JP5983396B2 - Colored polyamide resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a polyamide resin composition and a method for producing the same, and more particularly to a polyamide resin composition exhibiting oxygen absorption performance and a method for producing the same.

  Polyamide obtained from polycondensation reaction of xylylenediamine and aliphatic dicarboxylic acid, for example, polyamide obtained from metaxylylenediamine and adipic acid (hereinafter referred to as nylon MXD6) has high strength, high elastic modulus, oxygen, carbonic acid Since it shows low permeability to gaseous substances such as gas, odor and flavor, it is widely used as a gas barrier material in the field of packaging materials. Nylon MXD6 has better thermal stability when melted than other gas barrier resins, and therefore coextruded or coextruded with thermoplastic resins such as polyethylene terephthalate (hereinafter abbreviated as PET), nylon 6 and polypropylene. Injection molding or the like is possible. Therefore, nylon MXD6 is used as a gas barrier layer constituting a multilayer structure.

  In recent years, nylon MXD6 is added and mixed with a small amount of transition metal compound to give nylon MXD6 an oxygen-absorbing function, and this is used as an oxygen barrier material constituting containers and packaging materials. Nylon MXD6 absorbs the incoming oxygen and nylon MXD6 also absorbs oxygen remaining inside the container, so that a method for improving the storage stability of the contents over conventional containers using oxygen-barrier thermoplastic resin is practical. (See, for example, Patent Documents 1 and 2).

On the other hand, oxygen absorbers have been used for a long time to remove oxygen in the container. For example, Patent Documents 3 and 4 describe an oxygen-absorbing multilayer body and an oxygen-absorbing film in which an oxygen absorbent such as iron powder is dispersed in a resin. Patent Document 5 describes a product having an oxygen scavenging layer containing an ethylenically unsaturated compound such as polybutadiene and a transition metal catalyst such as cobalt, and an oxygen barrier layer such as polyamide.
However, the oxygen absorbing multilayer body and the oxygen absorbing film in which an oxygen absorbent such as iron powder is dispersed in the resin use iron powder, so that the metal detector used for the inspection of the packaging container cannot be used. There are limitations. In addition, a resin containing an ethylenically unsaturated compound such as polybutadiene and a transition metal catalyst such as cobalt is uncomfortable due to low molecular weight compounds due to oxidation and decomposition of the ethylenically unsaturated compound such as polybutadiene by an oxygen absorption reaction. There is a problem that odor is generated and the color tone and strength of the molded article are impaired.

  In response to this problem, the present inventors have succeeded in developing a polyamide resin that exhibits sufficient oxygen absorption performance without containing metal, does not generate unpleasant odor, and has extremely good transparency ( Patent Document 6). In addition, the present inventors have succeeded in developing a polyamide resin composition having further improved oxygen absorption performance without deteriorating the transparency of the polyamide resin (Patent Document 7).

JP 2003-341747 A Japanese Patent No. 2991437 JP-A-2-72851 Japanese Patent Laid-Open No. 4-90848 Japanese Patent Laid-Open No. 5-115776 International Publication No. 2011/081099 International Publication No. 2012/090797

Packaging containers used for foods, beverages and the like that require an oxygen absorbing function may be colored because they require not only oxygen barrier properties but also barriers such as ultraviolet rays. In this case, in addition to blending an ethylenically unsaturated compound such as polybutadiene and a transition metal catalyst such as cobalt, it is also necessary to blend a colorant, so that the mixing operation becomes complicated, and the oxygen absorption accelerator Since the masterbatch and the colorant masterbatch are prepared separately, there is a problem that the material cost increases.
The problem to be solved by the present invention is to provide a polyamide resin composition that can exhibit further superior oxygen absorption performance at a low cost and satisfies the coloring required for a molded article.

  As a result of intensive studies, the inventors have blended a polyamide resin described in Patent Document 6 with a colorant containing one or more metal atoms selected from iron, manganese, copper and zinc. Furthermore, it has been found that it exhibits excellent oxygen absorption performance.

［前記一般式（Ｉ−３）中、ｍは２〜１８の整数を表す。前記一般式（ＩＩ−１）中、ｎは２〜１８の整数を表す。前記一般式（ＩＩ−２）中、Ａｒはアリーレン基を表す。前記一般式（ＩＩＩ）中、Ｒは置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表す。］
＜２＞上記＜１＞に記載のポリアミド樹脂組成物を製造する方法であって、前記着色剤（Ｂ）と熱可塑性樹脂（Ｘ）とを溶融混合してマスターバッチを得る工程、及び該マスターバッチを前記ポリアミド樹脂（Ａ）と溶融混練する工程を含む、ポリアミド樹脂組成物の製造方法。
＜３＞上記＜１＞に記載のポリアミド樹脂組成物を含有する成形体。 The present invention provides the following polyamide resin composition and method for producing the same, and a molded article containing the polyamide resin composition.
<1> An aromatic diamine unit represented by the following general formula (I-1), an alicyclic diamine unit represented by the following general formula (I-2), and a following general formula (I-3) 25 to 50 mol% of diamine units containing at least 50 mol% in total of at least one diamine unit selected from the group consisting of linear aliphatic diamine units,
A dicarboxylic acid unit containing a total of 50 mol% or more of a linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) and / or an aromatic dicarboxylic acid unit represented by the following general formula (II-2) 25 to 50 mol%,
A polyamide resin (A) containing 0.1 to 50 mol% of a structural unit represented by the following general formula (III), and a color containing one or more metal atoms selected from iron, manganese, copper and zinc Agent (B)
A polyamide resin composition comprising:

[In the general formula (I-3), m represents an integer of 2 to 18. In the general formula (II-1), n represents an integer of 2 to 18. In the general formula (II-2), Ar represents an arylene group. In the general formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ]
<2> A method for producing the polyamide resin composition according to <1>, wherein the master is obtained by melt-mixing the colorant (B) and the thermoplastic resin (X), and the master The manufacturing method of a polyamide resin composition including the process of melt-kneading a batch with the said polyamide resin (A).
<3> A molded article containing the polyamide resin composition according to <1>.

  The polyamide resin composition of the present invention can exhibit excellent oxygen absorption performance without causing deterioration of the oxygen barrier property due to oxidative degradation of the resin during production, and can improve designability by coloring. Moreover, the molded object obtained using the polyamide resin composition of this invention, especially a container, can suppress deterioration of the content by shielding ultraviolet rays etc. by coloring while being excellent in oxygen absorption performance.

The polyamide resin composition of the present invention comprises a specific polyamide resin (A) described later (hereinafter also referred to as “oxygen-absorbing polyamide resin”), and a colorant (B) containing a specific metal atom described later. Including.
The content of the colorant (B) is preferably 1 to 5000 mass ppm, more preferably 1 to 2000 mass ppm, and further preferably 3 to 1000 as a metal atom concentration with respect to 100 mass% of the polyamide resin composition. It is ppm by mass, particularly preferably 5 to 500 ppm by mass.
The polyamide resin composition of the present invention may further contain other components as long as the effects of the present invention are not impaired. In addition, when a polyamide resin composition contains another component in this invention, it is set as a polyamide resin composition including another component.

［前記一般式（Ｉ−３）中、ｍは２〜１８の整数を表す。前記一般式（ＩＩ−１）中、ｎは２〜１８の整数を表す。前記一般式（ＩＩ−２）中、Ａｒはアリーレン基を表す。前記一般式（ＩＩＩ）中、Ｒは置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表す。］
ただし、前記ジアミン単位、前記ジカルボン酸単位、前記３級水素含有カルボン酸単位の合計は１００モル％を超えないものとする。ポリアミド樹脂（Ａ）は、本発明の効果を損なわない範囲で、前記以外の構成単位を更に含んでいてもよい。 1. Polyamide resin (A)
In the present invention, the polyamide resin (A) is an aromatic diamine unit represented by the following general formula (I-1), an alicyclic diamine unit represented by the following general formula (I-2), and the following general formula. 25 to 50 mol% of diamine units containing at least 50 mol% in total of at least one diamine unit selected from the group consisting of linear aliphatic diamine units represented by (I-3), and the following general formula (II-1) 25 to 50 mol% of dicarboxylic acid units including a total of 50 mol% or more of the linear aliphatic dicarboxylic acid units represented by formula (II) and the aromatic dicarboxylic acid units represented by the following general formula (II-2): A tertiary hydrogen-containing carboxylic acid unit (preferably a structural unit represented by the following formula (III)) is contained in an amount of 0.1 to 50 mol%.

[In the general formula (I-3), m represents an integer of 2 to 18. In the general formula (II-1), n represents an integer of 2 to 18. In the general formula (II-2), Ar represents an arylene group. In the general formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ]
However, the total of the diamine unit, the dicarboxylic acid unit, and the tertiary hydrogen-containing carboxylic acid unit shall not exceed 100 mol%. The polyamide resin (A) may further contain structural units other than those described above as long as the effects of the present invention are not impaired.

  In the polyamide resin (A), the content of the tertiary hydrogen-containing carboxylic acid unit is 0.1 to 50 mol%. If the content of the tertiary hydrogen-containing carboxylic acid unit is less than 0.1 mol%, sufficient oxygen absorption performance is not exhibited. On the other hand, if the content of the tertiary hydrogen-containing carboxylic acid unit exceeds 50 mol%, the tertiary hydrogen content is too high, and the physical properties such as gas barrier properties and mechanical properties of the polyamide resin (A) are lowered. When the secondary hydrogen-containing carboxylic acid is an amino acid, the peptide bond is continuous, so that the heat resistance is not sufficient, and a cyclic product composed of a dimer of amino acids is formed, thereby inhibiting polymerization. The content of the tertiary hydrogen-containing carboxylic acid unit is preferably 0.2 mol% or more, more preferably 1 mol% or more, and preferably from the viewpoint of oxygen absorption performance and the properties of the polyamide resin (A). It is 40 mol% or less, More preferably, it is 30 mol% or less.

In the polyamide resin (A), the content of the diamine unit is 25 to 50 mol%, and preferably 30 to 50 mol% from the viewpoint of oxygen absorption performance and polymer properties. Similarly, in the polyamide resin (A), the content of the dicarboxylic acid unit is 25 to 50 mol%, preferably 30 to 50 mol%.
The proportion of the content of the diamine unit and the dicarboxylic acid unit is preferably substantially the same from the viewpoint of the polymerization reaction, and the content of the dicarboxylic acid unit is ± 2 mol% of the content of the diamine unit. More preferred. If the content of the dicarboxylic acid unit exceeds the range of ± 2 mol% of the content of the diamine unit, the degree of polymerization of the polyamide resin (A) becomes difficult to increase, so it takes a lot of time to increase the degree of polymerization, Deterioration is likely to occur.

1-1. Diamine Unit The diamine unit in the polyamide resin (A) is an aromatic diamine unit represented by the general formula (I-1), an alicyclic diamine unit represented by the general formula (I-2), and the above The diamine unit contains a total of 50 mol% or more of at least one diamine unit selected from the group consisting of linear aliphatic diamine units represented by general formula (I-3), and the content is preferably 70. It is at least mol%, more preferably at least 80 mol%, still more preferably at least 90 mol%, and preferably at most 100 mol%.

  Examples of the compound that can constitute the aromatic diamine unit represented by the general formula (I-1) include orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine. These can be used alone or in combination of two or more.

Examples of the compound that can constitute the alicyclic diamine unit represented by the formula (I-2) include bis (amino) such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane. Methyl) cyclohexanes. These can be used alone or in combination of two or more.
Bis (aminomethyl) cyclohexanes have structural isomers, but by increasing the cis-isomer ratio, the crystallinity is high and good moldability can be obtained. On the other hand, if the cis-isomer ratio is lowered, a transparent material with low crystallinity can be obtained. Therefore, when it is desired to increase the crystallinity, the cis-isomer content ratio in the bis (aminomethyl) cyclohexane is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more. . On the other hand, when it is desired to lower the crystallinity, the cis body content ratio in the bis (aminomethyl) cyclohexanes is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less. .

In said general formula (I-3), m represents the integer of 2-18, Preferably it is 3-16, More preferably, it is 4-14, More preferably, it is 6-12.
Examples of the compound that can constitute the linear aliphatic diamine unit represented by the general formula (I-3) include ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and heptamethylenediamine. And aliphatic diamines such as octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, but are not limited thereto. Among these, hexamethylenediamine is preferable. These can be used alone or in combination of two or more.

  As the diamine unit in the polyamide resin (A), in addition to imparting excellent gas barrier properties to the polyamide resin (A), it improves transparency and color tone and facilitates moldability of general-purpose thermoplastic resins. From the viewpoint, it preferably contains an aromatic diamine unit represented by the general formula (I-1) and / or an alicyclic diamine unit represented by the general formula (I-2). From the viewpoint of imparting appropriate crystallinity to (A), it is preferable to include a linear aliphatic diamine unit represented by the general formula (I-3). In particular, from the viewpoint of oxygen absorption performance and the properties of the polyamide resin (A), it is preferable that the aromatic diamine unit represented by the general formula (I-1) is included.

  The diamine unit in the polyamide resin (A) is a metaxylylenediamine unit from the viewpoint of facilitating the moldability of a general-purpose thermoplastic resin in addition to exhibiting excellent gas barrier properties in the polyamide resin (A). The content is preferably 50 mol% or more, and the content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less.

  Examples of the compound that can constitute a diamine unit other than the diamine unit represented by any one of the general formulas (I-1) to (I-3) include aromatic diamines such as paraphenylenediamine, and 1,3-diaminocyclohexane. Alicyclic diamines such as 1,4-diaminocyclohexane, N-methylethylenediamine, 2-methyl-1,5-pentanediamine, and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane Examples include, but are not limited to, group diamines, polyether diamines having ether bonds represented by Huntsman's Jeffamine and elastamine (both are trade names), and the like. These can be used alone or in combination of two or more.

1-2. Dicarboxylic acid unit The dicarboxylic acid unit in the polyamide resin (A) is represented by the general formula (II-1) from the viewpoints of reactivity during polymerization and crystallinity and moldability of the polyamide resin (A). The chain aliphatic dicarboxylic acid unit and / or the aromatic dicarboxylic acid unit represented by the general formula (II-2) is contained in the dicarboxylic acid unit in a total of 50 mol% or more, and the content is preferably 70 mol%. Above, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less.

  Examples of the compound that can constitute a dicarboxylic acid unit other than the dicarboxylic acid unit represented by the general formula (II-1) or (II-2) include oxalic acid, malonic acid, fumaric acid, maleic acid, 1,3- Examples of the dicarboxylic acid include benzenediacetic acid and 1,4-benzenediacetic acid, but are not limited thereto.

  In the dicarboxylic acid unit in the polyamide resin (A), the content ratio of the linear aliphatic dicarboxylic acid unit to the aromatic dicarboxylic acid unit (linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit) is particularly limited. Rather, it is determined appropriately according to the application. For example, when the purpose is to increase the glass transition temperature of the polyamide resin (A) to lower the crystallinity of the polyamide resin (A), the linear aliphatic dicarboxylic acid units / aromatic dicarboxylic acid units are both units. When the total is 100, the molar ratio is preferably 0/100 to 60/40, more preferably 0/100 to 40/60, and still more preferably 0/100 to 30/70. Further, when the purpose is to lower the glass transition temperature of the polyamide resin (A) to impart flexibility to the polyamide resin (A), the linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit is When the total is 100, the molar ratio is preferably 40/60 to 100/0, more preferably 60/40 to 100/0, and still more preferably 70/30 to 100/0.

1-2-1. The linear aliphatic dicarboxylic acid unit polyamide resin (A) gives the polyamide resin composition of the present invention the flexibility necessary for a packaging material or packaging container in addition to imparting an appropriate glass transition temperature and crystallinity. In the case of the object, it preferably contains a linear aliphatic dicarboxylic acid unit represented by the general formula (II-1).
In said general formula (II-1), n represents the integer of 2-18, Preferably it is 3-16, More preferably, it is 4-12, More preferably, it is 4-8.
Examples of the compound that can constitute the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1, Examples thereof include, but are not limited to, 10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, and the like. These can be used alone or in combination of two or more.

  The kind of the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) is appropriately determined according to the use. The linear aliphatic dicarboxylic acid unit in the polyamide resin (A) retains heat resistance after heat sterilization of packaging materials and packaging containers, in addition to imparting excellent gas barrier properties to the polyamide resin composition of the present invention. From the viewpoint, it is preferable that at least one selected from the group consisting of an adipic acid unit, a sebacic acid unit, and a 1,12-dodecanedicarboxylic acid unit is contained in a total of 50 mol% in the linear aliphatic dicarboxylic acid unit. The content is more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less.

  The linear aliphatic dicarboxylic acid unit in the polyamide resin (A) is a linear adipic acid unit from the viewpoint of the gas barrier properties of the polyamide resin composition of the present invention and the thermal properties such as an appropriate glass transition temperature and melting point. It is preferable to contain 50 mol% or more in the aliphatic dicarboxylic acid unit. Further, the linear aliphatic dicarboxylic acid unit in the polyamide resin (A) is converted from the sebacic acid unit to the linear aliphatic dicarboxylic acid from the viewpoint of imparting appropriate gas barrier properties and molding processability to the polyamide resin composition of the present invention. Preferably, the acid unit contains 50 mol% or more, and when the polyamide resin composition of the present invention is used for applications requiring low water absorption, weather resistance, and heat resistance, 1,12-dodecanedicarboxylic acid units are used. It is preferable to contain 50 mol% or more in the linear aliphatic dicarboxylic acid unit.

1-2-2. In the case where the aromatic dicarboxylic acid unit polyamide resin (A) is used for the purpose of facilitating the molding processability of packaging materials and packaging containers, in addition to imparting further gas barrier properties to the polyamide resin composition of the present invention, It preferably contains an aromatic dicarboxylic acid unit represented by the formula (II-2).
In the general formula (II-2), Ar represents an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
Examples of the compound that can constitute the aromatic dicarboxylic acid unit represented by the general formula (II-2) include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, but are not limited thereto. is not. These can be used alone or in combination of two or more.

  The kind of the aromatic dicarboxylic acid unit represented by the general formula (II-2) is appropriately determined according to the use. The aromatic dicarboxylic acid unit in the polyamide resin (A) is a total of at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit in the aromatic dicarboxylic acid unit. The content is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less. is there. Among these, it is preferable to contain isophthalic acid and / or terephthalic acid in the aromatic dicarboxylic acid unit. The content ratio of the isophthalic acid unit to the terephthalic acid unit (isophthalic acid unit / terephthalic acid unit) is not particularly limited and is appropriately determined according to the application. For example, from the viewpoint of reducing the appropriate glass transition temperature and crystallinity, when the total of both units is 100, the molar ratio is preferably 0/100 to 100/0, more preferably 0/100 to 60/40, More preferably, it is 0 / 100-40 / 60, More preferably, it is 0 / 100-30 / 70.

［前記一般式（ＩＩＩ）〜（Ｖ）中、Ｒ、Ｒ¹及びＲ²はそれぞれ置換基を表し、Ａ¹〜Ａ³はそれぞれ単結合又は２価の連結基を表す。ただし、前記一般式（ＩＶ）においてＡ¹及びＡ²がともに単結合である場合を除く。］ 1-3. Tertiary hydrogen-containing carboxylic acid unit In the present invention, the tertiary hydrogen-containing carboxylic acid unit in the polyamide resin (A) has at least one amino group and carboxyl group from the viewpoint of polymerization of the polyamide resin (A). Each having two or more carboxyl groups. Specific examples include structural units represented by any of the following general formulas (III), (IV), or (V).

[In the general formulas (III) to (V), R, R ¹ and R ² each represent a substituent, and A ^{1 to} A ³ each represent a single bond or a divalent linking group. However, the case where both A ¹ and A ² in the general formula (IV) are single bonds is excluded. ]

  The polyamide resin (A) contains a tertiary hydrogen-containing carboxylic acid unit. By containing such a tertiary hydrogen-containing carboxylic acid unit as a copolymerization component, the polyamide resin (A) can exhibit excellent oxygen absorption performance.

In the present invention, the mechanism by which the polyamide resin (A) having a tertiary hydrogen-containing carboxylic acid unit exhibits good oxygen absorption performance has not yet been clarified, but is estimated as follows. In a compound that can constitute a tertiary hydrogen-containing carboxylic acid unit, an electron-withdrawing group and an electron-donating group are bonded to the same carbon atom, so that unpaired electrons existing on the carbon atom are energetic. It is considered that a very stable radical is generated by a phenomenon called a captodative effect that is stabilized in a stable manner. That is, the carboxyl group is an electron withdrawing group, and the carbon to which the adjacent tertiary hydrogen is bonded becomes electron deficient (δ ⁺ ), so the tertiary hydrogen also becomes electron deficient (δ ⁺ ) Dissociates as a radical. When oxygen and water are present here, it is considered that oxygen reacts with this radical to show oxygen absorption performance. It has also been found that the higher the humidity and temperature, the higher the reactivity.

In the general formulas (III) to (V), R, R ¹ and R ² each represent a substituent. Examples of the substituent represented by R, R ¹ and R ² in the present invention include a halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group (1 to 15, preferably 1 to 6). Linear, branched or cyclic alkyl groups having the following carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl Group), an alkenyl group (a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, such as a vinyl group, an allyl group), an alkynyl group (2 to 10, preferably Alkynyl group having 2 to 6 carbon atoms, for example, ethynyl group, propargyl group), aryl group (6 to 16, preferably 6 to 10 carbon atoms) Group, for example, phenyl group, naphthyl group), heterocyclic group (obtained by removing one hydrogen atom from 5- or 6-membered aromatic or non-aromatic heterocyclic compound, 1 to 12 , Preferably monovalent groups having 2 to 6 carbon atoms, such as 1-pyrazolyl group, 1-imidazolyl group, 2-furyl group, cyano group, hydroxyl group, nitro group, alkoxy group (1-10, Preferably a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, for example, a methoxy group, an ethoxy group, an aryloxy group (6 to 12, preferably 6 to 8 carbon atoms) An oxy group, such as a phenoxy group, an acyl group (formyl group, 2-10, preferably an alkylcarbonyl group having 2-6 carbon atoms, or 7-12, preferably 7-9 carbon atoms. Arylcarbonyl group having, for example, acetyl group, pivaloyl group, benzoyl group), amino group (amino group, 1-10, preferably alkylamino group having 1-6 carbon atoms, 6-12, preferably Is an anilino group having 6 to 8 carbon atoms, or a heterocyclic amino group having 1 to 12, preferably 2 to 6 carbon atoms, such as an amino group, a methylamino group, an anilino group), a mercapto group An alkylthio group (an alkylthio group having 1 to 10, preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group), an arylthio group (6 to 12, preferably 6 to 8 carbon atoms). An arylthio group having, for example, a phenylthio group), a heterocyclic thio group (2 to 10, preferably 2 to 6 carbon atoms having a heterocyclic thio group, for example, - benzothiazolylthio group), an imido group (2 to 10, preferably an imido group having 4 to 8 carbon atoms, for example, N- succinimido group, N- phthalimido group).

Among these functional groups, those having a hydrogen atom may be further substituted with the above groups, for example, an alkyl group substituted with a hydroxyl group (for example, hydroxyethyl group), an alkyl group substituted with an alkoxy group (For example, methoxyethyl group), an alkyl group substituted with an aryl group (for example, benzyl group), an aryl group substituted with an alkyl group (for example, p-tolyl group), an aryloxy group substituted with an alkyl group ( Examples thereof include, but are not limited to, 2-methylphenoxy group.
In addition, when a functional group is further substituted, the carbon number mentioned above shall not include the carbon number of the further substituent. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. The following description of the number of carbon atoms shall be similarly understood unless otherwise specified.

In the general formulas (IV) and (V), A ^{1 to} A ³ each represents a single bond or a divalent linking group. However, the case where both A ¹ and A ² in the general formula (IV) are single bonds is excluded. Examples of the divalent linking group include a linear, branched or cyclic alkylene group (C1-C12, preferably C1-C4 alkylene group such as a methylene group or ethylene group), an aralkylene group (carbon number). Examples thereof include aralkylene groups having 7 to 30 carbon atoms, preferably 7 to 13 carbon atoms, such as benzylidene groups, arylene groups (arylene groups having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms such as phenylene groups), and the like. These may further have a substituent, and examples of the substituent include the functional groups exemplified above as substituents represented by R, R ¹ and R ² . Examples thereof include, but are not limited to, an arylene group substituted with an alkyl group (for example, a xylylene group).

  The polyamide resin (A) preferably contains at least one structural unit represented by any one of the general formulas (III), (IV), and (V). Among these, from the viewpoint of improving the availability of raw materials and oxygen absorption, a carboxylic acid unit having tertiary hydrogen on the α-carbon (carbon atom adjacent to the carboxyl group) is more preferable, and is represented by the general formula (III). The structural unit is particularly preferred.

R in the general formula (III) is as described above. Among them, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are more preferable, and a substituted or unsubstituted C 1-6 carbon atom is more preferable. An alkyl group and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms are more preferred, and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group are particularly preferred.
Specific examples of preferable R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, hydroxymethyl group, 1- Examples thereof include, but are not limited to, a hydroxyethyl group, a mercaptomethyl group, a methylsulfanylethyl group, a phenyl group, a naphthyl group, a benzyl group, and a 4-hydroxybenzyl group. Among these, a methyl group, an ethyl group, an isopropyl group, a 2-methylpropyl group, and a benzyl group are more preferable.

Compounds that can constitute the structural unit represented by the general formula (III) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine, 2 -Although alpha-amino acids, such as phenylglycine, phenylalanine, tyrosine, histidine, tryptophan, proline, can be illustrated, it is not limited to these.
Moreover, as a compound which can comprise the structural unit represented by the said general formula (IV), (beta) -amino acids, such as 3-aminobutyric acid, can be illustrated, and the structural unit represented by the said general formula (V) is comprised. Examples of the compound that can be used include, but are not limited to, dicarboxylic acids such as methylmalonic acid, methylsuccinic acid, malic acid, and tartaric acid.
These may be any of D-form, L-form and racemate, or allo-form. Moreover, these can be used individually or in combination of 2 or more types.

  Among these, α-amino acids having tertiary hydrogen in the α carbon are particularly preferable from the viewpoints of availability of raw materials and oxygen absorption improvement. Among α-amino acids, alanine is most preferable from the viewpoints of ease of supply, inexpensive price, ease of polymerization, and low yellowness (YI) of the polymer. Since alanine has a relatively low molecular weight and a high copolymerization rate per 1 g of the polyamide resin (A), the oxygen absorption performance per 1 g of the polyamide resin (A) is good.

  Further, the purity of the compound that can constitute the tertiary hydrogen-containing carboxylic acid unit is 95% or more from the viewpoint of the influence on the polymerization such as the delay of the polymerization rate and the influence on the quality such as the yellowness of the polymer. Preferably, it is 98.5% or more, more preferably 99% or more. Further, sulfate ions and ammonium ions contained as impurities are preferably 500 ppm or less, more preferably 200 ppm or less, and still more preferably 50 ppm or less.

［前記一般式（ＶＩ）中、ｐは２〜１８の整数を表す。］
前記ω−アミノカルボン酸単位の含有量は、ポリアミド樹脂（Ａ）の全構成単位中、好ましくは０．１〜４９．９モル％、より好ましくは３〜４０モル％、更に好ましくは５〜３５モル％である。ただし、前記のジアミン単位、ジカルボン酸単位、３級水素含有カルボン酸単位、及びω−アミノカルボン酸単位の合計は１００モル％を超えないものとする。
前記一般式（ＶＩ）中、ｐは２〜１８の整数を表し、好ましくは３〜１６、より好ましくは４〜１４、更に好ましくは５〜１２である。 1-4. The ω-aminocarboxylic acid unit polyamide resin (A) is added to the diamine unit, the dicarboxylic acid unit and the tertiary hydrogen-containing carboxylic acid unit when the polyamide resin composition of the present invention requires flexibility or the like. In addition, an ω-aminocarboxylic acid unit represented by the following general formula (VI) may be further contained.

[In said general formula (VI), p represents the integer of 2-18. ]
The content of the ω-aminocarboxylic acid unit is preferably 0.1 to 49.9 mol%, more preferably 3 to 40 mol%, still more preferably 5 to 35 in all the structural units of the polyamide resin (A). Mol%. However, the total of the diamine unit, dicarboxylic acid unit, tertiary hydrogen-containing carboxylic acid unit, and ω-aminocarboxylic acid unit shall not exceed 100 mol%.
In said general formula (VI), p represents the integer of 2-18, Preferably it is 3-16, More preferably, it is 4-14, More preferably, it is 5-12.

  Examples of the compound that can constitute the ω-aminocarboxylic acid unit represented by the general formula (VI) include ω-aminocarboxylic acid having 5 to 19 carbon atoms and lactam having 5 to 19 carbon atoms. Examples of the ω-aminocarboxylic acid having 5 to 19 carbon atoms include 6-aminohexanoic acid and 12-aminododecanoic acid, and examples of the lactam having 5 to 19 carbon atoms include ε-caprolactam and laurolactam. However, it is not limited to these. These can be used alone or in combination of two or more.

  The ω-aminocarboxylic acid unit preferably contains 6-aminohexanoic acid units and / or 12-aminododecanoic acid units in a total of 50 mol% or more in the ω-aminocarboxylic acid unit, and the content is More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more, Preferably it is 100 mol% or less.

1-5. Relative viscosity is used for the degree of polymerization of the polyamide resin (A). The preferred relative viscosity of the polyamide resin (A) is preferably 1.8 to 4.2, more preferably 1.9 to 4.0, and still more preferably 2 from the viewpoint of the strength and appearance of the molded product and molding processability. 0.0 to 3.8.
The relative viscosity here is 96% measured in the same manner as the dropping time (t) measured by dissolving a 1 g polyamide resin (A) in 100 mL of 96% sulfuric acid at 25 ° C. with a Canon Fenceke viscometer. It is the ratio of the drop time (t ₀ ) of sulfuric acid itself, and is represented by the following formula.
Relative viscosity = t / t ₀

1-6. Terminal Amino Group Concentration The oxygen absorption rate of the polyamide resin composition of the present invention and the oxidative deterioration of the polyamide resin composition due to oxygen absorption can be controlled by changing the terminal amino group concentration of the polyamide resin (A). . In the present invention, from the viewpoint of the balance between oxygen absorption rate and oxidative degradation, the terminal amino group concentration of the polyamide resin (A) is preferably in the range of 5 to 150 μeq / g, more preferably 10 to 100 μeq / g, and still more preferably 15 ˜80 μeq / g.
In the oxygen-absorbing resin composition in which a transition metal compound is added to polymetaxylylene adipamide, which is a conventional technique, oxygen absorption performance tends to decrease when the terminal amino group concentration increases. When the terminal amino group concentration affects other desired performance, the performance and oxygen absorption performance may not be compatible. However, in the polyamide resin composition of the present invention, if the terminal amino group concentration is within the above-mentioned range, there is no significant difference in the oxygen absorption performance of the polyamide by the transition metal compound. It is excellent in that the terminal amino group concentration of the resin (A) can be adjusted.

1-7. Method for Producing Polyamide Resin (A) The polyamide resin (A) comprises a diamine component that can constitute the diamine unit, a dicarboxylic acid component that can constitute the dicarboxylic acid unit, and the tertiary hydrogen-containing carboxylic acid unit. Can be produced by polycondensation of a tertiary hydrogen-containing carboxylic acid component and an ω-aminocarboxylic acid component capable of constituting the ω-aminocarboxylic acid unit, if necessary, and adjusting polycondensation conditions, etc. The degree of polymerization can be controlled. A small amount of monoamine or monocarboxylic acid may be added as a molecular weight modifier during polycondensation. Further, in order to suppress the polycondensation reaction and obtain a desired degree of polymerization, the ratio (molar ratio) between the diamine component and the carboxylic acid component constituting the polyamide resin (A) may be adjusted from 1.

  Examples of the polycondensation method of the polyamide resin (A) include, but are not limited to, a reactive extrusion method, a pressurized salt method, an atmospheric pressure dropping method, and a pressure dropping method. Moreover, the one where reaction temperature is as low as possible can suppress the yellowing and gelatinization of a polyamide resin (A), and the polyamide resin (A) of the stable property is obtained.

1-7-1. Reactive extrusion method In the reactive extrusion method, a polyamide (polyamide corresponding to the precursor of the polyamide resin (A)) comprising a diamine component and a dicarboxylic acid component or a polyamide (polyamide comprising a diamine component, a dicarboxylic acid component and an ω-aminocarboxylic acid component. This is a method in which a polyamide corresponding to a precursor of the resin (A)) and a tertiary hydrogen-containing carboxylic acid component are reacted by melting and kneading with an extruder. This is a method of incorporating a tertiary hydrogen-containing carboxylic acid component into a polyamide skeleton by an amide exchange reaction. In order to sufficiently react, a screw suitable for reactive extrusion is used, and a twin screw extruder having a large L / D is used. It is preferable to use it. When producing a polyamide resin (A) containing a small amount of a tertiary hydrogen-containing carboxylic acid unit, it is a simple method and suitable.

1-7-2. Pressure Salt Method The pressure salt method is a method of performing melt polycondensation under pressure using nylon salt as a raw material. Specifically, after preparing a nylon salt aqueous solution consisting of a diamine component, a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and an ω-aminocarboxylic acid component as necessary, the aqueous solution is concentrated, Next, the temperature is raised under pressure, and polycondensation is performed while removing condensed water. While gradually returning the inside of the can to normal pressure, the temperature was raised to about the melting point of polyamide resin (A) + 10 ° C. and held, and further, the pressure was gradually reduced to −0.02 MPaG and kept at the same temperature. Continue polycondensation. When a constant stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide resin (A).
The pressurized salt method is useful when a volatile component is used as a monomer, and is a preferable polycondensation method when the copolymerization rate of the tertiary hydrogen-containing carboxylic acid component is high. In particular, it is suitable for producing a polyamide resin (A) containing 15 mol% or more of tertiary hydrogen-containing carboxylic acid units in all structural units of the polyamide resin (A). By using the pressurized salt method, transpiration of the tertiary hydrogen-containing carboxylic acid component can be prevented, and further, polycondensation between the tertiary hydrogen-containing carboxylic acid components can be suppressed, and the polycondensation reaction can proceed smoothly. Therefore, a polyamide resin (A) excellent in properties can be obtained.

1-7-3. Normal pressure dropping method In the normal pressure dropping method, a diamine component is added to a mixture obtained by heating and melting a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and, if necessary, an ω-aminocarboxylic acid component under normal pressure. It is continuously dropped and polycondensed while removing condensed water. The polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the produced polyamide resin (A).
Compared with the pressurized salt method, the atmospheric pressure dropping method does not use water to dissolve the salt, so the yield per batch is large, and the reaction rate is not required for vaporization / condensation of raw material components. The process time can be shortened.

1-7-4. Pressure dropping method In the pressure dropping method, first, a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and, if necessary, an ω-aminocarboxylic acid component are charged into a polycondensation can, and each component is stirred. Melt mix to prepare the mixture. Next, the diamine component is continuously dropped into the mixture while the inside of the can is preferably pressurized to about 0.3 to 0.4 MPaG, and polycondensation is performed while removing condensed water. At this time, the polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the produced polyamide resin (A). When the set molar ratio is reached, the dropping of the diamine component is terminated, and while gradually raising the inside of the can to normal pressure, the temperature is raised to about the melting point of the polyamide resin (A) + 10 ° C. and held, and then −0.02 MPaG The pressure is gradually reduced until it is maintained at the same temperature, and the polycondensation is continued. When a constant stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide resin (A).
Like the pressurized salt method, the pressure dropping method is useful when a volatile component is used as a monomer, and is a preferred polycondensation method when the copolymerization rate of the tertiary hydrogen-containing carboxylic acid component is high. . In particular, it is suitable for producing a polyamide resin (A) containing 15 mol% or more of tertiary hydrogen-containing carboxylic acid units in all structural units of the polyamide resin (A). By using the pressure dropping method, the transpiration of the tertiary hydrogen-containing carboxylic acid component can be prevented, and further, the polycondensation between the tertiary hydrogen-containing carboxylic acid components can be suppressed, and the polycondensation reaction can proceed smoothly. Therefore, a polyamide resin (A) excellent in properties can be obtained. Furthermore, since the pressure drop method does not use water for dissolving the salt compared to the pressure salt method, the yield per batch is large, and the reaction time can be shortened as in the atmospheric pressure drop method. It is possible to obtain a polyamide resin (A) having a low yellowness, which can be suppressed.

1-7-5. Step for increasing the degree of polymerization The polyamide resin (A) produced by the above polycondensation method can be used as it is, but may be subjected to a step for further increasing the degree of polymerization. Further examples of the step of increasing the degree of polymerization include reactive extrusion in an extruder and solid phase polymerization. As a heating device used in solid phase polymerization, a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer are provided. A conical heating device can be preferably used, but a known method and device can be used without being limited thereto. In particular, when solid-phase polymerization of the polyamide resin (A) is performed, the rotating drum type heating device in the above-described device can seal the inside of the system and perform polycondensation in a state where oxygen that causes coloring is removed. It is preferably used because it is easy to proceed.

1-7-6. Phosphorus atom-containing compound, alkali metal compound In the polycondensation of the polyamide resin (A), it is preferable to add a phosphorus atom-containing compound from the viewpoint of promoting the amidation reaction.
Examples of the phosphorus atom-containing compound include phosphinic acid compounds such as dimethylphosphinic acid and phenylmethylphosphinic acid; hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, Diphosphite compounds such as calcium hypophosphite and ethyl hypophosphite; phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid, phenylphosphone Phosphonic acid compounds such as sodium phosphate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate; phosphonous acid, sodium phosphonite, lithium phosphonite, Phosphonous compounds such as potassium sulfonate, magnesium phosphonite, calcium phosphonite, phenylphosphonite, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite; Phosphorous acid, sodium hydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphorous acid, etc. A phosphoric acid compound etc. are mentioned.
Among these, hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite and the like are particularly preferable because they are highly effective in promoting amidation reaction and excellent in anti-coloring effect. In particular, sodium hypophosphite is preferred. In addition, the phosphorus atom containing compound which can be used by this invention is not limited to these compounds.
The addition amount of the phosphorus atom-containing compound is preferably 0.1 to 1000 ppm, more preferably 1 to 600 ppm, still more preferably 5 to 400 ppm in terms of the phosphorus atom concentration in the polyamide resin (A). If it is 0.1 ppm or more, the polyamide resin (A) is difficult to be colored during the polymerization, and the transparency becomes high. If it is 1000 ppm or less, the polyamide resin (A) is hardly gelled, and it is possible to reduce the mixing of fish eyes considered to be caused by the phosphorus atom-containing compound into the molded product, so that the appearance of the molded product is improved.

Moreover, it is preferable to add an alkali metal compound in combination with the phosphorus atom-containing compound in the polycondensation system of the polyamide resin (A). In order to prevent coloring of the polyamide resin (A) during the polycondensation, it is necessary to make a sufficient amount of the phosphorus atom-containing compound present. However, in some cases, the polyamide resin (A) may be gelled. In order to adjust the amidation reaction rate, it is preferable to coexist an alkali metal compound.
As the alkali metal compound, alkali metal hydroxide, alkali metal acetate, alkali metal carbonate, alkali metal alkoxide, and the like are preferable. Specific examples of the alkali metal compound that can be used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate. Sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium carbonate and the like, but can be used without being limited to these compounds. The ratio (molar ratio) between the phosphorus atom-containing compound and the alkali metal compound is such that the phosphorus atom-containing compound / alkali metal compound = 1.0 / 0.05 to from the viewpoint of controlling the polymerization rate and reducing the yellowness. The range of 1.0 / 1.5 is preferable, more preferably 1.0 / 0.1 to 1.0 / 1.2, and still more preferably 1.0 / 0.2 to 1.0 / 1. 1.

2. Colorant (B)
The colorant (B) used in the present invention contains one or more metal atoms selected from iron, manganese, copper and zinc. Among these metals, iron, copper and manganese are preferable from the viewpoint of oxygen absorption capacity and heat aging resistance.

  The colorant (B) is not particularly limited as long as it is a colorant containing one or more metal atoms selected from iron, manganese, copper, and zinc, and may be any of dyes and pigments, organic pigments and inorganic Any of pigments may be used.

  Organic pigments include phthalocyanine blue (copper phthalocyanine α crystal; pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, copper phthalocyanine β crystal; pigment blue 15: 3, pigment blue 15: 4), phthalocyanine green ( Copper phthalocyanine pigments such as halogenated copper phthalocyanine, pigment green 7, pigment green 36); I. And organic manganese complexes such as CI Pigment Red 48: 4, CI Pigment Red 52: 2, and CI Pigment Red 58: 4.

As organic pigments, pigment red 179 and pigment violet 29 having a perylene structure, pigment violet 19 having a quinacridone structure, pigment yellow 183 having a quinophthalone structure, pigment yellow 95 and pigment red 220 having a condensed azo structure, and a monoazo structure Pigment Yellow 191, Pigment Yellow 95 having anthracene structure, Pigment Yellow 147, Pigment Red 177, Pigment Yellow 110 having an isoindolinone structure, Pigment Orange 64 having a benzimidazolone structure, Pigment Yellow 180, Pigment Yellow 181 and Pigment Yellow 151, Pigment Red 254 having a diketoropyrrolopyrrole structure, naphthol structure Pigment Red 187 or the like having the like.
These organic pigments do not contain metals such as iron, manganese, copper and zinc as chemical structures. However, even a pigment that does not contain a metal as a chemical structure may contain a metal in an actual product form. In the present invention, even if the organic pigment does not contain a metal as a chemical structure, in the actual product form, what is detected iron, manganese, copper and zinc by the analysis method described in the examples below, Included in “colorants having one or more metal atoms from metals such as iron, manganese, copper and zinc”.

Examples of inorganic pigments include metal powders, oxides, cyanides, sulfides, and phosphates.
Examples of the metal powder include bronze powder and zinc powder.
Specific examples of the oxide-based colorant include iron oxide-based colorants such as iron oxide (Pigment Red 101), iron black (black iron oxide), dial (red iron oxide), and iron oxide yellow (Pigment Yellow 42). And zinc oxide colorants such as zinc white (zinc oxide). In addition, a composite oxide containing two or more metals may be used. Specific examples thereof include a zinc-iron-chromium composite oxide (Pigment Brown 33) and a zinc-iron composite oxide (Pigment Yellow). 119), iron-manganese composite oxide (Pigment Black 26), iron-cobalt-chromium composite oxide (Pigment Black 27), zinc chromate (Pigment Yellow 36), and the like.
Specific examples of cyanide-based colorants include bitumen (ferrocyanide) and the like.
Specific examples of the sulfide colorant include zinc sulfide.
Specific examples of the phosphate colorant include manganese violet (manganese ammonium pyrophosphate).

  The colorant (B) contains one or more metal atoms selected from oxides and cyanides containing at least one metal atom selected from iron, manganese, copper and zinc, and iron, manganese, copper and zinc. One or more colorants selected from anthracene colorants and copper phthalocyanine colorants are preferred, and one or more colorants selected from iron oxide colorants, ferrocyanide colorants, and copper phthalocyanine colorants. More preferred.

The particle size of the colorant (B) used in the present invention is preferably 0.5 mm or less, more preferably 0.1 mm or less. When the particle size of the metal compound is 0.5 mm or less, the metal compound can be uniformly dispersed throughout when mixed with the thermoplastic resin.
The particle diameter of the colorant dispersed in the thermoplastic resin is preferably 100 μm or less, more preferably 70 μm or less, from the viewpoints of colorability, mechanical property retention, barrier properties, and the like. On the other hand, the minor axis is preferably 50 μm or less.

3. Additives The polyamide resin composition of the present invention may contain additives within a range not impairing the effects of the present invention, depending on the required use and performance. Examples of additives include lubricants, crystallization nucleating agents, whitening inhibitors, matting agents, heat stabilizers, weathering stabilizers, UV absorbers, plasticizers, flame retardants, antistatic agents, anti-coloring agents, and antioxidants. Agents and the like. Further, if necessary, other resins and elastomers may be melt-mixed with the polyamide resin composition of the present invention.

3-1. Anti-whitening agent In the polyamide resin composition of the present invention, it is preferable to add a diamide compound and / or a diester compound as a whitening inhibitor after hot water treatment or after a long period of time. Diamide compounds and diester compounds are effective in suppressing whitening due to precipitation of oligomers. A diamide compound and a diester compound may be used alone or in combination.

  The diamide compound is preferably a diamide compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms. When the aliphatic dicarboxylic acid has 8 or more carbon atoms and the diamine has 2 or more carbon atoms, a whitening prevention effect can be expected. Further, when the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diamine has 10 or less carbon atoms, uniform dispersion in the resin composition is good. The aliphatic dicarboxylic acid may have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred. One kind of diamide compound may be used, or two or more kinds may be used in combination.

Examples of the aliphatic dicarboxylic acid include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30). Examples of the diamine include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine, and bis (aminomethyl) cyclohexane. A diamide compound obtained by combining these is preferred.
A diamide compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diamine mainly comprising ethylenediamine, or a diamide compound obtained from an aliphatic dicarboxylic acid mainly comprising montanic acid and a diamine having 2 to 10 carbon atoms is particularly preferred. Is a diamide compound obtained from an aliphatic dicarboxylic acid mainly composed of stearic acid and a diamine mainly composed of ethylenediamine.

  As the diester compound, a diester compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms is preferable. When the aliphatic dicarboxylic acid has 8 or more carbon atoms and the diol has 2 or more carbon atoms, an effect of preventing whitening can be expected. Further, when the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diol has 10 or less carbon atoms, uniform dispersion in the resin composition is good. The aliphatic dicarboxylic acid may have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred. One type of diester compound may be used, or two or more types may be used in combination.

Examples of the aliphatic dicarboxylic acid include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30). Examples of the diol include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, and cyclohexanedimethanol. A diester compound obtained by combining these is preferred.
Particularly preferred are diester compounds obtained from an aliphatic dicarboxylic acid mainly composed of montanic acid and a diol mainly composed of ethylene glycol and / or 1,3-butanediol.

  The content of the diamide compound and / or diester compound is preferably 0.005 to 0.5% by mass, more preferably 0.05 to 0.5% by mass, and still more preferably 0 with respect to 100% by mass of the resin composition. .12 to 0.5% by mass. By adding 0.005% by mass or more with respect to 100% by mass of the resin composition and using it together with the crystallization nucleating agent, a synergistic effect of preventing whitening can be expected. Further, when the addition amount is 0.5% by mass or less with respect to 100% by mass of the resin composition, it becomes possible to keep the fog value of the molded product obtained by molding the polyamide resin composition of the present invention low. .

3-2. Crystallization Nucleating Agent In the polyamide resin composition of the present invention, it is preferable to add a crystallization nucleating agent. In addition to improving transparency, it is also effective for whitening due to crystallization after hydrothermal treatment and after a long period of time. By adding a crystallization nucleating agent to the polyamide resin composition, the spherulite size can be visualized. It can be suppressed by setting it to 1/2 or less of the wavelength of light. In addition, when a diamide compound and / or a diester compound and a crystallization nucleating agent are used in combination, whitening suppression far superior to the degree expected from each whitening suppression effect can be obtained due to their synergistic effect.

  As inorganic crystallization nucleating agents, glass fillers (glass fibers, crushed glass fibers (milled fibers), glass flakes, glass beads, etc.), calcium silicate fillers (wollastonite, etc.), mica , Talc (powder talc and granular talc with rosin as binder), kaolin, potassium titanate whisker, boron nitride, layered silicate clay, nanofiller, carbon fiber, etc., usually used for thermoplastic resin It may be a thing and may use these 2 or more types together. The maximum diameter of the inorganic crystallization nucleating agent is preferably 0.01 to 5 μm. In particular, powder talc having a particle size of 3.0 μm or less is preferable, powder talc having a particle size of about 1.5 to 3.0 μm is more preferable, and powder talc having a particle size of 2.0 μm or less is particularly preferable. In addition, granular talc using rosin as a binder in this powdered talc is particularly preferable because the dispersed state in the polyamide resin composition is good. Organic crystallization nucleating agents include crystallization nucleating agents, capsules consisting of bilayer films of micro to nano level size, bis (benzylidene) sorbitol-based or phosphorus-based transparent crystal nucleating agents, rosinamide-based Gelling agents are preferred, and bis (benzylidene) sorbitol crystallization nucleating agents are particularly preferred.

  The content of the crystallization nucleating agent is preferably 0.005 to 2.0 mass%, more preferably 0.01 to 1.5 mass%, with respect to 100 mass% of the polyamide resin (A). By adding these at least one crystallization nucleating agent to the polyamide resin composition in combination with a diamide compound and / or a diester compound, a synergistic effect of preventing whitening can be obtained. In particular, the inorganic crystallization nucleating agent such as talc is 0.05 to 1.5% by mass with respect to 100% by mass of the polyamide resin (A), and the organic crystallization nuclei such as bis (benzylidene) sorbitol crystallization nucleating agent. The agent is particularly preferably used in an amount of 0.01 to 0.5% by mass with respect to 100% by mass of the polyamide resin (A).

  The bis (benzylidene) sorbitol-based crystallization nucleating agent is selected from bis (benzylidene) sorbitol and bis (alkylbenzylidene) sorbitol, and is a condensation product (diacetal compound) produced by acetalization reaction of sorbitol and benzaldehyde or alkyl-substituted benzaldehyde. And can be conveniently prepared by various synthetic methods known in the art. Here, the alkyl may be linear or cyclic, and may be saturated or unsaturated. A common synthesis method uses the reaction of 1 mole of D-sorbitol with about 2 moles of aldehyde in the presence of an acid catalyst. The reaction temperature varies widely depending on the characteristics (melting point, etc.) of the aldehyde used as the starting material for the reaction. The reaction medium may be an aqueous medium or a non-aqueous medium. One preferred method that can be used to prepare the diacetal is described in US Pat. No. 3,721,682. Although this disclosure is limited to benzylidene sorbitols, the bis (alkylbenzylidene) sorbitols used in the present invention can also be conveniently prepared by the methods described therein.

  Specific examples of the bis (benzylidene) sorbitol crystallization nucleating agent (diacetal compound) include bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (n-propylbenzylidene) sorbitol, bis (p -Isopropylbenzylidene) sorbitol, bis (p-isobutylbenzylidene) sorbitol, bis (2,4-dimethylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (2,4,5-trimethylbenzylidene) sorbitol, Examples thereof include bis (2,4,6-trimethylbenzylidene) sorbitol, bis (4-biphenylbenzylidene) sorbitol and the like.

  Examples of alkyl-substituted benzaldehydes suitable for preparing bis (benzylidene) sorbitol-based crystallization nucleating agents include p-methylbenzaldehyde, n-propylbenzaldehyde, p-isopropylbenzaldehyde, 2,4-dimethylbenzaldehyde, 3,4 -Dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 4-biphenylbenzaldehyde.

  When a crystallization nucleating agent such as talc, mica, or clay is added to the polyamide resin composition, the crystallization speed is accelerated twice or more as compared with the additive-free polyamide resin composition. There is no problem for injection molding applications that require a high molding cycle, but for drawn films and deep drawn cups formed from sheets, if the crystallization speed is too high, crystallization will not allow the film or sheet to be stretched and breakage will occur. Or formability such as unevenness of elongation is extremely reduced. However, bis (benzylidene) sorbitol-based crystallization nucleating agents do not accelerate the crystallization speed even when added to a polyamide resin composition, and are used for applications such as deep drawn cups formed from stretched films and sheets. The case is preferred.

  Further, the bis (benzylidene) sorbitol-based crystallization nucleating agent not only suppresses whitening but also improves oxygen barrier properties when added to the polyamide resin composition. It is particularly preferable to use a crystallization nucleating agent of bis (benzylidene) sorbitol, which can obtain both effects of suppressing whitening and improving oxygen barrier properties.

3-3. Layered silicate The polyamide resin composition of the present invention may contain a layered silicate. By adding layered silicate, not only oxygen gas barrier property but also barrier property against gas such as carbon dioxide gas can be imparted to the polyamide resin composition.

  The layered silicate is a 2-octahedral or 3-octahedral layered silicate having a charge density of 0.25 to 0.6. Examples of the 2-octahedral type include montmorillonite, beidellite, and the like. Examples of the octahedron type include hectorite and saponite. Among these, montmorillonite is preferable.

  The layered silicate is preferably obtained by expanding an interlayer of the layered silicate by previously bringing an organic swelling agent such as a polymer compound or an organic compound into contact with the layered silicate. As the organic swelling agent, a quaternary ammonium salt can be preferably used. Preferably, a quaternary ammonium salt having at least one alkyl group or alkenyl group having 12 or more carbon atoms is used.

  Specific examples of organic swelling agents include trimethyl dodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, trimethyl alkyl decyl ammonium salt, trimethyl alkyl decyl ammonium salt; trimethyl octadecenyl ammonium salt Trimethylalkenylammonium salts such as trimethyloctadecadienylammonium salt; triethylalkylammonium salts such as triethyldodecylammonium salt, triethyltetradecylammonium salt, triethylhexadecylammonium salt, triethyloctadecylammonium salt; tributyldodecylammonium salt, tributyltetradecyl Ammonium salt, tributyl hexadecyl ammonium salt, tri Tributylalkylammonium salts such as tiloctadecylammonium salt; dimethyldialkylammonium salts such as dimethyldidodecylammonium salt, dimethylditetradecylammonium salt, dimethyldihexadecylammonium salt, dimethyldioctadecylammonium salt, dimethylditallowammonium salt; dimethyl Dioctadecenyl ammonium salt, dimethyl dialkenyl ammonium salt such as dimethyl dioctadecadienyl ammonium salt; diethyl didodecyl ammonium salt, diethyl ditetradecyl ammonium salt, diethyl dihexadecyl ammonium salt, diethyl dioctadecyl ammonium salt, etc. Diethyl dialkyl ammonium salt; dibutyl didodecyl ammonium salt, dibutyl ditetradecyl ammonium salt, dibu Dibutyl dialkyl ammonium salts such as rudihexadecyl ammonium salt and dibutyl dioctadecyl ammonium salt; Methyl benzyl dialkyl ammonium salts such as methyl benzyl dihexadecyl ammonium salt; Dibenzyl dialkyl ammonium salts such as dibenzyl dihexadecyl ammonium salt; Tridodecyl Trialkylmethylammonium salts such as methylammonium salt, tritetradecylmethylammonium salt, trioctadecylmethylammonium salt; trialkylethylammonium salts such as tridodecylethylammonium salt; trialkylbutylammonium salts such as tridodecylbutylammonium salt; 4-amino-n-butyric acid, 6-amino-n-caproic acid, 8-aminocaprylic acid, 10-aminodecanoic acid, 12-aminodode Examples include ω-amino acids such as canic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. In addition, hydroxyl group and / or ether group-containing ammonium salts, among them, methyl dialkyl (PAG) ammonium salt, ethyl dialkyl (PAG) ammonium salt, butyl dialkyl (PAG) ammonium salt, dimethyl bis (PAG) ammonium salt, diethyl bis (PAG) ) Ammonium salt, dibutyl bis (PAG) ammonium salt, methyl alkyl bis (PAG) ammonium salt, ethyl alkyl bis (PAG) ammonium salt, butyl alkyl bis (PAG) ammonium salt, methyl tri (PAG) ammonium salt, ethyl tri (PAG) ammonium Salt, butyltri (PAG) ammonium salt, tetra (PAG) ammonium salt (wherein alkyl is carbon number such as dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc.) A quaternary ammonium containing at least one alkylene glycol residue such as a polyalkylene glycol residue, preferably a polyethylene glycol residue or a polypropylene glycol residue having 20 or less carbon atoms). Salts can also be used as organic swelling agents. Among them, trimethyldodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, dimethyl didodecyl ammonium salt, dimethyl ditetradecyl ammonium salt, dimethyl dihexadecyl ammonium salt, dimethyl dioctadecyl ammonium salt, dimethyl A ditallow ammonium salt is preferred. These organic swelling agents can be used alone or as a mixture of a plurality of types.

  The content of the layered silicate treated with the organic swelling agent is preferably 0.5 to 8% by mass, more preferably 1 to 6% by mass, and further preferably 2 to 5% with respect to 100% by mass of the polyamide resin composition. % By mass. If it is 0.5 mass% or more, the effect of improving the gas barrier property is sufficiently obtained, and if it is 8 mass% or less, problems such as pinholes due to deterioration of the flexibility of the polyamide resin composition hardly occur.

  In the polyamide resin composition, the layered silicate is preferably uniformly dispersed without locally agglomerating. The uniform dispersion here means that the layered silicate is separated into a flat plate shape in the polyamide resin composition, and 50% or more of them have an interlayer distance of 5 nm or more. Here, the interlayer distance refers to the distance between the centers of gravity of the flat objects. The larger the distance, the better the dispersion state, the better the appearance such as transparency, and the better the gas barrier properties such as oxygen and carbon dioxide.

3-4. Oxidizing organic compound In order to further enhance the oxygen absorption performance of the polyamide resin composition, an oxidizing organic compound may be added as long as the effects of the present invention are not impaired.
Oxidizing organic compounds are organic compounds that are oxidized automatically in the presence of oxygen or in the presence of any one of catalyst, heat, light, moisture, etc., and hydrogen can be easily extracted. Those having active carbon atoms that can be used in the following are preferred. Specific examples of such activated carbon atoms include those containing a carbon atom adjacent to a carbon-carbon double bond, a tertiary carbon atom having a carbon side chain attached thereto, and an active methylene group.
For example, vitamin C and vitamin E are also examples of oxidizing organic compounds. It also oxidizes polymers such as polypropylene that have tertiary hydrogen that is easily oxidized to molecules, and compounds that contain or contain carbon-carbon double bonds in the molecule, such as butadiene and isoprene. As an example of the organic compound. Among these, from the viewpoint of oxygen absorption capacity and processability, compounds and polymers having a carbon-carbon double bond are preferred, compounds containing a carbon-carbon double bond having 4 to 20 carbon atoms, and units derived therefrom. An oligomer or polymer containing is more preferred.
The content of the oxidizing organic compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and further preferably 0.5 to 3% by mass with respect to 100% by mass of the resin composition. is there.

3-5. Anti-gelling / fish eye reducing agent In the polyamide resin composition of the present invention, one or more carboxylic acids selected from sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate and derivatives thereof It is preferable to add acid salts. Examples of the derivative include 12-hydroxystearic acid metal salts such as calcium 12-hydroxystearate, magnesium 12-hydroxystearate, and sodium 12-hydroxystearate. By adding the carboxylic acid salts, it is possible to prevent gelation of the polyamide resin composition that occurs during the molding process and to reduce fish eyes in the molded article, thereby improving the suitability of the molding process. It is particularly preferable to use sodium acetate having a high metal salt concentration per gram as a more effective gelling prevention, fish eye reduction, and anti-kogation prescription.

The amount of the carboxylate added is preferably 400 to 10,000 ppm, more preferably 800 to 5000 ppm, and still more preferably 1000 to 3000 ppm as the concentration in the polyamide resin composition. If it is 400 ppm or more, the thermal deterioration of the polyamide resin composition can be suppressed, and gelation can be prevented. Moreover, if it is 10000 ppm or less, a polyamide resin composition will not raise | generate a shaping | molding defect, and neither coloring nor whitening will occur. If carboxylate salts, which are basic substances, are present in the molten polyamide resin composition, it is presumed that the modification of the polyamide resin composition with heat is delayed to suppress the formation of a gel that is considered to be a final modified product.
The carboxylates described above are excellent in handling properties, and among them, metal stearate is preferable because it is inexpensive and has an effect as a lubricant, and can stabilize the molding process. Further, the shape of the carboxylate is not particularly limited, but when the powder and the smaller particle size are dry-mixed, it is easy to uniformly disperse in the oxygen absorption barrier layer. Is preferably 0.2 mm or less, and more preferably 0.1 mm or less.

3-6. Antioxidant In the polyamide resin composition of the present invention, it is preferable to add an antioxidant from the viewpoint of controlling oxygen absorption performance and suppressing deterioration of mechanical properties. Examples of the antioxidant include copper-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and thio-based antioxidants. Antioxidants and phosphorus antioxidants are preferred.

  Specific examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4′-butylidenebis (3-methyl). -6-tert-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio)- 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-tert-butylphenol), N, N′-hexamethylenebis (3,5-di-t -Butyl-4-hydroxy-hydroxycinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium, tris- (3,5-di-t-butyl-4) -Hydroxybenzyl) -isocyanurate, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol , Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,2′-methylene- Bis- (4-ethyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O -Cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-te Raoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, bis [3,3′-bis- (4′-hydroxy-3′-tert-butylphenyl) butyric acid] glycol ester, 1,3 5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, d-α-tocopherol, etc. It is done. These can be used alone or as a mixture thereof. Specific examples of commercially available hindered phenol compounds include Irganox 1010 and Irganox 1098 manufactured by BASF (both are trade names).

  Specific examples of phosphorus antioxidants include triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl- 4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol Examples thereof include organic phosphorus compounds such as diphosphite, tetra (tridecyl-4,4′-isopropylidenediphenyl) diphosphite, and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite. These can be used alone or as a mixture thereof.

  The content of the antioxidant can be used without particular limitation as long as it does not impair the various performances of the composition. However, from the viewpoint of controlling oxygen absorption performance and suppressing deterioration of mechanical properties, the polyamide resin composition is 100% by mass. Preferably it is 0.001 to 3 mass%, More preferably, it is 0.01 to 1 mass%.

4). Production method of polyamide resin composition The polyamide resin composition of the present invention can be produced by mixing the polyamide resin (A) and the colorant (B).
A conventionally well-known method can be used for mixing of the polyamide resin (A) and the colorant (B). For example, there is a method of mixing the polyamide resin (A) and the colorant (B) in a mixer such as a tumbler or a mixer. At that time, in order to prevent classification after mixing of the colorant (B), after a viscous liquid is attached to the polyamide resin (A) as a spreading agent, the colorant (B) is added and mixed. It can also be taken. It is also possible to employ a method in which the colorant (B) is dissolved in an organic solvent, this solution and the polyamide resin (A) are mixed, and simultaneously or later heated to remove the organic solvent and adhere to the polyamide. Furthermore, when melt-kneading using an extruder, a coloring agent (B) can also be added in an extruder using the supply apparatus different from a polyamide resin (A).

Moreover, the polyamide resin composition of the present invention can also be produced by a master batch method. As a specific method for producing the polyamide resin composition of the present invention, the step of obtaining a master batch by melt-mixing the colorant (B) and the thermoplastic resin (X), and the master batch as a polyamide resin (A) And a method including a step of melt kneading. The step of obtaining the master batch may be a step of obtaining a master batch by melting and mixing the colorant (B), the thermoplastic resin (X), and the surfactant, and the amount of the surfactant added in this case Is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the colorant (B).
As the thermoplastic resin (X), any resin such as polyolefin, polyester, polyamide and the like can be used. From the viewpoints of moldability, barrier properties and transparency, polyester is preferable, and polyethylene terephthalate is more preferable.
The polyamide resin composition of the present invention can also be produced by a masterbatch method without using the thermoplastic resin (X). In this case, the method for producing the polyamide resin composition of the present invention includes a step of melting and mixing a part of the polyamide resin (A) and the colorant (B) to obtain a master batch, and the master batch from the remaining polyamide. A method including a step of melt kneading with the resin (A) is preferable.
According to the master batch method using the thermoplastic resin (X), the colorant (B) can be uniformly dispersed in the polyamide resin composition, and the polyamide resin (A) and Reaction of the colorant (B) with the polyamide resin (A) can be suppressed from oxidative degradation.

  The above additives may be added to the polyamide resin (A) and / or the thermoplastic resin (X) in advance, or may be added during the production of the resin composition.

  In the case of a method using a master batch, the mass ratio [(B) / (X)] of the colorant (B) to the thermoplastic resin (X) should be 10 to 15000 mass ppm as the metal atom concentration. More preferably, it is 50-10000 mass ppm, More preferably, it is 100-5000 mass ppm. When the metal atom concentration is 10 mass ppm or more, the resulting polyamide resin composition has sufficient oxygen absorption capacity. Moreover, if a metal concentration is 15000 mass ppm or less, the whole quantity of a coloring agent (B) can be melt-mixed with a thermoplastic resin (X).

The thermoplastic resin (X) and the colorant (B) can be mixed by a melt kneading method using a conventionally known extruder. Moreover, a coloring agent (B) can also be added in an extruder using the supply apparatus different from a thermoplastic resin (X).
In addition, also when adding an additive etc., it can add by the method similar to the above-mentioned.

  Further, the mixing ratio of the polyamide resin (A) and the master batch depends on the concentration of the master batch, but considering the oxygen barrier property and oxygen absorbing ability of the polyamide resin (A) itself, the polyamide resin (A): master batch The batch mass ratio is preferably in the range of 99: 1 to 50:50.

5. Use of Polyamide Resin Composition The polyamide resin composition of the present invention can be used for any application that requires oxygen barrier properties and oxygen absorption performance. For example, the polyamide resin composition of the present invention may be filled alone in a sachet or the like and used as an oxygen absorbent.
Representative examples of the use of the polyamide resin composition of the present invention include, but are not limited to, molded materials such as packaging materials and packaging containers. The polyamide resin composition of the present invention can be processed and used as at least a part of the molded body. For example, the polyamide resin composition of the present invention can be used as at least a part of a film-like or sheet-like packaging material, and various pouches such as bottles, trays, cups, tubes, flat bags, standing pouches, etc. It can be used as at least part of a packaging container. The thickness of the layer made of the polyamide resin composition of the present invention is not particularly limited, but preferably has a thickness of 1 μm or more.

There are no particular limitations on the method for producing a molded product such as a packaging material or packaging container, and any method can be used. For example, for forming a film-like or sheet-like packaging material or a tube-like packaging material, a polyamide resin composition melted through a T die, a circular die, or the like can be produced by extruding from an attached extruder. . In addition, the film-form molded object obtained by the above-mentioned method can also be processed into a stretched film by extending | stretching this. The bottle-shaped packaging container can be obtained by injecting a molten polyamide resin composition into a mold from an injection molding machine to produce a preform, and then heating to a stretching temperature and blow-drawing.
Containers such as trays and cups are manufactured by injecting a molten polyamide resin composition into a mold from an injection molding machine, or by forming a sheet-like packaging material by a molding method such as vacuum molding or pressure molding. Can be obtained. The packaging material and the packaging container can be manufactured through various methods regardless of the above-described manufacturing method.

The molded body using the polyamide resin composition of the present invention may have a single layer structure or a multilayer structure.
The molded article having a single layer structure may be composed only of the polyamide resin composition of the present invention, or may be composed of a blend of the polyamide resin composition of the present invention and another resin.
In the case of a molded article having a multilayer structure, the layer configuration is not particularly limited, and the number and type of layers are not particularly limited. For example, when the layer formed from the polyamide resin composition of the present invention is a layer (P) and the other resin layer is a layer (Q), it consists of one layer (P) and one layer (Q). A P / Q configuration may be employed, and a Q / P / Q three-layer configuration comprising one layer (P) and two layers (Q) may be employed. Further, a five-layer configuration of Q1 / Q2 / P / Q2 / Q1 composed of one layer (P) and two types (4) of layers (Q) of the layer (Q1) and the layer (Q2) may be used. Furthermore, an arbitrary layer such as an adhesive layer (AD) may be included as necessary. For example, a seven-layer configuration of Q1 / AD / Q2 / P / Q2 / AD / Q1 may be used. When the molded body of the present invention is a multilayered molded body, the other resin layer (Q) may contain a colorant.
The molded article of the present invention preferably has a metal atom concentration of 1 to 5000 ppm by mass, more preferably 1 to 2000 ppm by mass, still more preferably 3 to 1000 ppm by mass, and particularly preferably 5 to 500 ppm by mass.

Since the packaging container using the polyamide resin composition of the present invention is excellent in oxygen absorption performance and oxygen barrier performance and excellent in flavor retention of contents, it is suitable for packaging various articles.
Preserved items include milk, dairy products, juice, coffee, tea, alcoholic beverages; liquid seasonings such as sauces, soy sauce, dressings, soups, stews, curries, infant foods, nursing foods, etc. Cooked foods; pasty foods such as jam and mayonnaise; fishery products such as tuna and fish and shellfish; dairy products such as cheese and butter; processed meat products such as meat, salami, sausage and ham; Eggs, noodles, cooked rice, cooked rice, processed rice products such as rice bran; powdered seasonings, powdered coffee, powdered milk for infants, powdered diet foods, dried vegetables, rice crackers, and other dried foods Chemicals such as agricultural chemicals and insecticides; pharmaceuticals; cosmetics; pet foods; miscellaneous goods such as shampoos, rinses and detergents; semiconductor integrated circuits and electronic devices; It can be.

  In addition, before and after the filling of these objects to be stored, the packaging container and the objects to be stored can be sterilized in a form suitable for the objects to be stored. Sterilization methods include hot water treatment at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultra-high temperature heat treatment at 130 ° C. or higher, electromagnetic wave sterilization of ultraviolet rays, microwaves, gamma rays, etc., ethylene oxide And gas sterilization such as hydrogen peroxide and hypochlorous acid.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
In the following examples, regarding the units constituting the copolymer,
The unit derived from metaxylylenediamine is “MXDA”,
The unit derived from adipic acid is “AA”,
The unit derived from isophthalic acid is “IPA”,
A unit derived from L-alanine is referred to as “L-Ala”.
Polymetaxylylene adipamide is referred to as “N-MXD6”.

  The α-amino acid content, relative viscosity, terminal amino group concentration, glass transition temperature and melting point of the polyamide resin obtained in Production Example were measured by the following methods. Moreover, the film was produced from the polyamide resin obtained by the manufacture example, and the oxygen absorption amount was measured with the following method.

(1) α-amino acid content
The α-amino acid content of the polyamide resin was quantified using ¹ H-NMR (400 MHz, manufactured by JEOL Ltd., trade name: JNM-AL400, measurement mode: NON ( ¹ H)). Specifically, a 5 mass% solution of polyamide resin was prepared using formic acid-d as a solvent, and ¹ H-NMR measurement was performed.

(2) Relative viscosity 1 g of the pellet-like sample was precisely weighed and dissolved in 100 ml of 96% sulfuric acid at 20-30 ° C. with stirring. After completely dissolving, 5 ml of the solution was quickly taken into a Cannon-Fenceke viscometer and allowed to stand for 10 minutes in a constant temperature bath at 25 ° C., and then the drop time (t) was measured. Further, the dropping time (t ₀ ) of 96% sulfuric acid itself was measured in the same manner. The relative viscosity was calculated from t and t _{0 according} to the following formula.
Relative viscosity = t / t ₀

(3) Terminal amino group concentration [NH ₂ ]
The polyamide resin is precisely weighed and dissolved in a phenol / ethanol = 4/1 volume solution by stirring at 20-30 ° C. After complete dissolution, the inner wall of the container is washed with 5 ml of methanol while stirring, and 0.01 mol / L hydrochloric acid is dissolved. The terminal amino group concentration [NH ₂ ] was determined by neutralization titration with an aqueous solution.

(4) Glass transition temperature and melting point DSC measurement (differential scanning calorimetry) using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60) under a nitrogen stream at a heating rate of 10 ° C / min. The glass transition temperature (Tg) and the melting point (Tm) were determined.

(5) Oxygen absorption amount Using a 30mmφ twin screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.) equipped with a T die, the thickness of the polyamide resin was increased from the polyamide resin at a cylinder T die temperature of (polyamide resin melting point + 20 ° C). An unstretched single layer film having a thickness of about 100 μm was formed.
Two test pieces of 10 cm x 10 cm cut out from the produced unstretched single layer film were charged into a 25 cm x 18 cm three-side sealed bag made of an aluminum foil laminated film together with cotton containing 10 ml of water, and the amount of air in the bag Was sealed to 400 ml. The humidity in the bag was 100% RH (relative humidity). After storing at 40 ° C. for 7 days, after 14 days, and after 28 days, the oxygen concentration in the bag was measured with an oxygen concentration meter (trade name: LC-700F, manufactured by Toray Engineering Co., Ltd.). The amount of oxygen absorbed was calculated from the oxygen concentration.

Production Example 1 (Production of polyamide resin 1)
Weighed precisely in a pressure-resistant reaction vessel with an internal volume of 50 L equipped with a stirrer, partial condenser, full condenser, pressure regulator, thermometer, dripping tank and pump, aspirator, nitrogen inlet pipe, bottom exhaust valve, and strand die. Adipic acid (Asahi Kasei Chemicals Co., Ltd.) 13000 g (88.96 mol), L-alanine (Sinogel amino acid co.ltd) 880.56 g (9.88 mol), sodium hypophosphite 11.7 g (0.11 mol) Then, 6.06 g (0.074 mol) of sodium acetate was added, and after sufficiently replacing with nitrogen, the inside of the reaction vessel was sealed, and the temperature was raised to 170 ° C. with stirring while keeping the inside of the vessel at 0.4 MPa. After reaching 170 ° C., dropping of 12082.2 g (88.71 mol) of metaxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Inc.) stored in the dropping tank into the molten raw material in the reaction vessel was started, While maintaining 0.4 MPa, the temperature inside the reaction vessel was continuously raised to 240 ° C. while removing the condensed water produced outside the system. After completion of the dropwise addition of metaxylylenediamine, the inside of the reaction vessel was gradually returned to normal pressure, and then the inside of the reaction vessel was reduced to 80 kPa using an aspirator to remove condensed water. After observing the stirring torque of the stirrer during decompression, stop stirring when the specified torque is reached, pressurize the inside of the reaction tank with nitrogen, open the bottom drain valve, extract the polymer from the strand die and form a strand Cooled and pelletized with a pelletizer. Next, this pellet was charged into a stainless steel drum-type heating device and rotated at 5 rpm. The atmosphere in the reaction system was raised from room temperature to 140 ° C. under a small nitrogen flow. When the reaction system temperature reached 140 ° C., the pressure was reduced to 1 torr or less, and the system temperature was further increased to 180 ° C. in 110 minutes. From the time when the system temperature reached 180 ° C., the solid state polymerization reaction was continued at the same temperature for 180 minutes. After completion of the reaction, the decompression was terminated, the system temperature was lowered under a nitrogen stream, and the pellet was taken out when the temperature reached 60 ° C. to obtain an MXDA / AA / L-Ala copolymer (polyamide resin 1). . In addition, the preparation composition ratio of each monomer was metaxylylenediamine: adipic acid: L-alanine = 47.3: 47.4: 5.3 (mol%).

Production Example 2 (Production of polyamide resin 2)
MXDA / AA in the same manner as in Production Example 1 except that the composition ratio of each monomer was metaxylylenediamine: adipic acid: L-alanine = 44.4: 44.5: 11.1 (mol%). / L-Ala copolymer (polyamide resin 2) was obtained.

Production Example 3 (Production of polyamide resin 3)
MXDA / AA in the same manner as in Production Example 1 except that the composition ratio of each monomer was metaxylylenediamine: adipic acid: L-alanine = 33.3: 33.4: 33.3 (mol%). / L-Ala copolymer (polyamide resin 3) was obtained.

Production Example 4 (Production of polyamide resin 4)
The dicarboxylic acid component was changed to a mixture of isophthalic acid (manufactured by ADI International Chemical Co., Ltd.) and adipic acid, and the composition ratio of each monomer was changed to metaxylylenediamine: adipic acid: isophthalic acid: L- MXDA / AA / IPA / L-Ala copolymer (polyamide resin 4) in the same manner as in Production Example 1 except that alanine = 44.3: 39.0: 5.6: 11.1 (mol%) Got.

Production Example 5 (Production of polyamide resin 5)
N-MXD6 was carried out in the same manner as in Production Example 1 except that L-alanine was not added and the charged composition ratio of each monomer was metaxylylenediamine: adipic acid = 49.8: 50.2 (mol%). (Polyamide resin 5) was obtained.

  Table 1 shows the charged monomer composition of the polyamide resins 1 to 5 and the measurement results of the α-amino acid content, relative viscosity, terminal amino group concentration, glass transition temperature, melting point, and oxygen absorption amount of the obtained polyamide resin.

MB Production Example 1 (Manufacture of master batch 1)
Isophthalic acid copolymerized polyethylene terephthalate (PET) (manufactured by Nippon Unipet Co., Ltd., grade name: BK2180) is used as the thermoplastic resin (X), and copper phthalocyanine blue colorant (manufactured by BASF Corporation) is used as the colorant (B). (Product name: Heliogen Blue K7090, copper content: 6.5%) was dry blended to 4000 ppm with respect to PET, using a twin screw extruder equipped with a full flight screw of φ32 mm, rotating at 80 rpm, The melt-mixed mixture at 265 ° C. was extruded into a strand shape, air-cooled, and pelletized to obtain master batch pellets (master batch 1). Subsequently, the metal atoms contained in the obtained master batch 1 were quantified by the following method. The results are shown in Table 2.

<Quantification of metal atoms in colorant and masterbatch>
A master batch or 2 g of the colorant was precisely weighed in a platinum crucible, and after pre-combustion, it was ashed in an electric furnace at 800 ° C. for 3 hours. After cooling, 2 ml of nitric acid was added in 6 portions and completely evaporated and dried on a hot plate at 300 to 350 ° C. Next, 3 ml of hydrochloric acid was added, heated to 200-250 ° C., dried to the extent that hydrochloric acid remained at the bottom of the crucible, made up to 25 ml with distilled water, and kept at 20 ° C. with a cooling device to prepare a sample. . This sample was subjected to atomic absorption analysis using an atomic absorption spectrophotometer (trade name: AA-6500, manufactured by Shimadzu Corporation), and metal atoms were quantified.

MB production example 2 (production of masterbatch 2)
Master batch pellets were obtained in the same manner as MB Production Example 1 except that the polyamide resin 2 of Production Example 2 was used as the thermoplastic resin (X) (Master Batch 2). Further, in the same manner as in MB Production Example 1, metal atoms contained in the obtained master batch 2 were quantified. The results are shown in Table 2.

MB production example 3 (production of masterbatch 3)
Master batch pellets were obtained in the same manner as MB Production Example 1 except that the polyamide resin 5 of Production Example 5 was used as the thermoplastic resin (X) (Master Batch 3). Further, in the same manner as in MB Production Example 1, metal atoms contained in the obtained master batch 3 were quantified. The results are shown in Table 2.

MB production example 4 (production of masterbatch 4)
Master as in MB Production Example 1 except that copper phthalocyanine-based green colorant (manufactured by BASF, trade name: Heliogen Green K9360, copper content: 2.85%) was used as the colorant (B). Batch pellets were obtained (masterbatch 4). Further, in the same manner as in MB Production Example 1, metal atoms contained in the obtained master batch 4 were quantified. The results are shown in Table 2.

MB production example 5 (manufacture of masterbatch 5)
Except that an iron (III) oxide-based red colorant (manufactured by BASF, trade name: Sicotrans Red K2915, iron content: 51%) was used as the colorant (B), the same as in MB Production Example 1, Master batch pellets were obtained (master batch 5). Further, in the same manner as in MB Production Example 1, metal atoms contained in the obtained master batch 5 were quantified. The results are shown in Table 2.

MB Production Example 6 (Manufacture of master batch 6)
Master batch pellets were obtained in the same manner as MB Production Example 5 except that the polyamide resin 2 of Production Example 2 was used as the thermoplastic resin (X) (Master Batch 6). Further, in the same manner as in MB Production Example 1, metal atoms contained in the obtained master batch 6 were quantified. The results are shown in Table 2.

MB production example 7 (production of masterbatch 7)
Master batch in the same manner as in MB Production Example 1, except that anthraquinone yellow colorant (manufactured by BASF, trade name: Filester Yellow RNB, iron content: 1.8%) was used as the colorant (B). Pellets were obtained (master batch 7). Further, in the same manner as in MB Production Example 1, metal atoms contained in the obtained master batch 7 were quantified. The results are shown in Table 2.

(Master batch 8)
A PET-based iron oxide-based brown colored master batch (manufactured by Nippon Pigment Co., Ltd., trade name: RX-2550-11x Kai 3, iron content: 1.2%) was used as master batch 8. In the same manner as in MB Production Example 1, metal atoms contained in the master batch 8 were quantified. The results are shown in Table 2.

(Master batch 9)
A polybutylene terephthalate (PBT) -based organic copper-based brown colored masterbatch (manufactured by Clariant, trade name: Renol Brown, copper content: 0.95%) was used as the masterbatch 9. In the same manner as in MB Production Example 1, the metal atoms contained in the master batch 9 were quantified. The results are shown in Table 2.

Next, in Examples 1 to 37 and Comparative Examples 1 to 12, a coextruded multilayer film, a PET blend bottle, a PET multilayer bottle, and an unstretched film were prepared using the polyamide resins 1 to 5 and the master batches 1 to 9. Then, oxygen permeability measurement, delamination resistance evaluation, melt residence test and tensile test were carried out.
Measurement of oxygen permeability of co-extruded multilayer films, PET blend bottles and PET multilayer bottles obtained in Examples and Comparative Examples, evaluation of delamination resistance of PET multilayer bottles, and melt retention test and tensile test of unstretched films Was performed by the following method.

(1) Oxygen transmission rate (OTR) of co-extruded multilayer film, PET blend bottle and PET multilayer bottle
The oxygen transmission rate of the coextruded multilayer film is measured using an oxygen transmission rate measuring device (manufactured by MOCON, model: OX-TRAN 2/21) in an atmosphere of 23 ° C. and a relative humidity of 60% according to ASTM D3985. Measured for 30 days.
The oxygen permeability of the PET blend bottle and the PET multilayer bottle was measured using an oxygen permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2-61) at 23 ° C. and 50% relative humidity outside the molded body. The oxygen transmission rate of the bottle until 90 days after molding was measured in accordance with ASTM D3985 under an atmosphere with an internal relative humidity of 100%.
The lower the measured value, the better the oxygen barrier property.

(2) Delamination resistance of PET multilayer bottle Based on ASTM D2463-95 Procedure B, delamination height was measured by a bottle drop test. The higher the delamination height, the better the delamination resistance.
First, after filling a bottle with water and capping, the bottle was dropped and the presence or absence of delamination was visually determined. The bottle was dropped vertically so that the bottom was in contact with the floor. The drop height interval was 15 cm, and the number of test containers was 30. The test was performed immediately after filling with water and after 90 days at 40 ° C. and 50% relative humidity after filling with water.

(3) Melt retention test of unstretched film Four unstretched films with a thickness of 250 μm are stacked, cut into a circle with a diameter of about 40 mm, sandwiched between polytetrafluoroethylene sheets, and the sheet is moved up and down with a metal plate. The metal plates were sandwiched and fixed with bolts. Then, it pressed with the pressure of 50 kg / cm < ² > on the hot press heated at 290 degreeC, and heated for 24 hours. After heating for 24 hours, the metal plate was taken out, rapidly cooled, and taken out at room temperature.
Subsequently, 100 mg of this sample was weighed and placed in a test tube capable of being sealed, and the sample was dried at 60 ° C. for 30 minutes with a constant temperature dryer (the mass at this time is referred to as “sample mass”). Immediately after the sample was dried, 10 ml of hexafluoroisopropanol (manufactured by Junsei Chemical Co., Ltd., hereinafter sometimes referred to as “HFIP”) was added to the test tube, covered, left to stand for 24 hours, and dissolved. Next, the membrane was filtered under reduced pressure through a pre-weighed 0.3 μm pore polytetrafluoroethylene membrane filter, and the residue remaining on the membrane filter was washed with HFIP. Thereafter, the filter with the residue attached was naturally dried for 24 hours. Subsequently, the dried residue and the total mass of the filter were weighed, and after determining the amount of HFIP insoluble component (gel mass) of the retained sample from the difference between the weight of the membrane filter weighed in advance, the gel fraction was measured before HFIP immersion. The mass% of the HFIP insoluble component relative to the staying sample was calculated from the following formula.
Gel fraction (%) = (gel mass / sample mass) × 100

(4) Tensile test of unstretched film A non-stretched film having a thickness of 100 μm is stored in a thermostatic bath at 40 ° C. and 80% RH for 30 days to absorb oxygen, and is kept in a constant temperature and humidity chamber at 23 ° C. and 50% RH for one week. After humidity conditioning, a tensile test was performed. As a comparison, a sample that was not stored for 30 days in an environment of 40 ° C. and 80% RH was prepared, and a tensile test was performed after conditioning in a constant temperature and humidity chamber at 23 ° C. and 50% RH for one week (initial value).
・ Tensile test conditions Tensile tester: manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Strograph V-1C
Film direction: MD
Film width: 10mm
Tensile speed: 50 mm / min

[Co-extruded multilayer film (5-layer construction)]
Example 1
A multilayer film production apparatus equipped with three extruders, a feed block, a T die, a cooling roll, a winder and the like was used. Dry blend of polyamide resin 1 and masterbatch 2 from the first extruder so that the mixing ratio (mass ratio) of polyamide resin 1 / masterbatch 2 is 95/5. From the machine, polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec, grade: FY6) is 230 ° C. From the third extruder, an adhesive resin (manufactured by Mitsui Chemicals, trade name: Admer, grade: QB515) is extruded at 220 ° C., and through feed block, (outer layer) polypropylene layer / adhesive resin layer / polyamide resin 1 + masterbatch 2 layer / adhesive resin layer / polypropylene layer (inner layer) A multilayer film was produced. The thickness of each layer was 60/5/40/5/60 (μm).

Examples 2-7, Comparative Example 1
Coextruded multilayer films were prepared in the same manner as in Example 1 except that the type of polyamide resin (A), the type of masterbatch, and the mixing ratio of the polyamide resin (A) and the masterbatch were changed.

Comparative Example 2
A coextruded multilayer film was prepared in the same manner as in Example 1 except that the material constituting the polyamide resin 1 + master batch 2 layer in Example 1 was changed to only the polyamide resin 1 without mixing the master batch.

Comparative Example 3
A coextruded multilayer film was prepared in the same manner as in Example 1 except that the material constituting the polyamide resin 1 + master batch 2 layer in Example 1 was changed to only the polyamide resin 5 without mixing the master batch.

[Co-extruded multilayer film (5-layer construction, biaxial stretching)]
Example 8
The multilayer film obtained in Example 1 was stretched 3 times in the MD direction and 3 times in the TD direction at a stretching temperature of 115 ° C. using a biaxial stretching device (tenter method) manufactured by Toyo Seiki Seisakusho Co., Ltd. The film was heat-fixed at 160 ° C. for 30 seconds to prepare a biaxially stretched film having a thickness of about 19 μm.

Comparative Example 4
The multilayer film obtained in Comparative Example 3 was stretched in the same manner as in Example 8 to prepare a biaxially stretched film.

[Co-extruded multilayer stretched film (3-layer construction, biaxial stretching)]
Example 9
Using a multilayer film manufacturing apparatus equipped with three extruders, feed block, T die, cooling roll, winder, etc., nylon 6 (N6) (Ube Industries, Ltd.) from the first and third extruders ), Product name: UBE nylon 6, grade: 1022B) at 250 ° C., the polyamide resin 2 and masterbatch 2 were mixed from the second extruder at a polyamide resin 2 / masterbatch 2 mixing ratio (mass ratio) of 90. / 10 was extruded at 250 ° C., and a multilayer film (A1) having a two-kind / three-layer structure of nylon 6 layer / polyamide resin 2 layer / nylon 6 layer was produced through a feed block. The thickness of each layer was 80/80/80 (μm).
Next, using a batch type biaxial stretching machine (manufactured by Toyo Seiki Co., Ltd., center stretch type biaxial stretching machine), heating temperature 120 ° C., stretching speed 3000 mm / min, heat setting temperature 190 ° C., heat setting time 30 A film biaxially stretched 4 times in length and 4 times in width in seconds was obtained. In addition, the thickness of each layer after extending | stretching became 5/5/5 (micrometer).

Example 10
A biaxially stretched film was prepared in the same manner as in Example 9 except that the master batch 2 in Example 9 was changed to the master batch 6.

Comparative Example 5
A biaxially stretched film was prepared in the same manner as in Example 9 except that the material constituting the polyamide resin 2 + master batch 2 layer in Example 9 was changed to only the polyamide resin 2 without mixing the master batch.

  Table 3 shows the measurement results of oxygen permeability after 5 days and 30 days after the production of the coextruded multilayer films of Examples 1 to 10 and Comparative Examples 1 to 5.

The coextruded multilayer films of Examples 1 to 7 retained oxygen absorption performance even after 30 days and exhibited good oxygen permeability. On the other hand, the coextruded multilayer film of Comparative Example 2 that did not use a masterbatch even when a specific polyamide resin (A) was used showed good oxygen absorption performance after 5 days, but deteriorated over time. The performance could not be maintained for a long time. In the coextruded multilayer film of Comparative Example 3 using N-MXD6 that does not use the specific polyamide resin defined in the present invention and the coextruded multilayer film of Comparative Example 1 in which a master batch is added to N-MXD6, the oxygen absorption performance The oxygen permeability was not good.
Furthermore, the five-layer structure biaxially stretched multilayer film of Example 8 had better oxygen permeability for a longer period than the biaxially stretched multilayer film using only N-MXD6 of Comparative Example 4. Similarly, the three-layered biaxially stretched multilayer film of Examples 9 and 10 had better oxygen permeability for a longer period than the biaxially stretched multilayer film using only the polyamide resin (A) of Comparative Example 5. .

[PET blend bottle]
Example 11
Injection molding (Parison) by filling the cavity by injecting the required amount of resin composition mixed with polyamide resin (A), masterbatch 1 and polyethylene terephthalate resin (PET) from the injection cylinder under the following conditions. (22.5 g) was obtained. As the polyethylene terephthalate resin, polyethylene terephthalate (made by Nippon Unipet Co., Ltd.) having an intrinsic viscosity (mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio), measuring temperature: 30 ° C.) is 0.83. , Trade name: BK-2180). As the polyamide resin (A), the polyamide resin 2 produced in Production Example 2 was used, and the master batch 1 was used as the master batch. The blending ratio of PET and masterbatch 1 was PET / masterbatch 1 = 90/10 (mass ratio). The blend ratio of the polyamide resin (A) was polyamide resin (A) / (PET and masterbatch) = 3/97 (mass ratio).
After cooling the obtained parison, as a secondary process, the parison was heated and biaxial stretch blow molding was performed to produce a bottle.

(Parison shape)
The total length was 95 mm, the outer diameter was 22 mm, and the wall thickness was 2.7 mm. Note that an injection molding machine (manufactured by Meiki Seisakusho Co., Ltd., model: M200, 4 pieces) was used for manufacturing the parison.
(Parison molding conditions)
Injection cylinder temperature: 280 ° C
Resin channel temperature in mold: 280 ° C
Mold cooling water temperature: 15 ° C

(Bottle shape obtained by secondary processing)
The total length was 160 mm, the outer diameter was 60 mm, the inner volume was 370 ml, and the wall thickness was 0.28 mm. The draw ratio was 1.9 times in length and 2.7 times in width. The bottom shape is a champagne type. The body has dimples. In the secondary processing, a blow molding machine (manufactured by Frontier Co., Ltd., model: EFB1000ET) was used.
(Secondary processing conditions)
Heating temperature of injection molded body: 100 ° C
Stretching rod pressure: 0.5 MPa
Primary blow pressure: 0.5 MPa
Secondary blow pressure: 2.4 MPa
Primary blow delay time: 0.32 sec
Primary blow time: 0.30 sec
Secondary blow time: 2.0 sec
Blow exhaust time: 0.6 sec
Mold temperature: 30 ℃

Examples 12-22, Comparative Example 6
A PET blend bottle was prepared in the same manner as in Example 11 except that the type of polyamide resin (A), the type of masterbatch, the blending ratio of PET and masterbatch, and the blending ratio of the polyamide resin (A) were changed. .

Comparative Example 7
A PET blend bottle was prepared in the same manner as in Example 11 except that only the polyamide resin 2 was used as the material constituting the parison without mixing the masterbatch.

  Table 4 shows the measurement results of oxygen permeability of the PET blend bottles of Examples 11 to 22 and Comparative Examples 6 and 7.

  The PET blend bottles of Examples 11 to 22 have good oxygen for a long period of time as compared with the PET blend bottle of Comparative Example 6 in which the master batch was added to N-MXD6 and the PET blend bottle of Comparative Example 7 not using the master batch. The transmittance was shown.

[PET multilayer bottle (3-layer configuration)]
Example 23
Under the following conditions, the material constituting the layer (b) is injected from the injection cylinder, and then the material constituting the layer (a) is injected from another injection cylinder at the same time as the material constituting the layer (b). (B) / (a) / (b) three-layer injection molded body (parison) (22.5 g) by injecting a necessary amount of the material constituting the layer (b) to fill the cavity. Obtained.
As a material constituting the layer (b), polyethylene terephthalate (Nippon Unipet (using a mixed solvent of intrinsic viscosity (phenol / tetrachloroethane = 6/4 (mass ratio), measurement temperature: 30 ° C.) of 0.83) was used as the material constituting the layer (b). Co., Ltd., trade name: BK-2180) was used. As a material constituting the layer (a), the polyamide resin 1 and the master batch 6 were dry blended so that the mixing ratio (mass ratio) of the polyamide resin 1 / master batch 6 was 90/10.
After cooling the obtained parison, as a secondary process, the parison was heated and biaxial stretch blow molding was performed to produce a bottle. The mass of the layer (a) with respect to the total mass of the obtained bottle was 5% by mass.

(Parison shape)
The total length was 95 mm, the outer diameter was 22 mm, the wall thickness was 2.7 mm, the outer layer (b) barrel thickness was 1520 μm, the layer (a) barrel thickness was 140 μm, and the inner layer (b) barrel thickness was 1040 μm. Note that an injection molding machine (manufactured by Meiki Seisakusho Co., Ltd., model: M200, 4 pieces) was used for manufacturing the parison.
(Parison molding conditions)
Injection cylinder temperature for layer (a): 250 ° C.
Injection cylinder temperature for layer (b): 280 ° C
Resin channel temperature in mold: 280 ° C
Mold cooling water temperature: 15 ° C

(Bottle shape obtained by secondary processing)
The total length was 160 mm, the outer diameter was 60 mm, the inner volume was 370 ml, the wall thickness was 0.28 mm, the outer layer (b) trunk thickness was 152 μm, the layer (a) trunk thickness was 14 μm, and the inner layer (b) trunk thickness was 114 μm. The draw ratio was 1.9 times in length and 2.7 times in width. The bottom shape is a champagne type. The body has dimples. In the secondary processing, a blow molding machine (manufactured by Frontier Co., Ltd., model: EFB1000ET) was used.
(Secondary processing conditions)
Heating temperature of injection molded body: 100 ° C
Stretching rod pressure: 0.5 MPa
Primary blow pressure: 0.5 MPa
Secondary blow pressure: 2.4 MPa
Primary blow delay time: 0.32 sec
Primary blow time: 0.30 sec
Secondary blow time: 2.0 sec
Blow exhaust time: 0.6 sec
Mold temperature: 30 ℃

Examples 24-32, Comparative Example 8
Except that the type of polyamide resin (A), the type of masterbatch, the mixing ratio of the polyamide resin (A) and masterbatch, and the mass of the layer (a) with respect to the total mass of the bottle were changed, respectively, as in Example 23 A PET multilayer bottle was prepared.

Example 33
PET multilayer bottle as in Example 23, except that the material constituting the layer (b) was dry blended so that the mixing ratio (mass ratio) of PET / masterbatch 6 was 90/10 It was created.

Comparative Example 9
As a material constituting the layer (a), a PET multilayer bottle was prepared in the same manner as in Example 23 except that only the polyamide resin 2 was used without mixing the master batch.

  Table 5 shows the measurement results of oxygen permeability and delamination height of the PET multilayer bottles of Examples 23 to 33 and Comparative Examples 8 and 9.

  The PET multilayer bottles of Examples 23 to 33 are the PET multilayer bottles of Comparative Example 9 in which the N-MXD6 base masterbatch is used for N-MXD6, and no colorant is added without using the masterbatch. It showed better oxygen permeability compared to the bottle. Moreover, regarding the delamination resistance, the PET multilayer bottles of Examples 23 to 33 showed the same performance as Comparative Examples 8 and 9.

Example 34
Polyamide resin 2 and masterbatch 2 were dry blended so that the mixing ratio (mass ratio) of polyamide resin 2 / masterbatch 2 was 90/10. It was put into a hopper and extruded at a rotational speed of 70 rpm and 260 ° C. to obtain an unstretched film having a thickness of 250 μm and a thickness of 100 μm. A 250 μm film was subjected to a melt residence test at 290 ° C. for 24 hours to obtain a gel fraction. Moreover, the tensile test was implemented using the 100 micrometer film and the tensile breaking strength was calculated | required.

Examples 35-37, Comparative Example 10
Except for changing the type of polyamide resin (A), the type of masterbatch, and the mixing ratio of the polyamide resin (A) and the masterbatch, an unstretched film was prepared in the same manner as in Example 34, A tensile test was performed to determine the gel fraction and the tensile strength at break.

  In Table 6, the measurement result of the gel fraction obtained from the melt residence test of the unstretched films of Examples 34 to 37 and Comparative Example 10 and the tensile strength at break obtained from the tensile test are shown.

  The gel fraction of the unstretched film of Examples 34 to 37 using the master batch and the tensile strength at break by the tensile test are equivalent to those of Comparative Example 10 in which no master batch is added, and gel formation is suppressed. It has been found that it has excellent heat resistance. Moreover, since the deterioration of mechanical properties is low, it can be understood that there is no practical problem even if it is distributed in the form of an actual packaging container and absorbs oxygen. From this result, even when continuously forming the molded bodies of Examples 1 to 33, it is possible to reduce production troubles such as koge and gel, and a decrease in mechanical properties caused by oxygen absorption (for example, It can be seen that the delamination resistance, etc.) can also be reduced.

  The polyamide resin composition of the present invention is excellent in oxygen absorption. Therefore, for example, the polyamide resin composition of the present invention is suitable for use as an oxygen absorbent by filling a sachet or the like. As a more preferable usage form of the polyamide resin composition of the present invention, use in packaging containers such as packaging materials and PET bottles can be mentioned. The packaging material and the packaging container using the polyamide resin composition of the present invention enable necessary coloring, express excellent oxygen absorption performance, and can preserve the contents in a good state.

Claims (16)

An aromatic diamine unit represented by the following general formula (I-1), an alicyclic diamine unit represented by the following general formula (I-2), and a straight chain represented by the following general formula (I-3) 25 to 50 mol% of diamine units containing at least 50 mol% in total of at least one diamine unit selected from the group consisting of aliphatic diamine units;
A dicarboxylic acid unit containing a total of 50 mol% or more of a linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) and / or an aromatic dicarboxylic acid unit represented by the following general formula (II-2) 25 to 50 mol%,
A polyamide resin (A) containing 0.1 to 50 mol% of a structural unit represented by the following general formula (III), and a color containing one or more metal atoms selected from iron, manganese, copper and zinc Agent (B)
A colored polyamide resin composition comprising:

[In the general formula (I-3), m represents an integer of 2 to 18. In the general formula (II-1), n represents an integer of 2 to 18. In the general formula (II-2), Ar represents an arylene group. In the general formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ] The colored polyamide resin composition according to claim 1, wherein R in the general formula (III) is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. object. The colored polyamide resin composition according to claim 1 or 2, comprising 1 to 5000 ppm by mass of the colorant (B) as a metal atom concentration. The colored polyamide resin composition according to any one of claims 1 to 3, wherein the diamine unit contains 50 mol% or more of a metaxylylenediamine unit. The linear aliphatic dicarboxylic acid unit contains at least one selected from the group consisting of an adipic acid unit, a sebacic acid unit, and a 1,12-dodecanedicarboxylic acid unit in total of 50 mol% or more. The colored polyamide resin composition according to any one of the above. The aromatic dicarboxylic acid unit contains at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit in a total of 50 mol% or more. A colored polyamide resin composition according to claim 1. The polyamide resin (A) further contains an ω-aminocarboxylic acid unit represented by the following general formula (VI) in an amount of 0.1 to 49.9 mol% in all structural units of the polyamide resin (A). Item 7. The colored polyamide resin composition according to any one of Items 1 to 6.

[In said general formula (VI), p represents the integer of 2-18. ] The colored polyamide resin composition according to claim 7, wherein the ω-aminocarboxylic acid unit contains a total of 50 mol% or more of 6-aminohexanoic acid units and / or 12-aminododecanoic acid units. The colored polyamide resin composition according to any one of claims 1 to 8, wherein the polyamide resin (A) has a relative viscosity of 1.8 or more and 4.2 or less. The colorant (B) contains one or more metal atoms selected from oxides and cyanides containing at least one metal atom selected from iron, manganese, copper and zinc, iron, manganese, copper and zinc. The colored polyamide resin composition according to any one of claims 1 to 9, which is one or more colorants selected from anthracene colorants and copper phthalocyanine colorants. The colored polyamide resin composition according to any one of claims 1 to 10, wherein the colorant (B) is at least one selected from iron oxide colorants, ferrocyanide colorants, and copper phthalocyanine colorants. object. A method for producing the colored polyamide resin composition according to any one of claims 1 to 11, wherein the colorant (B) and the thermoplastic resin (X) are melt-mixed to obtain a master batch, and A method for producing a colored polyamide resin composition, comprising a step of melt-kneading the master batch with the polyamide resin (A). The colored polyamide resin composition according to claim 12, wherein a mass ratio [(B) / (X)] of the colorant (B) to the thermoplastic resin (X) is 10 to 15000 mass ppm as a metal atom concentration. Manufacturing method. The colored polyamide resin composition according to claim 12 or 13, wherein a mixing ratio of the master batch and the polyamide resin (A) is 99: 1 to 50:50 as a mass ratio of the polyamide resin (A): master batch. Manufacturing method. The molded object containing the colored polyamide resin composition in any one of Claims 1-11.   The molded object of Claim 15 whose metal atom density | concentration is 1-5000 mass ppm.