WO2016104455A1

WO2016104455A1 - Polyamide resin composition, and polyamide resin molded article

Info

Publication number: WO2016104455A1
Application number: PCT/JP2015/085726
Authority: WO
Inventors: 福田　誠; 上平　茂生; 倫弘小川
Original assignee: 富士フイルム株式会社
Priority date: 2014-12-26
Filing date: 2015-12-21
Publication date: 2016-06-30
Also published as: JPWO2016104455A1

Abstract

Provided are a polyamide resin composition and a molded article thereof, the polyamide resin composition comprising polyamide and at least one linear imino ether group-containing compound selected from imino ether compounds represent by formula (1) and multimers thereof. R² represents an alkyl group, an aryl group, or an alkoxy group, R³ represents an alkyl group or an aryl group represented by formula (2) or (3), and R¹¹-R¹³ each independently represents a hydrogen atom, an alkyl group, or an aryl group. R³¹-R³³ each independently represents a hydrogen atom or a substituent group, and can be connected to form a ring. R⁴¹ represents a substituent group, n represents an integer of 0-5, and when a plurality of R⁴¹ is present, the plurality of R⁴¹ can be the same or different. * represents a bonding position with a nitrogen atom.

Description

Polyamide resin composition and polyamide resin molded article

The present disclosure relates to a polyamide resin composition and a polyamide resin molded article.

Various resin moldings are used in various fields such as machine parts, electronic parts, construction materials, films and the like. Although resin and an additive are selected according to a use, these resin moldings are known that the resin synthesize | combined using carboxylic acid will deteriorate by hydrolysis.
For example, polyamides are stable in alkaline media but neutral or susceptible to hydrolysis in the presence of acids.
In addition, for example, polyesters such as polyethylene terephthalate (PET) used as bottles for beverages and protective sheets for solar cells are also degraded by hydrolysis.

In order to inhibit the hydrolysis of the resin synthesized using these carboxylic acids, an end capping agent (hereinafter sometimes referred to as a "sealing agent") that seals (deactivates) the terminal carboxy group is used. Be done.
For example, in JP-A-6-16933, in order to provide a polyamide having hydrolysis resistance in an acidic medium, it is proposed to add 0.1 to 5% by mass of polycarbodiimide as a sealing agent to polyamide. It is done.

Also, for example, in JP-A-2010-031174, it is proposed to improve hydrolysis resistance by adding a cyclic iminoether compound such as oxazoline as a sealing agent to polyester such as polyethylene terephthalate (PET). ing.

However, when a resin molded product is produced using a polyamide resin composition containing a carbodiimide compound as disclosed in JP-A-6-16933 as a terminal blocking agent, the isocyanate gas volatilizes during molding.
In addition, when producing a resin molded product using a cyclic iminoether compound represented by oxazoline as described in JP-A-2010-031174 as a sealing agent, polyoxazoline has low reactivity and molding Sometimes it is a problem that the resin thickens. On the other hand, low molecular weight oxazolines have problems with gas vaporization and thickening.

The present invention has been made in view of the above circumstances, and is a polyamide resin capable of suppressing generation of volatile gas and thickening during molding and producing a resin molded product having hydrolysis resistance. It is intended to provide a composition.
Another object of the present invention is to provide a polyamide resin molded product which is resistant to hydrolysis and which can be produced by suppressing the generation of volatile gas and thickening.

In order to achieve the above object, the following invention is provided.

<1> A polyamide and at least one chained iminoether group-containing compound selected from an iminoether compound represented by the following general formula (1) and a multimer of the iminoether compound represented by the general formula (1) And a polyamide resin composition.

In the general formula (1), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ³ represents R ¹¹ represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3), and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.

In formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. R ³¹ , R ³² and R ³³ may be linked to each other to form a ring. In Formula (3), R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. In the general formulas (2) and (3), * represents a position to be bonded to a nitrogen atom.

<2> is an aryl group R ³ is represented by the general formula (3) in the general formula (1) Polyamide resin composition according to <1>.

The polyamide resin composition as described in <1> or <2> whose iminoether compound represented by <3> General formula (1) is a chain-like iminoether group containing compound represented by following General formula (5) .

In formula (5), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ²¹ represents a substituent, m represents an integer of 0 to 5, when R ²¹ there are a plurality, even more R ²¹ is the same as each other or different, a ring together You may form. R ⁴¹ represents a substituent, n represents an integer of 0 to 5, when R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, a ring together You may form.
<4> Any one of <1> to <3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (6) The polyamide resin composition as described in 1).

In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L ¹ has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety.
<5> Any one of <1> to <3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (7) The polyamide resin composition as described in 1).

In the general formula (7), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ¹¹ and R ¹² And R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. p represents an integer of 2 to 4, and p represents a p-valent group in which L ² is a arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent. Represents

<6> Any one of <1> to <3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (8) The polyamide resin composition as described in 1).

In general formula (8), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ⁴¹ represents a substituent And n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L ³ represents a p-valent group in which the bonding end with the oxygen atom is an alkylene part. In the alkylene moiety of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.

The polyamide resin composition according to any one of <1> to <6>, which comprises 0.1 to 2.0 parts by mass of a chain iminoether group-containing compound with respect to 100 parts by mass of the <7> polyamide.
The polyamide resin molded object shape | molded using the polyamide resin composition as described in any one of <8><1>-<7>.

According to the present invention, there is provided a resin composition capable of suppressing generation of a volatilized gas at the time of molding and thickening and capable of producing a polyamide resin molded product having hydrolysis resistance.
Further, according to the present invention, there is provided a polyamide resin molded article which is resistant to hydrolysis and which can be produced while suppressing the generation of volatile gas and thickening.

Hereinafter, the polyamide resin composition and the polyamide resin molded article of the present disclosure will be specifically described. In the following description, “to” representing a numerical range means a range including numerical values described as the lower limit value and the upper limit value.

<Polyamide resin composition>
The polyamide resin composition of the present disclosure comprises at least one chain selected from a polyamide, an iminoether compound represented by the following general formula (1), and a multimer of an iminoether compound represented by the general formula (1) And an iminoether group-containing compound (hereinafter sometimes simply referred to as a "chain iminoether group-containing compound").

In addition, as for the "chain iminoether group-containing compound" in the present disclosure, the entire iminoether group (sometimes referred to as -N = C-O- or "iminoether moiety") contained in the iminoether compound has a cyclic structure. Iminoether compounds which are not incorporated into at least a portion of which constitute at least a part of the chain portion of the iminoether compound. In addition, with the multimer of the iminoether compound represented by the general formula (1), at least one partial structure linked to the chain iminoether group (-N = C-O-) in the general formula (1) is linked A chain iminoether group-containing compound synthesized via an iminoether compound represented by the general formula (1), which means a chain iminoether group-containing compound which has two or more partial structures other than a linking group In addition, a chain iminoether group-containing compound synthesized without passing through the iminoether compound represented by the general formula (1) is also included.

By using the polyamide resin composition of the present disclosure, it is possible to suppress the generation and thickening of the volatilized gas derived from the sealing agent, and to produce a polyamide resin molded article having hydrolysis resistance. The reason is presumed as follows.

An iminoether compound represented by the general formula (1) or an iminoether compound represented by the general formula (1) in which an iminoether group (-N = C-O-) is in a chain form (non-cyclic) When a resin composition containing an ether group-containing compound and a polyamide is heat-melted and molded as in the following reaction scheme, a chain iminoether portion and a terminal carboxy group of polyamide (waveline is a portion other than the terminal carboxy group of polyamide) An amide compound and a carboxylic acid ester are formed by reaction with (1) and the alkyl moiety linked to the iminoether group is cleaved and esterified and added to the carboxy group at the end of the polyamide.

Accordingly, no isocyanate gas is generated which is generated when molding is performed using a carbodiimide compound as a sealing agent, and an increase in molecular weight of polyamide is suppressed, so that thickening at the time of molding is suppressed. In addition, the iminoether compound represented by the general formula (1) reacts with the carboxy group of the polyamide terminal or the carboxy group of a low molecular weight component such as a monomer as described in the above scheme to deactivate the carboxy group. Hydrolyzability is improved.

On the other hand, when the iminoether moiety containing an iminoether group is cyclic, it is considered that the polyamide is added to the iminoether moiety, and the viscosity is increased by increasing the molecular weight of the polymer. In particular, in the case where the cyclic iminoether moiety is bifunctional or more (dimer or more), it is considered that a large number of polyamides are added to cause significant thickening.

(Synthesis method of imino ether compound)
As a method of synthesizing the iminoether compound represented by the general formula (1), a method in which an amide compound is imidoyl chloride, reaction with an alkoxide, and a method in which an aniline compound and an ortho ester compound are reacted. Although any method may be used as a synthesis method of the iminoether compound represented by General formula (1), it is preferable to use the method of making an aniline compound and an ortho ester compound react. A polyamide resin composition to which an iminoether compound synthesized by a method of reacting an aniline compound and an ortho ester compound is added is preferable because hydrolysis resistance and color tone become better. It is considered that this is attributed to the absence of the coloring matter and the reagent and reaction product which deteriorate the hydrolysis resistance in the method of reacting the aniline compound with the ortho ester compound. Moreover, the method of reacting an aniline compound and an ortho ester compound is preferable also from the point which can synthesize | combine an imino ether compound by a short process.

The ortho ester compound used for the synthesis of the iminoether compound represented by the general formula (1) is preferably a compound represented by the following general formula (9).

In the general formula (9), R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, R ⁵¹ and R ⁵² And R ⁵³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

Examples of ortho ester compounds used for the synthesis of iminoether compounds represented by the general formula (1) include trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, Triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tributyl orthopropionate, trimethyl orthobenzoate, trimethyl orthobenzoate And triethyl orthobenzoate, tributyl orthobenzoate, and tribenzyl orthobenzoate.

The ortho ester compound may be a commercially available product or may be synthesized. In the case of synthesis, it can be synthesized by imidating a nitrile compound such as hydrogen cyanide, acetonitrile, propionitrile, n-butyronitrile, benzonitrile or the like and reacting with an alcohol or a method of reacting trichlorobenzene with an alkoxide.

(polyamide)
The polyamide used in the present disclosure is not particularly limited and includes aliphatic polyamides and aromatic polyamides.

Aliphatic polyamides that can be used in the present disclosure include, for example, nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 666, nylon 610, nylon 612, and the like.

Commercially available aliphatic polyamides can also be used in the present disclosure. For example, Unitika Co., Ltd. product A1030 BRL (nylon 6), Toray Industries, Inc. amilan (registered trademark) CM1017 (nylon 6), CM 2001 (nylon 610), CM 3007 (nylon 66), DMS Japan ENPLA Co., Ltd. TW341 (product name) Nylon 46), manufactured by Daicel Eponik KK, Vestamide (registered trademark) D16 (nylon 612), manufactured by Arkema Corporation, Rilsan (registered trademark) B BMN O TLD (nylon 12), Rilsan (registered trademark) A BMN BK TLD (nylon 11), Ube Industries, Ltd., UBE nylon (registered trademark) 2020B (nylon 66), UBE nylon (registered trademark) 5013 B (nylon 666), UBESTA (registered trademark) 3014 B (nylon 12), etc. It can be mentioned.

These aliphatic polyamides may be used alone or in combination of two or more.

As the aromatic polyamide which can be used in the present disclosure, for example, an aromatic polyamide which is polymerized by dehydration condensation of a diamine and a dicarboxylic acid and in which an aromatic compound is used as either a diamine or a dicarboxylic acid it can.
Aliphatic diamines, alicyclic diamines, aromatic diamines and the like can be used as diamines, and diamines represented by the following general formula (A) can be used as aliphatic diamines or alicyclic diamines. R ₁ in the following formula represents an aliphatic or alicyclic alkylene group represented by C _n H _2n (n = 6 to 12).
H ₂ N-R ₁ -NH ₂ (A)
As the diamine represented by the general formula (A), it is particularly preferable to use hexamethylenediamine and 2-methylpentamethylenediamine in that they can exhibit excellent properties even at high temperatures.

As the aromatic diamine, xylylene diamine, metaxylylene diamine and the like can be used.

As the dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and the like can be used, and as aliphatic dicarboxylic acid or alicyclic dicarboxylic acid, it is represented by the following general formula (B) Dicarboxylic acid can be used. R ₂ in the following formula represents an aliphatic or alicyclic alkylene group represented by C _n H _2n (n = 4 to 25).
HOOC-R ₂ -COOH (B)

Adipic acid etc. can be used as aliphatic dicarboxylic acid.
As the aromatic dicarboxylic acid, terephthalic acid, methylterephthalic acid, naphthalene dicarboxylic acid, isophthalic acid and the like can be used.
As the aromatic dicarboxylic acid, it is particularly preferable to use terephthalic acid and isophthalic acid in that they can exhibit excellent properties even at high temperatures.

In the synthesis of the aromatic polyamide, these diamines and dicarboxylic acids may be used alone or in combination of two or more kinds. Furthermore, if necessary, components other than diamine and dicarboxylic acid may be contained.

As the aromatic polyamide used in the present disclosure, a condensation polymer of metaxylylenediamine and adipic acid or adipic acid halide is preferable.

Commercially available aromatic polyamides can also be used. For example, MX nylon S6001 (nylon MXD6) manufactured by Mitsubishi Gas Chemical Co., Ltd., Kuraray Co., Ltd., Genesta (registered trademark) N1000A (nylon 9T), etc. may be mentioned.

These aromatic polyamides may be used singly or in combination of two or more.

In addition, since the reactivity of an iminoether compound becomes high, so that the molding temperature of a resin composition is high, it is preferable to use polyamide with high melting | fusing point or glass transition temperature. Specifically, the melting point or glass transition temperature of the polyamide is preferably 200 ° C. or higher. On the other hand, if the molding temperature is too high, the unreacted iminoether compound or the generated carboxylic acid ester is easily volatilized, and therefore the melting point or glass transition temperature of the polyamide is preferably 300 ° C. or less.

The molecular weight of the polyamide used in the present disclosure is not particularly limited, but the weight average molecular weight is preferably in the range of 5 × 10 ³ to 10000 × 10 ³ , more preferably 10 × 10 ³ to 5000 × 10 ^3. Preferably, it is in the range of 30 × 10 ³ to 1000 × 10 ³ . In addition, the measurement of a weight average molecular weight can be performed using gel permeation chromatography (GPC). Specifically, chloroform / hexafluoroisopropanol = 9/1 (volume ratio) is used as a solvent, polystyrene gel is used, and weight average molecular weight using a conversion molecular weight calibration curve previously obtained from a constitution curve of standard monodispersed polystyrene You can ask for

In particular, nylon resins, which are aliphatic polyamides, generally have low hydrolysis resistance, but in the present disclosure, hydrolysis resistance is obtained by adding an iminoether compound represented by the general formula (1) or a multimer thereof. This is particularly effective when using a nylon-based resin because it can significantly improve the properties.

(Chain-like iminoether group-containing compound)
The chain iminoether group-containing compound used in the present disclosure is an iminoether compound represented by the following general formula (1) or a multimer of the iminoether compound represented by the general formula (1).

In the general formula (1), the alkyl group represented by R ² is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms of the alkyl group represented by R ^2, indicate the number of carbon that does not contain a substituent group. The alkyl group represented by R ² may be linear or branched. The alkyl group represented by R ² may be a cycloalkyl group. The alkyl group represented by R ² is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, n-pentyl, A sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, a cyclohexyl group and the like can be mentioned. The alkyl group represented by R ² is more preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group or a cyclohexyl group.
The alkyl group represented by R ² may further have a substituent. Examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amido group, hydroxyl group, ester group, ether group, aldehyde group and the like.

The aryl group represented by R ² is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Number of carbon atoms of the aryl group represented by R ^2, indicate the number of carbon that does not contain a substituent group. The aryl group represented by R ^2, a phenyl group, a naphthyl group can be exemplified a phenyl group is particularly preferred.
The aryl group represented by R ² may further have a substituent. As the substituent, the above-mentioned substituents, that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified. The substituent is not particularly limited as long as it does not interfere with the reaction of the iminoether group with the carboxy group.

The alkoxy group represented by R ² is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms Is particularly preferred. Number of carbon atoms of the alkoxy group represented by R ^2, indicate the number of carbon that does not contain a substituent group. The alkoxy group represented by R ² may be linear, branched or cyclic. Preferred examples of the alkoxy group represented by R ² may be a group at the end of the alkyl group represented by R ² -O- is linked.
The alkoxy group represented by R ² may further have a substituent. As the substituent, the above-mentioned substituents, that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified. The substituent is not particularly limited as long as it does not interfere with the reaction of the iminoether group with the carboxy group.

R ³ represents an alkyl group represented by the above general formula (2) or an aryl group represented by the above general formula (3). In formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. When R ³¹ , R ³² and R ³³ are substituents, the substituents represented by R ³¹ , R ³² and R ³³ may be linked to each other to form a ring. Examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amido group, hydroxyl group, ester group, ether group, aldehyde group and the like. R ³¹ , R ³² and R ³³ may all be hydrogen atoms or may be the same substituent, or may be different substituents.
The alkyl group represented by the general formula (2) may be linear or branched. The alkyl group represented by the general formula (2) may be a cycloalkyl group.
In Formula (3), R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of R ⁴¹ may be the same as or different from each other, and may be linked to each other to form a ring. As the substituent, the above-mentioned substituents, that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified. . n is more preferably 0 to 3, and still more preferably 0 to 2.

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. As the alkyl group and the aryl group, the alkyl group and the aryl group that can be taken by R ² can be similarly exemplified. R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring.

The polyamide resin composition of the present disclosure may contain, as a chain iminoether group-containing compound, a multimer of the iminoether compound represented by General Formula (1). For example, a chain iminoether group-containing compound containing as a repeating unit a structure excluding at least one of R ² , R ³ or R ¹¹ to R ^{13 in} the general formula (1) is preferable.

The iminoether compound represented by the general formula (1) is preferably represented by the following general formula (4) from the viewpoint of easiness of synthesis.

In General Formula (4), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ¹¹ and R ¹² And R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring.

In the general formula (4), R ² , R ¹¹ , R ¹² and R ¹³ have the same meaning as each other in the general formula (1), and preferred ranges are also the same. In Formula (4), R ⁴¹ has the same meaning as R ⁴¹ in Formula (3), and the preferred range is also the same. n is preferably 0 to 3, and more preferably 0 to 2.

The iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound in which R ³ in the general formula (1) is represented by the general formula (3) from the ease of synthesis, that is, It is preferable to be represented by Formula (5).

In formula (5), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ²¹ represents a substituent, m represents an integer of 0 to 5, when R ²¹ there are a plurality, even more R ²¹ is the same as each other or different, a ring together You may form. R ⁴¹ represents a substituent, n represents an integer of 0 to 5, when R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, a ring together You may form.

In the general formula ^(5), R ^{11, R 12} and ^{R 13} are the same as those in formula (1), and preferred ranges are also the same. In formula (5), R ⁴¹ has the same meaning as R ⁴¹ in formula (3), and the preferred range is also the same. The R ²¹ can also be exemplified the same substituents as ^{R 41} in the general formula (3).

In the general formula (5), n is preferably 0 to 3, and more preferably 0 to 2. m is preferably 0 to 3, and more preferably 0 to 2.

As the multimer of the iminoether compound represented by the general formula (1), a chain iminoether group-containing compound represented by the following general formula (6) is preferable in terms of easiness of synthesis and suppression of generation of volatilization gas.

In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L ¹ has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety. The alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.

In the general formula ^(6), R ^{11, R 12} and ^{R 13} are the same as those in formula (1), and preferred ranges are also the same. In Formula (6), R ⁴¹ has the same meaning as R ⁴¹ in Formula (3), and the preferred range is also the same. n is preferably 0 to 3, and more preferably 0 to 2.

In General Formula (6), L ¹ is an alkoxy moiety which may have a substituent, an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent, at the end of the bond to a carbon atom It represents a p-valent group which is a ren moiety. p is an integer of 2 to 4, and p is preferably 2 or 3. The alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
Specific examples of the divalent group include, for example, an alkylene group which may have a substituent, an arylene group which may have a substituent, and an alkoxylene group which may have a substituent. Further, the terminal of the bond with the carbon atom is an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or an alkoxylene moiety which may have a substituent, as a partial structure, -SO _2- , -CO-, substituted or unsubstituted alkylene moiety, substituted or unsubstituted alkenylene moiety, alkynylene moiety, substituted or unsubstituted phenylene moiety, substituted or unsubstituted biphenylene moiety, substituted or unsubstituted naphthylene And groups containing at least one selected from -O-, -S- and -SO-. The alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
Preferably, for example, substituted or unsubstituted phenylene group, substituted or unsubstituted biphenylene group, substituted or unsubstituted naphthylene group, ethylene group, n-butylene group, substituted or unsubstituted cyclohexylene group, substituted or unsubstituted group -C ₆ H ₁₀ -C ₆ H _10- , substituted or unsubstituted -C ₆ H ₁₀ -CH ₂ -C ₆ H _10- , substituted or unsubstituted -C ₆ H ₄ -C (CH ₃ ) ₂ _-C ₆ H ₄ -, -C substituted or unsubstituted _{_{_{_{6 H 4 -CH 2 -C 6 H}}}} 4 -, substituted or unsubstituted _{_{-C 6 H 4 -C (O)}} -C 6 H 4 -, substituted or unsubstituted _{_{_{-C 6 H 4 -O-C 6}}} H 4 -, -C substituted or unsubstituted _{_{_{6 H 4 -S-C 6 H}}} 4 -, substituted or unsubstituted _-C 6 _H 4 -SO ₂ -C ₆ H ₄ -, also substituted Ku is unsubstituted _{_{_{_{-C 6 H 4 -C (CF 3}}}} ) 2 -C 6 H 4 -, substituted or unsubstituted _{_{-C 6 H 4 -NHC (O)}} -C 6 H 4 -, substituted or unsubstituted of _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (CH 3) 2 -C 6 H 4 -O-C 6 H 4 -, substituted or unsubstituted _{_{_{-C 6 H 4 -O-C 6}}} H _{_{_{4 -C (O) -C 6 H}}} 4 -O-C 6 H 4 -, -C 6 H 4 substituted or unsubstituted _{_{_{_{-O-C 6 H 4 -SO 2}}}} -C 6 H 4 -O-C 6 _H ₄ -, _-C 6 H ₄ substituted or unsubstituted _{_{_{_{-O-C 6 H 4 -S-}}}} C 6 H 4 -O-C 6 H 4 -, -C 6 substituted or unsubstituted _H 4 -O- _{_{_{(C 6 H 4) 2 -O}}} -C 6 H 4 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (CF 3) 2 -C 6 H 4 -O-C 6 ₄ -, and the like.
As a specific example of a trivalent group, the group which remove | eliminated one hydrogen atom from the structure which has a substituent among the groups mentioned as an example of a bivalent group is mentioned, for example.
As a specific example of a tetravalent group, the group which remove | eliminated two hydrogen atoms from the structure which has a substituent among the groups mentioned as an example of a bivalent group is mentioned, for example.

In the present disclosure, by setting p in the general formula (6) to 2 to 4, a compound having two or more iminoether moieties in one molecule can be obtained, and a more excellent end capping effect can be exhibited. it can. Furthermore, the iminoether value (total molecular weight / number of iminoether groups) can be lowered by using a compound having two or more iminoether moieties in one molecule, and an iminoether compound can be efficiently reacted with a carboxy group. it can.

As the multimer of the iminoether compound represented by the general formula (1), a chain iminoether group-containing compound represented by the following general formula (7) is also preferable in terms of easiness of synthesis and suppression of generation of volatilization gas.

In the general formula (7), R ² , R ¹¹ , R ¹² and R ¹³ have the same meanings as each other in the general formula (1), and the preferred ranges are also the same.

In the general formula (7), L ² represents a p-valent group which is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, at the end of the bond to the nitrogen atom. L ² is preferably a p-valent group in which the end of the bond to the nitrogen atom is an arylene moiety which may have a substituent. p is an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of L ² include an arylene group which may have a substituent, and a cycloalkylene group which may have a substituent. The end of the bond to the nitrogen atom is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, and as a partial structure, —SO ₂ —, —CO—, substituted or unsubstituted , An substituted or unsubstituted alkenylene moiety, an alkynylene moiety, a substituted or unsubstituted phenylene moiety, a substituted or unsubstituted biphenylene moiety, a substituted or unsubstituted naphthylene moiety, -O-, -S- and -SO- And groups containing at least one selected from
Preferably, for example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted -C ₆ H ₁₀ -C ₆ H ₁₀ -, substituted or unsubstituted _{_{_{_{-C 6 H 10 -CH 2 -C 6}}}} H 10 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -C (CH 3}}}} ) 2 -C 6 H 4 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -CH 2 -C 6}}}} H 4 -, substituted or unsubstituted _{_{-C 6 H 4 -C (O)}} -C 6 H 4 -, substituted or unsubstituted _-C 6 H _{_{_{4 -O-C 6 H 4 -}}} , substituted or unsubstituted _{_{_{_{-C 6 H 4 -SC 6 H 4}}}} -, -C substituted or unsubstituted _{_{_{_{6 H 4 -SO 2 -C 6 H}}}} 4 -, substituted or unsubstituted _-C 6 _H 4 -C substitution _{_{_{_{CF 3) 2 -C 6 H 4}}}} -, substituted or unsubstituted _{_{-C 6 H 4 -NHC (O)}} -C 6 H 4 -, -C substituted or unsubstituted _{_{_{6 H 4 -O-C 6 H}}} 4 _{_{_{_{-C (CH 3) 2 -C 6}}}} H 4 -O-C 6 H 4 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (O) -C 6 H 4 -O -C ₆ H ₄ -, _-C 6 _H 4 substituted or unsubstituted _{_{_{_{-O-C 6 H 4 -SO 2}}}} -C 6 H 4 -O-C 6 H 4 -, substituted or unsubstituted _-C 6 H _{_{_{_{4 -O-C 6 H 4 -S}}}} -C 6 H 4 -O-C 6 H 4 -, -C 6 substituted or unsubstituted _{_{_{_{H 4 -O- (C 6 H 4}}}} ) 2 -O-C 6 H ₄ -, a substituted or unsubstituted _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (CF 3) 2 -C 6 H 4 -O-C 6 H 4 -, and the like.

As the multimer of the iminoether compound represented by the general formula (1), a chain iminoether group-containing compound represented by the following general formula (8) is also preferable in terms of easiness of synthesis and suppression of generation of volatilization gas.

In General Formula (8), R ² is synonymous with R ² in General Formula (1), and its preferable range is also the same. In Formula (8), R ⁴¹ has the same meaning as R ⁴¹ in Formula (3), and the preferred range is also the same. n is preferably 0 to 3, and more preferably 0 to 2. R ² may link to R ⁴¹ to form a ring.

In general formula (8), L ³ represents a p-valent group in which the end of the bond to the oxygen atom is an alkylene part. In the alkylene moiety of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent. p is an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of L ^3, include an alkylene group. The end of the bond to the oxygen atom is an alkylene moiety, and as a partial structure, -SO _2- , -CO-, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted Examples thereof include a group containing at least one selected from a phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, -O-, -S- and -SO-.
Preferably, for example, ethylene group, n-butylene group, substituted or unsubstituted -CH ₂ -C (CH ₃ ) ₂ -CH _2- , substituted or unsubstituted -CH ₂ -C ₆ H ₄ -CH _2- , Etc.

The molecular weight (total molecular weight / number of iminoether groups) per iminoether group of the chain iminoether group-containing compound used in the present disclosure is preferably 1000 or less, more preferably 750 or less, and 500 or less Is more preferred. By setting the molecular weight per iminoether group to 1000 or less, it becomes possible to seal the terminal carboxy group of the polyamide with a low addition amount.
On the other hand, the molecular weight per iminoether group of the chain iminoether group-containing compound is 300 or more from the viewpoint of suppressing the volatilization of the reaction product or the unreacted chain iminoether group-containing compound when producing the molded product. Is preferred.

Although the preferable specific example of the iminoether compound represented by General formula (1) and its multimer is shown below, the chain-like iminoether group containing compound which can be used by this indication is not limited to these.

The polyamide resin composition of the present disclosure includes a polyamide and at least one linear iminoether group-containing compound selected from an iminoether compound represented by the general formula (1) and an oligomer thereof, at the time of molding. It is possible to effectively suppress the generation of volatile gas and thickening, and to produce a polyamide resin molded product having hydrolysis resistance.
Moreover, the color taste of a molded object can also be controlled by adjusting the addition amount of a chain-like iminoether group containing compound.

The polyamide resin composition of the present disclosure preferably contains 0.05 to 5.0 parts by mass of the chain iminoether group-containing compound with respect to 100 parts by mass of the polyamide. By setting the addition amount of the chain iminoether group-containing compound to 0.05 parts by mass or more with respect to 100 parts by mass of polyamide, generation of volatilized gas and thickening are effectively suppressed, and a polyamide resin molded body Resistance to hydrolysis can be further improved. On the other hand, yellowishness can be suppressed by the said addition amount of the iminoether compound represented by General formula (1) being 5.0 mass parts or less.
In addition to the improvement of the hydrolysis resistance of the polyamide resin molded product and the suppression of the generation of volatilized gas and the thickening during molding, from the viewpoint of effectively suppressing the yellowishness, a chain imino relative to 100 parts by mass of the polyamide More preferably, the ether group-containing compound is contained in an amount of 0.1 to 2.0 parts by mass.
The polyamide resin composition of the present disclosure may use a single chain iminoether group-containing compound singly or in combination of two or more thereof, but may use a combination of a plurality of chain iminoether group-containing compounds. When it does, it is preferable that a total amount is the said range.

The polyamide resin composition of the present disclosure can be added to various additives such as a compatibilizer, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and the like as long as the effects of the present invention are not significantly impaired. The composition may contain an inhibitor, a brightener, a colorant, a conductive agent, an ultraviolet absorber, a flame retardant, a flame retardant aid, a pigment, a dye and the like.

The polyamide resin composition of the present disclosure does not refuse to contain an end capping agent other than the iminoether compound described above, as long as the effects of the present invention are not significantly impaired. The polyamide resin composition of this indication can also use together the terminal blocker chosen from a carbodiimide compound, an epoxy compound, and an oxazoline compound other than the iminoether compound mentioned above, for example.

<Polyamide resin molding>
The molding method at the time of manufacturing a polyamide resin molded object using the polyamide resin composition of this indication is not specifically limited, What is necessary is just to apply the well-known molding method according to a use, such as injection molding and extrusion molding. For example, a polyamide resin molded body having a desired shape can be obtained by heating and melting and kneading to a temperature equal to or higher than the melting point of the polyamide contained in the polyamide resin composition of the present disclosure and injection molding. The polyamide resin composition of the present disclosure is a polyamide resin having hydrolysis resistance and suppressing volatilization and thickening of by-products derived from the chain iminoether group-containing compound even when heated at the time of kneading or molding. Moldings can be produced.

The application of the polyamide resin composition of the present disclosure is not particularly limited. For example, machine parts, parts for telecommunications equipment, transport machine parts, office machinery parts, gasoline tanks, various electric and electronic parts, miscellaneous goods, building materials, films, fish nets and It can be suitably used as a fishing tool such as Tegs, a gear, a fastener, an intake pipe, a radiator tank, a resin molded product such as a cooling fan.

Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the examples shown below. In addition, "part" is mass reference | standard unless there is particular notice.

In the examples, first, the following exemplified compounds were synthesized as iminoether compounds.

Synthesis Example 1
<Synthesis of iminoether (1)>

In a 5 L three-necked flask, 600 g (2.80 mol) of triethoxymethylbenzene, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid The mixture was charged with 2.5 mmol) and stirred under heating reflux for 2 hours. The reaction system temperature was brought to 100 ° C. or lower, and the refluxed ethanol was removed by a Dean-Stark apparatus. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature, methanol was added and crystallized to obtain 777 g (yield 95%) of iminoether (1). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 2
<Synthesis of iminoether (2)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid The mixture was charged with 2.5 mmol) and stirred under heating reflux for 2 hours. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature and methanol was added to crystallize to obtain 745 g (yield 95%) of iminoether (2). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 3
<Synthesis of iminoether (3)>

In a 5-L three-necked flask, 338 g (2.80 mol) of trimethyl orthoacetate, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid (2 .5 mmol) was added and stirred for 2 hours under heating and reflux. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature, and methanol was added to crystallize to obtain 615 g (yield 92%) of iminoether (3). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 4
<Synthesis of iminoether (4)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 310 g (1.28 mol) of 4,4'-diaminobenzanilide, 480 ml of toluene and 0.24 g (2.5 mmol) of methanesulfonic acid are charged, and heated to reflux. Stir for 2 hours below. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature, and methanol was added to crystallize to obtain 504 g (yield 85%) of iminoether (4). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 5
<Synthesis of iminoether (5)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 191.8 g (1.28 mol) of 4-aminoacetanilide, 480 ml of toluene and 0.24 g (2.5 mmol) of methanesulfonic acid are charged, and heated under reflux 2 Stir for hours. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature and methanol was added to crystallize to obtain 309 g (yield 90%) of iminoether (5). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 6
<Synthesis of iminoether (6)>

In a 5-L three-necked flask, 210 g (1.0 mol) of 4,4'-methylenebis (cyclohexylamine), 243 g (2.4 mol) of triethylamine and 1.0 L of dimethylacetamide are charged, and 336 g (2.4 mol) of benzoyl chloride in an ice bath After dropwise addition, the mixture was stirred at room temperature for 1 hour. 2.0 L of 1 mol / L hydrochloric acid water was added, and the mixture was stirred for 1 hour, and filtered to obtain 397 g (yield 95%) of an intermediate product (6-1). The obtained compound was identified by ¹ H-NMR.

In a 5 L three-necked flask, 300 g of the intermediate product (6-1) and 1.0 L of thionyl chloride were added, and after stirring at 65 ° C. for 2 hours, excess thionyl chloride was removed under reduced pressure. After cooling to room temperature, 1.0 ml of THF (tetrahydrofuran) was added, and 310 g (1.6 mol) of sodium methylate 28 mass% methanol solution (trade name: SM-28) was added dropwise under an ice bath, and then 1 hour at room temperature It stirred. After adding 1.5 L of ethyl acetate and 1.0 L of pure water, liquid separation was carried out, after drying with magnesium sulfate, the solid was obtained by concentrating. Thereto, 2.0 L of methanol was added, and stirred at room temperature for 1 hour, followed by filtration to obtain 288 g (yield 90%) of iminoether (6). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 7
<Synthesis of iminoether (7)>

In a 5 L flask, 296 g (2.4 mol) of 2-aminobenzyl alcohol, 243 g (2.4 mol) of triethylamine and 1.5 L of dimethylacetamide are charged, and 203 g (1.0 mol) of terephthalic acid chloride is added in portions under an ice bath. After stirring for 1 hour, 2.0 L of 1 mol / L hydrochloric acid water was added, and the mixture was stirred for 1 hour, followed by filtration to obtain 357 g (yield 95%) of an intermediate product (7-1). The obtained compound was identified by ¹ H-NMR.

In a 5 L three-necked flask, 300 g (0.8 mol) of the intermediate product (7-1) and 1.0 L of thionyl chloride were added, and after stirring at 65 ° C. for 2 hours, excess thionyl chloride was concentrated and removed. After adding 1.0 L of methanol, 386 g (2.0 mol) of sodium methylate 28 mass% methanol solution (trade name: SM-28) is slowly added dropwise under an ice bath, and 1 hour at room temperature, 50 hours at 40 ° C. It stirred. The precipitate is filtered and methanol is removed under reduced pressure, and 1.5 L of ethyl acetate is added, separated, dried over magnesium sulfate, crystallized by adding methanol, and filtered to obtain an iminoether (7). 136 g (50% yield) were obtained. The obtained compound was identified by ¹ H-NMR.

Synthesis Example 8
<Synthesis of iminoether (8)>

A solution of 92.4 g (0.75 mol) of p-anisidine, 59 g (0.75 mol) of pyridine in 500 ml of N, N-dimethylacetamide under ice-cooling, 50 g (0.19 mol) of N, N-dimethyl trimesic acid trichloride A solution of 100 ml of acetamide was added dropwise. After heating up to room temperature, it stirred for 3 hours. The reaction solution was slowly added to 5 L of water to precipitate a solid. The solid was separated by filtration, and the obtained solid was dispersed in methanol and filtered again. This operation was repeated twice, and the obtained solid was dried to obtain 96.8 g (yield 97%) of an intermediate product (8-1).

A suspension of 26.3 g (50 mmol) of the intermediate product (8-1) in 100 ml of thionyl chloride was stirred for 3 hours while heating under reflux. After confirming that the reaction system became transparent, the mixture was further stirred for 2 hours. After thionyl chloride was distilled off, 200 ml of tetrahydrofuran was added, and 21.2 g (110 mol) of a sodium methylate 28% by mass methanol solution (trade name: SM-28) was added dropwise under ice-cooling. The temperature of the system was raised to room temperature, and after stirring for 10 minutes, ethyl acetate / water was added to separate the layers. The organic phase was washed with water and the organic phase was dried over magnesium sulfate. After the solvent was distilled off, purification was performed by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as an eluent. The solvent was distilled off to obtain 25.0 g (yield 88%) of iminoether (8). The obtained compound was identified by ¹ H-NMR.

<Synthesis of iminoether (9)>
Synthesis Example 9

Under ice-cooling, 95 g (0.5 mol) of benzoyl chloride was slowly added to a solution of 46.5 g (0.5 mol) of aniline and a solution of 44 g (0.6 mol) of pyridine in N, N-dimethylacetamide under ice cooling. The temperature of the reaction system was raised to room temperature, and the completion of the reaction was confirmed by TLC. After 50 ml of methanol was added, the reaction solution was slowly added to 5 liters of water to precipitate a solid. The solid was separated by filtration, and the obtained solid was dispersed in methanol and filtered again. This operation was repeated twice, and the obtained solid was dried to obtain 89.7 g (yield 91%) of an intermediate product (9-1).

A suspension of 9.9 g (50 mmol) of intermediate product (9-1) in 400 ml of thionyl chloride and a catalytic amount of N, N-dimethylformamide was stirred for 18 hours while heating under reflux. After confirming that the reaction system was completely dissolved, the mixture was further stirred for 2 hours. Thereafter, thionyl chloride was distilled off to obtain 10.8 g (quant.) Of an intermediate product (9-2).

After 2.0 g (50 mmol) of sodium hydride (60% by mass) was dispersed with hexane and allowed to stand, the supernatant hexane was removed with a Pasteur pipette. This operation was repeated twice and 50 ml of a tetrahydrofuran solution was added. Under ice-cooling, 1.6 g (25 mmol) of ethylene glycol was added. It confirmed visually that generation | occurrence | production of the bubble was complete | finished from system inside, and the tetrahydrofuran solution of ethylene dimethoxide was prepared.

150 ml of a tetrahydrofuran solution of 10.8 g (50 mmol) of the intermediate product (9-2) was cooled to −5 ° C., and the prepared tetrahydrofuran solution of ethylene dimethoxide was added dropwise. The temperature of the system was raised to room temperature, and after stirring for 30 hours, ethyl acetate / water was added to separate the layers. The organic phase was washed with water and the organic phase was dried over magnesium sulfate. After the solvent was distilled off, purification was performed by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as an eluent. The solvent was distilled off to obtain 6.5 g (yield 62%) of iminoether (9). The obtained compound was identified by ¹ H-NMR.

Example 1
One part by mass of iminoether (1) is added to 100 parts by mass of nylon 6 (manufactured by Unitika, A1030 BRL, melting point 225 ° C.), dry mixed together, and melt mixed at 250 ° C. with a twin-screw kneader It extruded and produced the pellet. The obtained pellet was dried and injection-molded at 250 ° C. to prepare a plate-like test piece (100 mm × 100 mm, thickness: 0.3 mm).

-Performance evaluation of polyamide resin moldings-
Each of the obtained test pieces was evaluated for hydrolysis resistance (moisture and humidity resistance 1 and 2), volatilization of iminoether-derived compound, and color.

(Moisture resistant 1)
The obtained plate-like test piece is stored at 120 ° C. under water vapor at a relative humidity of 100%, and the breaking elongation (%) of the test piece after storage shows the test before storage It evaluated by the following reference | standard by measuring the storage time (the breaking elongation retention half life) used as 50% with respect to the breaking elongation (%) which a piece shows. The obtained results are shown in Table 1 below.
A: elongation at break retention half life of 50 days or more B: elongation at break retention half life of 40 days to less than 50 days C: elongation at break retention half life of 25 days to less than 40 days D: elongation at break Retention half-life less than 25 days

(Moisture resistant 2)
The obtained plate-like test piece is stored in a citric acid aqueous solution at pH 4 at 100 ° C., and the breaking elongation (%) exhibited by the test piece after storage is the test piece before storage It evaluated by the following reference | standard by measuring the storage time (breaking elongation retention half life) used as 50% with respect to the breaking elongation (%) which this shows. The obtained results are shown in Table 1 below.
A: elongation at break retention half life of 50 days or more B: elongation at break retention half life of 40 days to less than 50 days C: elongation at break retention half life of 25 days to less than 40 days D: elongation at break Retention half-life less than 25 days

(Volatile)
The amount of the volatile component was measured by gas chromatography (trade name: P & T-GC / MS, manufactured by JASCO Corporation) according to the following conditions with respect to the obtained test piece, and evaluated based on the following criteria. The volatile component contains a compound derived from iminoether, and specifically includes an iminoether compound and an amide compound. The amount of volatile components generated during molding is reflected in the content of volatile components derived from iminoether contained in the test piece. That is, when the detected amount of the volatilization component is small, it means that the volatilization of the iminoether compound and the amide compound is small and the production environment of the molded product is improved. The obtained results are shown in Table 1 below.

<Condition>
The test piece was heated for 10 minutes at a kneading temperature (250 ° C. in Example 1) in a closed container, and the generated gas was detected.
A: Compounds derived from imino ether are below the detection limit.
B: Compound derived from iminoether was detected at a concentration of 10 ppm or less.
C: Compound derived from iminoether was detected at a concentration of more than 10 ppm.

(Color)
The obtained test pieces were visually evaluated according to the following criteria.
A: Yellowishness is equivalent to Comparative Example 1 and acceptable level.
B: Yellowishness is larger than Comparative Example 1 and unacceptable level.

(Formability)
The resin pressure at the time of molding was confirmed by the pressure gauge of the extruder and evaluated according to the following criteria.
A: Increase in resin pressure is 0% or more and less than 50% in comparison with Comparative Example 1 B: Comparison with Comparative Example 1 is 50% or more and less than 100% in C: Comparison with Comparative Example 1 and resin 100% or more increase in pressure

Comparative Example 1
Test pieces were prepared and evaluated in the same manner as in Example 1 except that the iminoether (1) was not added.

[Examples 2 to 8, Comparative Example 5]
Test pieces were prepared and evaluated in the same manner as in Example 1 except that the compounds described in Table 1 were added instead of the iminoether (1).

[Example 9]
The mixing temperature and the injection molding temperature were changed to 290 ° C. by changing nylon 6 (manufactured by Unitika, A1030 BRL, melting point 225 ° C.) to nylon 66 (manufactured by Ube Industries, UBE nylon (registered trademark) 2020 B, melting point 265 ° C.) Test pieces were produced in the same manner as in Example 1 except for the evaluation.

[Example 10]
Except that nylon 6 (Unitika manufactured by Unitika, A1030 BRL, melting point 225 ° C.) was changed to nylon 12 (manufactured by Ube Industries, Inc., UBESTA (registered trademark) 3014 B, melting point 175 ° C.) and kneading temperature and injection molding temperature were changed to 200 ° C. A test piece was produced and evaluated in the same manner as in Example 1.

[Examples 11 to 15]
Test pieces were prepared and evaluated in the same manner as in Example 1 except that the addition amount of the iminoether (1) was changed as described in Table 1, respectively.

Comparative Example 2
Test pieces were prepared and evaluated in the same manner as in Example 1 except that Stabaxol (registered trademark) P400 (manufactured by Line Chemie Co., Ltd.) was added instead of the iminoether (1).

Comparative Example 3
Test pieces were prepared and evaluated in the same manner as in Example 1 except that tetramethylenebisoxazoline (TMBO) having the following structure synthesized in the following Synthesis Example 10 was added instead of the iminoether (1) and added.

Synthesis Example 10
<Composition of TMBO>

In a 5-L flask, 500 g (2.47 mol) of diethyl adipate and 1500 g (9.9 mol) of ethanolamine were charged, and ethanol generated was distilled off while stirring at 170 ° C. for 1 hour. After cooling to room temperature, benzene and methanol were added for recrystallization, and filtration was performed to obtain 471 g (yield 82%) of an intermediate product TMBO-1. The obtained compound was identified by ¹ H-NMR.

185.7 g (0.8 mol) of TMBO-1 and 1.0 L of chloroform were charged into a 5 L three-necked flask, and 238 g (2.0 mol) of thionyl chloride was added dropwise under an ice bath, and the mixture was stirred at room temperature for 2 hours. After excess thionyl chloride is distilled off under reduced pressure, 1.0 L of methanol is added, and 771.7 g (4.0 mol) of a sodium methylate 28% by mass methanol solution (trade name: SM-28) is slowly added dropwise to obtain a room temperature The mixture was stirred at 40 ° C. for 30 hours under 2 hours. The reaction solution was cooled to room temperature, filtered, and the solvent was evaporated under reduced pressure. Then, 1.0 L of ethyl acetate was added, and after filtering, ethyl acetate was evaporated under reduced pressure. The obtained oily compound was distilled and purified at 128 ° C. and 133.3 Pa (1 Torr) to obtain 118 g (75% yield) of TMBO. The obtained compound was identified by ¹ H-NMR.

Comparative Example 4
Test pieces were prepared and evaluated in the same manner as in Example 1 except that Epocross (registered trademark) RPS (an oxazoline group-containing reactive polystyrene, manufactured by Nippon Shokubai Co., Ltd.) was added instead of the iminoether (1).

The resins and sealants used in Examples and Comparative Examples and the evaluation results are shown in Table 1 below. In addition, in Table 1, the addition amount of a sealing agent is an addition amount with respect to 100 mass parts of resin.

From the above Table 1, the polyamide resin compositions of the respective examples to which the chain iminoether group-containing compound according to the present disclosure is added as a sealing agent can suppress the generation of gas at the time of molding, and the increase in resin pressure is suppressed. , Was excellent in moldability. Moreover, the obtained polyamide resin molded product (test piece) was excellent in moist heat resistance, and the content of the volatilization component in the resin was small.
In Comparative Example 5, since the reactivity of the cyclic iminoether (7) is low, the hydrolysis resistance of the molded product is inferior, and it is considered that the moldability is lowered by the partial reaction, high molecular weight formation and thickening. .

The disclosure of Japanese Patent Application 2014-265716, filed December 26, 2014, is incorporated herein by reference in its entirety.
All documents, patents, patent applications, and technical standards described herein are specifically and individually indicated that each individual document, patent, patent application, and technical standard is incorporated by reference. To the same extent, incorporated herein by reference.

Claims

A polyamide, and at least one chained iminoether group-containing compound selected from an iminoether compound represented by the following general formula (1) and a multimer of the iminoether compound represented by the general formula (1) Polyamide resin composition.

In the general formula (1), R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R 3 represents R 11 represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3), and R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.

In formula (2), R 31 , R 32 and R 33 each independently represent a hydrogen atom or a substituent. R 31 , R 32 and R 33 may be linked to each other to form a ring. In Formula (3), R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring. In the general formulas (2) and (3), * represents a position to be bonded to a nitrogen atom.
The polyamide resin composition according to claim 1 R 3 is an aryl group represented by the general formula (3) in the general formula (1).
The polyamide resin composition according to claim 1 or 2, wherein the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (5).

In formula (5), R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R 21 represents a substituent, m represents an integer of 0 to 5, when R 21 there are a plurality, even more R 21 is the same as each other or different, a ring together You may form. R 41 represents a substituent, n represents an integer of 0 to 5, when R 41 there are a plurality, even more R 41 is the same as each other or different, a ring together You may form.
4. The compound according to any one of claims 1 to 3, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (6). The polyamide resin composition as described.

In General Formula (6), R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L 1 has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety.
The multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (7) The polyamide resin composition as described.

In the general formula (7), R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R 11 and R 12 And R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. p represents an integer of 2 to 4, and p represents a p-valent group in which L 2 is a arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent. Represents
4. The compound according to any one of claims 1 to 3, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (8). The polyamide resin composition as described.

In general formula (8), R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R 41 represents a substituent And n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L 3 represents a p-valent group in which the bonding end with the oxygen atom is an alkylene part. In the alkylene moiety of L 3 , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
The polyamide resin composition according to any one of claims 1 to 6, which comprises 0.1 to 2.0 parts by mass of the linear iminoether group-containing compound with respect to 100 parts by mass of the polyamide.
A polyamide resin molding molded using the polyamide resin composition according to any one of claims 1 to 7.