2 hours while releasing water out of the system. Then, the content was discharged from the reaction container onto a cooling belt, and this was vacuum dried at 100° C. for 24 hours to obtain a polyamide resin oligomer. The obtained polyamide resin oligomer was pulverized, dried, and solid-phase polymerized at 50 Pa and 240° C. to obtain nylon 10T having ηr=2.48 and a melting point of 318° C.

Reference Example 2 ((A-4) Nylon 4T/6T=40/60 (weight ratio))
A 4T salt, which is an equimolar salt of tetramethylenediamine and terephthalic acid, and a 6T salt, which is an equimolar salt of hexamethylenediamine and terephthalic acid, were mixed in a weight ratio of 40:60. 0.5 mol% of tetramethylenediamine and hexamethylenediamine were added in excess with respect to the total aliphatic diamine. Further, 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials in total. This was placed in a polymerization vessel, sealed, and purged with nitrogen. After heating was started and the internal pressure of the can reached 2.0 MPa, the internal pressure of the can was 2.0 MPa and the internal temperature of 240° C. was maintained for 2 hours while releasing water out of the system. Then, the contents were discharged from the polymerization can onto a cooling belt, and this was vacuum dried at 100° C. for 24 hours to obtain a polyamide resin oligomer. The obtained polyamide resin oligomer was pulverized, dried, and solid-phase polymerized at 50 Pa and 240° C. to obtain nylon 4T/6T=40/60 having ηr=2.48 and a melting point of 336° C.

Reference Example 3 (B-1)
To 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) and the average number of epoxy groups in one molecule After premixing 7 parts, molecular weight 1330, molecular weight/functional group number in one molecule=190) 10 parts by weight, using a PCM30 type twin screw extruder manufactured by Ikegai, at a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm. The mixture was melt-kneaded for 3.5 minutes and pelletized with a hot cutter. The pellets thus obtained were again fed to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 53%, the degree of branching was 0.29, and the hydroxyl value was 1280 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 4 (B-2)
A compound represented by the general formula (1) and/or its compound was prepared in the same manner as in Reference Example 3 except that the screw rotation speed of the twin-screw extruder was changed to 300 rpm and the melt-kneading time was changed to 0.9 minutes. A condensate pellet was obtained. The reaction rate of the obtained compound was 2%, the degree of branching was 0.15, and the hydroxyl value was 1350 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH and OR in the general formula (1) was 3 or more.

Reference example 5 (B-3)
To 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), 10 parts by weight of phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), 1,8-diazabicyclo After premixing 0.3 part by weight of (5,4,0)-undecene-7 (manufactured by Tokyo Chemical Industry Co., Ltd.), a cylinder temperature of 200° C. was obtained using a PCM30 twin screw extruder manufactured by Ikegai Corporation. Then, the mixture was melt-kneaded for 3.5 minutes under the condition that the screw rotation speed was 100 rpm, and pelletized by a hot cutter. The obtained pellets were fed to an extruder, and the remelting and kneading step was further performed 6 times to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 96%, the degree of branching was 0.39, and the hydroxyl value was 1170 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 6 (B-4)
Aliphatic polycarbodiimide (“Carbodilite” (registered trademark) LA-1, manufactured by Nisshinbo Chemical Co., Ltd.) per 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), and the average number of carbodiimide groups in one molecule After premixing 24 parts, molecular weight 6000, molecular weight/functional group number in one molecule=250) 10 parts by weight, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., cylinder temperature 200° C., screw rotation speed 100 rpm The mixture was melt-kneaded for 3.5 minutes under the above conditions and pelletized with a hot cutter. The pellets thus obtained were again fed to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 89%, the degree of branching was 0.37, and the hydroxyl value was 1110 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of carbodiimide groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 7 (B-5)
In a 1 L capacity autoclave equipped with a stirrer, 508 g (1.0 mol) of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), 254 g of toluene and 0.3 g of potassium hydroxide were charged and heated to 90°C. The mixture was stirred to obtain a slurry liquid. Then, the mixture was heated to 130° C., and 132 g (3 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. The temperature inside the autoclave increased with the introduction of ethylene oxide. Cooling was added at any time to keep the reaction temperature at 140°C or lower. After the reaction, the pressure was reduced to 1.3 kPa or less at 140° C. to remove excess ethylene oxide and a by-produced polymer of ethylene glycol. Then, it was neutralized with acetic acid and adjusted to pH 6 to 7 to obtain ethylene glycol-modified dipentaerythritol.

343 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol was weighed in an electromagnetic induction rotary stirring autoclave with an internal volume of 500 ml, and 3 g of an external reduction-treated 5% ruthenium-alumina powder catalyst manufactured by NE Chemcat was charged, and nitrogen substitution was performed. I went. Subsequently, 26 g (1.53 mol) of ammonia was added, and hydrogen (0.18 mol) was injected under pressure so that the total pressure became 2.0 MPaG at room temperature (25° C.). While stirring under the conditions of 1000 rpm, the reaction temperature was heated to 220°C. The initial maximum pressure at 220° C. was 9.8 MPaG. The pressure dropped from 9.8 MPaG to 8.4 MPaG in 4 hours. After confirming that there was no pressure drop, the reaction was continued for 0.5 hour. Then, the reaction product was cooled, taken out, filtered to remove the catalyst, and dipentaerythritol polyoxyethylene hexamine was obtained.

After preliminarily mixing 10 parts by weight of a phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) with 100 parts by weight of the obtained dipentaerythritol polyoxyethylene hexamine, ) Using a PCM30 type twin-screw extruder manufactured by Ikegai, melt-kneading for 3.5 minutes under the conditions of a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm, and pelletizing with a hot cutter, / Or pellets of the condensate thereof were obtained. The reaction rate of the obtained compound was 49%, the degree of branching was 0.25, and the amine value was 500 mgKOH/g. The number of amino groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 8 (B-6)
After preliminarily mixing 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.) with 500 parts by weight of a phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), A PCM30 type twin-screw extruder manufactured by Ikegai Co., Ltd. is used to melt-knead for 3.5 minutes under the conditions of a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm, and pelletized by a hot cutter, which is represented by the general formula (1). A pellet of the compound and/or its condensate was obtained. The reaction rate of the obtained compound was 33%, the degree of branching was 0.23, and the hydroxyl value was 540 mgKOH/g. The number of hydroxyl groups in one molecule was smaller than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 9 (B-7)
To 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A type epoxy resin (“jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Co., Ltd.) and the number of epoxy groups in one molecule is 2 , Molecular weight 1650, molecular weight/functional group number in one molecule=825) 33.3 parts by weight are premixed, and then using a PCM30 type twin screw extruder manufactured by Ikegai, at a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm. The mixture was melt-kneaded for 3.5 minutes and pelletized with a hot cutter. The pellets thus obtained were again fed to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 56%, the degree of branching was 0.34, and the hydroxyl value was 1200 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 10 (B-8)
To 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A type epoxy resin ("jER" (registered trademark) 1007 manufactured by Mitsubishi Chemical Co., Ltd., and the number of epoxy groups in one molecule is 2) , 3900 parts by weight, molecular weight 2900, number of functional groups in one molecule=1450) were premixed, and then using a PCM30 type twin-screw extruder manufactured by Ikegai Co., Ltd., a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm. The mixture was melt-kneaded for 3.5 minutes under the above conditions and pelletized with a hot cutter. The pellets thus obtained were again fed to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 52%, the degree of branching was 0.32, and the hydroxyl value was 1160 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 11 (B-9)
To 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A type epoxy resin ("jER" (registered trademark) 1010 manufactured by Mitsubishi Chemical Co., Ltd., the number of epoxy groups in one molecule is 2) , Molecular weight 5500, molecular weight/number of functional groups per molecule=2750) 33.3 parts by weight were premixed, and then using a PCM30 type twin-screw extruder manufactured by Ikegai Co., Ltd., a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm. The mixture was melt-kneaded for 3.5 minutes under the above conditions and pelletized with a hot cutter. The pellets thus obtained were again fed to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 50%, the degree of branching was 0.29, and the hydroxyl value was 1100 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 12 (B-10)
100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., 2 epoxy groups in one molecule, molecular weight 340, molecular weight/1) After premixing 33.3 parts by weight of the functional group number in the molecule=170), a PCM30 twin screw extruder manufactured by Ikegai Co., Ltd. was used for 3.5 minutes under the conditions of a cylinder temperature of 200° C. and a screw rotation speed of 100 rpm. The mixture was melt-kneaded and pelletized with a hot cutter. The pellets thus obtained were again fed to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and/or its condensate. The reaction rate of the obtained compound was 88%, the degree of branching was 0.32, and the hydroxyl value was 1290 mgKOH/g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 13 (Nylon 66 masterbatch containing C-1:CuI/KI (weight ratio)=0.23)
2.0 parts by weight of copper iodide and 21.7 parts by weight of 40% potassium iodide aqueous solution were premixed with 100 parts by weight of nylon 66 ("Amilan" CM3001-N manufactured by Toray Industries, Inc.). Then, using a TEX30 type twin-screw extruder (L/D: 45.5) manufactured by Japan Steel Works, Ltd., the mixture was melt-kneaded under the conditions of a cylinder temperature of 275° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. .. Then, it was vacuum dried at 80° C. for 8 hours to prepare masterbatch pellets having a copper content of 0.60% by weight.

Reference Example 14 (E-1)
26.7 parts by weight of the (B-1) compound was premixed with 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), and then TEX30 type manufactured by Japan Steel Works, Ltd. Using a twin-screw extruder (L/D: 45.5), the mixture was melt-kneaded under the conditions of a cylinder temperature of 245° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. Then, it was vacuum dried at 80° C. for 8 hours to prepare high-concentration premixed pellets.

Reference Example 15 (E-2)
After pre-mixing 26.7 parts by weight of the (B-8) compound with 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), TEX30 type manufactured by Japan Steel Works, Ltd. Using a twin-screw extruder (L/D: 45.5), the mixture was melt-kneaded under the conditions of a cylinder temperature of 245° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. Then, it was vacuum dried at 80° C. for 8 hours to prepare high-concentration premixed pellets.

In addition, the (A) polyamide resin, (b) hydroxyl group and/or amino group-containing compound, (b') epoxy group and/or carbodiimide group-containing compound, and (D) filler used in this example and comparative example are as follows. Is the street.
(A-1): Nylon 66 resin (“Amilan” (registered trademark) CM3001-N manufactured by Toray Industries, Inc.) having a melting point of 260° C., ηr=2.78.
(A-3): Nylon 6 resin having a melting point of 225° C. (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), ηr=2.70.
(A-5): Nylon 12 resin having a melting point of 176° C. (“UBESTA” (registered trademark) 3024B manufactured by Ube Industries, Ltd.), ηr=2.50.
(B-1): Dipentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 254, hydroxyl value 1325 mg KOH/g, number of hydroxyl groups 6 in one molecule 6.
(B-2): dipentaerythritol polyoxyethylene hexamine, molecular weight 608, amine value 554 mgKOH/g.
(B'-1): Phenolic novolac type epoxy resin ("EPPN" (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), the average number of epoxy groups in one molecule is 7, molecular weight 1330, molecular weight/1 molecule 190 functional groups.
(D-1): Glass fiber with circular cross section (T-275H manufactured by Nippon Electric Glass Co., Ltd.), cross section diameter of 10.5 μm, surface treatment agent: silane coupling agent, binding agent: carboxylic acid type, fiber length 3 mm ..
(D-2): Glass fiber having a circular cross section (T-717H manufactured by Nippon Electric Glass Co., Ltd.), cross section diameter of 10.5 μm, surface treatment agent: silane coupling agent, binding agent: epoxy type, fiber length 3 mm.

(Examples 1 to 4 , 7 , 8 , 10 to 19 , Comparative Examples 1 to 12 )
For the (A) polyamide resin, (b') epoxy group and/or carbodiimide group-containing compound, and (C) copper compound shown in the table, the cylinder set temperature was set to the melting point of the polyamide resin +15°C, and the screw rotation speed was set to 200 rpm ( It was supplied to the twin-screw extruder from the main feeder of TEX30 type twin-screw extruder (L/D=45) manufactured by Japan Steel Works, Ltd., and melt-kneaded. This main feeder was connected to the position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, the position of the upstream end of the screw segment. Then, (B) compound, (b) hydroxyl group and/or amino group-containing compound, (D) filler, and (E) high-concentration premix shown in the table are fed from a side feeder to a twin-screw extruder and melt-kneaded. did. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The screw configuration of the twin-screw extruder is such that (B) the total length of the kneading zone upstream of the supply position of the compound or the like is Ln1, and the total length of the kneading zone downstream of the supply position of the (B) compound or the like. When the length is Ln2, Ln1/L is 0.14 and Ln2/L is 0.07. Further, among the resin pressures indicated by the resin pressure gauges installed in a plurality of full flight zones, the minimum resin pressure Pfmin and the resin pressure indicated by the resin pressure gauges installed in a plurality of kneading zones The difference from the maximum resin pressure Pkmax (Pkmax-Pfmin) was as shown in the table. The gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter.

The obtained pellets were dried under reduced pressure at 80° C. (135° C. in Examples 17 and 19) for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A). Polyamide resin melting point +15° C., mold temperature: 80° C. (140° C. in Example 17 and 160° C. in Example 19), a rod-shaped test piece having a thickness of 6.4 mm, and an ASTM No. 1 having a thickness of 3.2 mm. A dumbbell test piece and a square plate (film gate) having a thickness of 80 mm×80 mm×3 mm were respectively injection-molded to obtain various test pieces (molded products).

The evaluation results of each example and comparative example are shown in Tables 1 to 3. The tensile strength retention rates before and after the hot water resistance test treatment are Example 2:80%, Example 3:94%, Example 14:86%, and Example 15:108%. , Example 10:B, Example 11:A, Example 12:A, Example 14:B, Example 16:A, Comparative Example 3:B, Comparative Example 4:B, Comparative Example 5:B. It was

In Examples 1 to 4, 7, 8, 10 to 19 as compared with Comparative Examples 1 to 12 , the peak strength ratio of the carboxyl groups of the molded product having a thickness of 6.4 mm was 5.0 or less, so that heat aging was performed. It was possible to obtain a molded product having excellent properties, calcium chloride resistance and surface appearance.

In Examples 2 and 7, the reaction rate of the (B) compound was in a preferable range as compared with Comparative Examples 10 and 11 , so that the compatibility between the (A) polyamide resin and the (B) compound was improved, and heat resistance was improved. It was possible to obtain a molded product having excellent aging resistance and calcium chloride resistance.

In Example 2, compared with Comparative Example 12 , the number of hydroxyl groups in one molecule of the (B) compound is greater than the number of epoxy groups, and thus a molded article having better heat aging resistance and calcium chloride resistance is obtained. I was able to.

In comparison with Example 2, Example 13 uses the (C) copper compound, so that the compatibility between the (A) polyamide resin and the (B) compound is improved, and the heat aging resistance and calcium chloride resistance are superior. A molded product could be obtained.

Example 14 was compared with Example 2, Example 15 was compared with Example 3, and Example 16 was compared with Example 11 because a high-concentration premix was prepared and melt-kneaded twice. The compatibility between the polyamide resin (A) and the compound (B) was further improved, and as a result, a molded product having excellent heat aging resistance and calcium chloride resistance could be obtained.

In Examples 2 and 17, the melting point of the (A) polyamide resin was in a preferable range as compared with Examples 18 and 19, so that the compatibility between the (A) polyamide resin and the (B) compound was further improved, As a result, it was possible to obtain a molded product having excellent heat aging resistance and calcium chloride resistance.

Compared with Example 2, Example 3 contained glass fibers of the epoxy-based sizing agent in Example 15 compared with Example 14, so that a molded article having excellent hot water resistance could be obtained.

The molecular weight and the value obtained by dividing the molecular weight by the number of functional groups in one molecule are in preferred ranges in Examples 11 and 12 as compared with Example 10 and in Example 16 as compared with Example 14. Since the compound (B') contains the compound (B) obtained by reacting the epoxy group- and/or carbodiimide group-containing compound, a molded product having more excellent heat and humidity resistance could be obtained.

The molded article of the embodiment of the present invention takes advantage of its excellent heat aging resistance, calcium chloride resistance, and surface appearance, and is used for automobile engine peripheral parts, automobile underhood parts, automobile gear parts, automobile interior parts, automobile exterior parts, and absorbent parts. It is preferably used for automobile applications such as exhaust system parts, engine cooling water system parts, automobile electrical components, and electric/electronic parts such as LED reflectors and SMT connectors.

1 solvent peak

Claims (7)

A molded product having a thickness of 0.56 mm or more obtained by molding a polyamide resin composition, which is obtained by Fourier transform infrared spectroscopy after heat treatment at 150° C. for 1000 hours in the air, and carboxyl on the surface of the molded product. and the peak intensity Y groups, the ratio of the peak intensity Z of the carboxyl group (Y / Z) of 5.0 I der less at a depth of 0.28mm from the surface of the molded article,
The polyamide resin composition has (B) a hydroxyl group and/or an amino group and an epoxy group and/or a carbodiimide group with respect to 100 parts by weight of the (A) polyamide resin, and has a hydroxyl group and an amino group in one molecule. 0.1 to 20 parts by weight of a compound in which the sum of the numbers of the above is larger than the sum of the numbers of the epoxy groups and the carbodiimide groups in one molecule, and the (B) compound is the (b) hydroxyl group and / Alternatively, it is a reaction product of an amino group-containing compound and (b′) an epoxy group and/or a carbodiimide group-containing compound, and the reaction rate of a hydroxyl group or an amino group with an epoxy group or a carbodiimide group is 10 to 90%, A molded article in which the molecular weight of the compound (b') containing an epoxy group and/or a carbodiimide group is 800 or more and 10000 or less . When heat-treated at 150° C. for 1000 hours in the air, the concentration V of the compound (B) in the polyamide resin composition on the surface of the molded product obtained by Fourier transform infrared spectroscopy and the depth of 0.28 mm from the surface of the molded product. claim 1 molded article according the ratio of the concentration W of the compound (B) of the polyamide resin composition (V / W) is 1.2 to 5.0 in of. The molded article according to claim 1 or 2, wherein the compound (B) is a compound having a structure represented by the following general formula (1) and/or a condensate thereof.

In the above general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH _2, and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0-20. An increase in the concentration of carboxyl groups in the polyamide resin composition at a depth of up to 0.2 mm from the surface of the molded product is 4×10 ⁻⁵ mol/g or less when heat-treated at 130° C. for 100 hours in the air. The molded product according to any one of 1 to 3 . Based on 100 parts by weight of (A) polyamide resin, (B) has a hydroxyl group and/or an amino group and an epoxy group and/or a carbodiimide group, and the sum of the number of hydroxyl groups and amino groups in one molecule is 1 Ri Na blended more compounds from 0.1 to 20 parts by weight than the sum of the number of epoxy groups and carbodiimide groups in the molecule, (B) the compound, and (b) a hydroxyl and / or amino group-containing compound, (B') a reaction product with an epoxy group and/or carbodiimide group-containing compound, the reaction rate of a hydroxyl group or amino group with an epoxy group or carbodiimide group is 10 to 90%, and (b') epoxy A rod-shaped test piece having a thickness of 6.4 mm obtained by injection-molding a polyamide resin composition, which is a polyamide resin composition having a molecular weight of a group and/or carbodiimide group-containing compound of 800 or more and 10000 or less . After heat treatment at 150° C. for 1000 hours, peak intensity Y of the carboxyl group on the surface of the rod-shaped test piece obtained by Fourier transform infrared spectroscopy and peak intensity Z of the carboxyl group at a depth of 0.28 mm from the surface of the rod-shaped test piece. A polyamide resin composition having a ratio (Y/Z) of 5.0 or less. When the rod-shaped test piece was heat-treated at 150° C. for 1000 hours in the atmosphere, the concentration V of the (B) compound in the polyamide resin composition on the surface of the rod-shaped test piece obtained by Fourier transform infrared spectroscopy and the bar-shaped test piece The polyamide resin composition according to claim 5 , wherein the ratio (V/W) with the concentration W of the (B) compound in the polyamide resin composition at a depth of 0.28 mm from the surface is 1.2 to 5.0. (B) Hydroxyl group- and/or amino group-containing compound and (b') epoxy group- and/or carbodiimide group-containing compound having a molecular weight of 800 or more and 1000 or less were previously reacted at a reaction rate of 10 to 90% to prepare (B). The method for producing a polyamide resin composition according to claim 5 or 6, wherein the compound is melt-kneaded with the polyamide resin (A).

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