JPWO2013002081A1 - Tubular container - Google Patents

Abstract

A tubular container including a layer formed from a resin composition containing a polyamide compound (A) and a resin (B), wherein the polyamide compound (A) contains 50 mol% or more of a specific diamine unit. A tubular container containing 25 to 50 mol%, 25 to 50 mol% of a dicarboxylic acid unit containing 50 mol% or more of a specific dicarboxylic acid unit, and 0.1 to 50 mol% of a specific structural unit.

Description

  The present invention relates to a tubular container having oxygen barrier performance and oxygen absorption performance.

  Tubular containers are used to store a wide variety of items such as foods, pharmaceuticals, cosmetics, sanitary materials such as toothpaste, chemicals such as adhesives, etc. The composition of the materials forming the container, the shape of the container, the manufacturing method, etc. Many are also seen. In order to prevent deterioration of contents, particularly deterioration due to oxygen, these tube-shaped containers have been used in the past in which an aluminum foil is laminated as a gas barrier layer. Aluminum foil is an excellent material that can completely block the permeation of gas such as oxygen, and has been used particularly as a container for pharmaceuticals.

  However, in tubular containers laminated with aluminum foil, it is extremely difficult to separate and collect the laminated resin and aluminum foil during resource recycling after use. There were problems such as making it difficult. As means for solving such problems, aluminum foil may be abbreviated as ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) or polymetaxylylene adipamide (hereinafter abbreviated as N-MXD6). Many tube-like containers have been proposed in which a thermoplastic resin having excellent gas barrier properties such as) and a resin film deposited with an inorganic oxide such as aluminum oxide or silicon oxide are deposited.

  However, in a container in which an inorganic oxide vapor deposition film is laminated, since the inorganic oxide is a vitreous and inflexible thin film and is a thin film that lacks flexibility, for example, heat or pressure is externally applied. When it acts, there is a problem that a crack or the like is easily generated and the gas barrier property is greatly lowered. The container with laminated gas barrier resin has the characteristics that the above-mentioned problems hardly occur, but the gas barrier performance is not perfect and the performance may deteriorate due to changes in temperature and humidity. Although it is possible to extend the content, deterioration due to oxidation of the contents is unavoidable and is not satisfactory.

  As means for eliminating the disadvantages of gas barrier thermoplastic resins, in recent years, a method of providing an oxygen-absorbing resin layer as one of the layers constituting a tubular container, or other thermoplastics laminated as a gas barrier resin layer or an intermediate layer A method of providing a resin layer with a layer in which an oxygen-absorbing compound is mixed has been proposed. For example, Patent Documents 1 and 2 disclose resin compositions and packaging materials composed of an oxidation catalyst containing polyolefin, EVOH, and a transition metal. Patent Documents 3 and 4 disclose oxygen-absorbing multilayer tubes in which an oxygen-absorbing gas barrier resin layer containing conjugated diene polymer cyclized product and EVOH as active ingredients is laminated. Patent Document 5 discloses a multilayer tube in which an oxygen-absorbing polyamide composed of N-MXD6, a low elastic modulus polyamide, and a metal catalyst compound containing a transition metal or the like is laminated as an oxygen barrier layer. Further, Patent Document 6 discloses a deoxygenating multilayer tube in which an oxygen absorbing layer in which an oxygen absorbent mainly composed of iron powder is dispersed in a thermoplastic resin is laminated.

Japanese Patent Laid-Open No. 05-156095 JP 05-170980 A JP 2006-335359 A JP 2006-335360 A JP 2004-181629 A JP 2002-103490 A

The tube-shaped container using the resin composition shown in Patent Documents 1 to 4 has a performance (oxygen barrier property) for blocking permeation of oxygen from the outside to the inside of the tube-shaped container, and in the tube-shaped container. Since it also has the ability to absorb residual oxygen in the head space and dissolved oxygen dissolved in the contents (oxygen absorption performance), it is excellent in the effect of suppressing oxidative deterioration of the contents. However, in any invention, in the process of exhibiting oxygen absorption performance, the oxidative degradation of polyolefin or conjugated diene polymer cyclized product proceeds rapidly by the catalyst, and causes low-molecular weight organic substances such as aldehydes and ketones. Will occur. Since these have the property of permeating the thermoplastic resin laminated as an inner layer, they may be mixed into the head space inside the container or may be dissolved in the contents, thereby impairing the flavor of the contents. There was a problem.
Even in the multilayer tube shown in Patent Document 5, oxygen absorption performance is expressed by utilizing the oxidative deterioration of the thermoplastic resin constituting the container as in Patent Documents 1 to 4, but N-MXD6's Oxidation is characterized in that it produces less off-flavor substances than the above. However, since N-MXD6 used as a structural material is oxidized and deteriorated, when the multilayer tube is used for a long time, the strength of the layer containing N-MXD6 decreases as oxygen absorption progresses, Cracks and the like are likely to occur, and the oxygen barrier property may be reduced. In addition, the tube-shaped container is often pressed by hand to extrude the contents. In such a case, the N-MXD6-containing layer with reduced strength is broken and delamination occurs. There is also a risk that the appearance of will deteriorate. Due to such concerns, the multilayer tube disclosed in Patent Document 5 has a limitation in use as a container for long-term storage.
Since the deoxidizing multilayer tube shown in Patent Document 6 is not accompanied by oxidative deterioration of the thermoplastic resin, there is no problem of generation of ketones or aldehydes, deterioration of the thermoplastic resin layer, and the main component of iron powder is not Because of its high oxygen absorption capacity, it exhibits the same content preservation as a container laminated with aluminum foil. However, since it is necessary to provide a separate barrier layer in addition to the oxygen absorbing layer, more materials are used than before, resulting in poor economic efficiency. Further, since metal powder is used as an oxygen absorbent, there is a problem that depending on the contents, the metal odor shifts to the contents and impairs the flavor. Furthermore, since a large amount of iron powder is mixed in the oxygen absorption layer, the container using it has no transparency, and its use range is limited.

  The problem to be solved by the present invention is a tube-like container capable of suppressing oxidative deterioration of the contents, does not impair the flavor of the contents, and does not reduce the strength of the layer that exhibits oxygen absorption performance even during long-term storage. The object is to provide a tubular container.

［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。］The present invention provides the following tubular containers.
A tubular container including a layer formed from a resin composition containing a polyamide compound (A) and a resin (B),
The polyamide compound (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 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%,
The tubular container containing 0.1-50 mol% of structural units represented by the following general formula (III).

[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 tube-like container of the present invention expresses oxygen barrier performance, can express oxygen absorption performance without containing a transition metal, and the oxygen absorption barrier layer decreases in strength as oxygen absorption progresses. Very small. Therefore, it is excellent in suppressing the oxidative deterioration of the contents, hardly generating substances that cause a strange odor or a change in flavor, and excellent in flavor retention. In addition, even during long-term use, the strength of the oxygen-absorbing barrier layer is maintained, so that cracks and appearance are unlikely to deteriorate.

  The tubular container of the present invention includes at least a layer formed from a resin composition containing a polyamide compound and a resin (hereinafter also referred to as “oxygen absorption barrier layer”). The tube-shaped container of the present invention may have a multilayer structure by further including an optional layer such as a fusion layer or an adhesive layer as necessary. By adopting a multilayer structure, the processability and physical properties of the container can be improved, and the handleability and design of the container can be enhanced.

1. Layer formed from a resin composition containing a polyamide compound and a resin (oxygen absorption barrier layer)
In the present invention, the oxygen-absorbing barrier layer is formed from a resin composition, and the resin composition will be described later in addition to a conventionally known resin (hereinafter sometimes referred to as “resin (B)”). By containing a specific polyamide compound (hereinafter sometimes referred to as “polyamide compound (A)”), excellent oxygen absorption performance and oxygen barrier performance can be exhibited.
In the present invention, the polyamide compound (A) contained in the resin composition may be one type or a combination of two or more types. Moreover, 1 type may be sufficient as resin (B) contained in a resin composition, and the combination of 2 or more types may be sufficient as it.

The suitable range of the mass ratio of the polyamide compound (A) and the resin (B) in the resin composition used in the present invention varies depending on the relative viscosity of the polyamide compound (A).
When the relative viscosity of the polyamide compound (A) is 1.8 or more and 4.2 or less, the mass ratio of the polyamide compound (A) / resin (B) may be selected from the range of 5/95 to 95/5. preferable. From the viewpoint of oxygen absorption performance and oxygen barrier performance, the content of the polyamide compound (A) is more preferably 10 parts by mass or more with respect to a total of 100 parts by mass of the polyamide compound (A) and the resin (B). More preferably, it is 30 parts by mass or more.
When the relative viscosity of the polyamide compound (A) is 1.01 or more and less than 1.8, it is desirable to contain a relatively large amount of the resin (B) from the viewpoint of moldability, and the polyamide compound (A) / The mass ratio of the resin (B) is preferably selected from the range of 5/95 to 50/50. From the viewpoint of oxygen absorption performance and oxygen barrier performance, the content of the polyamide compound (A) is more preferably 10 parts by mass or more with respect to a total of 100 parts by mass of the polyamide compound (A) and the resin (B). More preferably, it is 30 parts by mass or more.

In addition to the polyamide compound (A) and the resin (B), the resin composition used in the present invention may be referred to as an additive described later (hereinafter referred to as “additive (C)”) depending on the desired performance and the like. The total content of the polyamide compound (A) and the resin (B) in the resin composition is 90% by mass to 100% from the viewpoint of molding processability, oxygen absorption performance, and oxygen barrier performance. It is preferable that it is mass%, and it is more preferable that it is 95 mass%-100 mass%.
The thickness of the oxygen-absorbing barrier layer is preferably 2 to 100 μm, more preferably from the viewpoint of securing various physical properties such as flexibility required for the tubular container while improving the oxygen absorption performance and oxygen barrier performance. Is 5 to 90 μm, more preferably 10 to 80 μm.

1-1. Polyamide compound (A)
<Configuration of polyamide compound (A)>
In the present invention, the polyamide compound (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 general 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 compound (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 compound (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, when the content of the tertiary hydrogen-containing carboxylic acid unit exceeds 50 mol%, the tertiary hydrogen content is too large, and the physical properties such as gas barrier properties and mechanical properties of the polyamide compound (A) are deteriorated. 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 properties of the polyamide compound (A). It is 40 mol% or less, More preferably, it is 30 mol% or less.

In the polyamide compound (A), the content of diamine units 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 compound (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 compound (A) becomes difficult to increase, so it takes a lot of time to increase the degree of polymerization, Deterioration is likely to occur.

[Diamine unit]
The diamine unit in the polyamide compound (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 general formula. The total content of at least one diamine unit selected from the group consisting of linear aliphatic diamine units represented by (I-3) is 50 mol% or more in the diamine units, 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 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 general formula (I-2) include bis (1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like. Aminomethyl) 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 a diamine unit in the polyamide compound (A), in addition to imparting excellent gas barrier properties to the polyamide compound (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 properties of the polyamide compound (A), it is preferable that the aromatic diamine unit represented by the general formula (I-1) is included.

  The diamine unit in the polyamide compound (A) is a metaxylylenediamine unit from the viewpoint of facilitating moldability of a general-purpose thermoplastic resin in addition to exhibiting excellent gas barrier properties in the polyamide compound (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.

[Dicarboxylic acid unit]
The dicarboxylic acid unit in the polyamide compound (A) is a linear aliphatic group represented by the general formula (II-1) from the viewpoints of reactivity during polymerization and crystallinity and moldability of the polyamide compound (A). The 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% 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.

The linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) is necessary as a packaging material and a packaging container in addition to imparting an appropriate glass transition temperature and crystallinity to the polyamide compound (A). It is preferable at the point which can provide a softness | flexibility.
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 compound (A) provides excellent gas barrier properties to the polyamide compound (A), and from the viewpoint of maintaining heat resistance after heat sterilization of packaging materials and packaging containers. 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% or more 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 compound (A) is a linear aliphatic unit from the viewpoint of gas barrier properties of the polyamide compound (A) and thermal properties such as an appropriate glass transition temperature and melting point. It is preferable to contain 50 mol% or more in the dicarboxylic acid unit. In addition, the linear aliphatic dicarboxylic acid unit in the polyamide compound (A) is converted from the sebacic acid unit to the linear aliphatic dicarboxylic acid unit from the viewpoint of imparting appropriate gas barrier properties and molding processability to the polyamide compound (A). When the polyamide compound (A) is used for applications requiring low water absorption, weather resistance, and heat resistance, the 1,12-dodecanedicarboxylic acid unit is a linear aliphatic group. It is preferable to contain 50 mol% or more in the dicarboxylic acid unit.

The aromatic dicarboxylic acid unit represented by the general formula (II-2) facilitates molding processability of packaging materials and packaging containers in addition to imparting further gas barrier properties to the polyamide compound (A). It is preferable in that
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 compound (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.

  In the dicarboxylic acid unit in the polyamide compound (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 compound (A) to lower the crystallinity of the polyamide compound (A), the linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit is 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 compound (A) to impart flexibility to the polyamide compound (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.

  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.

[Tertiary hydrogen-containing carboxylic acid unit]
In the present invention, the tertiary hydrogen-containing carboxylic acid unit in the polyamide compound (A) has at least one amino group and one carboxyl group or two or more carboxyl groups from the viewpoint of polymerization of the polyamide compound (A). Have. 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. ]

  In the present invention, the polyamide compound (A) includes a tertiary hydrogen-containing carboxylic acid unit. By containing such a tertiary hydrogen-containing carboxylic acid unit as a copolymerization component, the polyamide compound (A) can exhibit excellent oxygen absorption performance without containing a transition metal.

In the present invention, the mechanism by which the polyamide compound (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).

  In this invention, it is preferable that a polyamide compound (A) contains at least 1 sort (s) of the structural unit represented by either of the said general formula (III), (IV) or (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 compound (A), oxygen absorption performance per 1 g of the polyamide compound (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.

[Ω-aminocarboxylic acid unit]
In the present invention, when the polyamide compound (A) needs flexibility and the like, in addition to the diamine unit, the dicarboxylic acid unit and the tertiary hydrogen-containing carboxylic acid unit, You may further contain the omega-aminocarboxylic acid unit represented by Formula (X).

［前記一般式（Ｘ）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、ポリアミド化合物（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（Ｘ）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。

[In said general formula (X), p represents the integer of 2-18. ]
The content of the ω-aminocarboxylic acid unit is preferably from 0.1 to 49.9 mol%, more preferably from 3 to 40 mol%, still more preferably from 5 to 35 in all the structural units of the polyamide compound (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 (X), 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 (X) 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.

[Polymerization degree of polyamide compound (A)]
Relative viscosity is used for the degree of polymerization of the polyamide compound (A). The relative viscosity of the polyamide compound (A) is not particularly limited, but is preferably 1.01 to 4.2.
As described above, the suitable range of the mass ratio of the polyamide compound (A) / resin (B) varies depending on the relative viscosity of the polyamide compound (A), and the relative viscosity of the polyamide compound (A) is 1.8 or more. When the ratio is 4.2 or less, the mass ratio of the polyamide compound (A) / resin (B) is preferably selected from the range of 5/95 to 95/5, and the relative viscosity of the polyamide compound (A) is 1. When it is 01 or more and less than 1.8, the mass ratio of polyamide compound (A) / resin (B) is preferably selected from the range of 5/95 to 50/50.
The relative viscosity here is 96% measured in the same manner as the dropping time (t) measured at 25 ° C. with a Cannon Fenceke viscometer by dissolving 1 g of polyamide compound (A) in 100 mL of 96% sulfuric acid. 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

[Terminal amino group concentration]
The oxygen absorption rate of the polyamide compound (A) and the oxidative deterioration of the polyamide compound (A) due to oxygen absorption can be controlled by changing the terminal amino group concentration of the polyamide compound (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 compound (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.

<Production method of polyamide compound (A)>
The polyamide compound (A) includes a diamine component that can constitute the diamine unit, a dicarboxylic acid component that can constitute the dicarboxylic acid unit, and a tertiary hydrogen-containing carboxylic acid component that can constitute the tertiary hydrogen-containing carboxylic acid unit. And, if necessary, it can be produced by polycondensation with the ω-aminocarboxylic acid component that can constitute the ω-aminocarboxylic acid unit, and the degree of polymerization can be controlled by adjusting the polycondensation conditions and the like. it can. 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 compound (A) may be adjusted from 1.

  Examples of the polycondensation method of the polyamide compound (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 gelation of a polyamide compound (A), and the polyamide compound (A) of the stable property is obtained.

[Reactive extrusion method]
In the reactive extrusion method, a polyamide composed of a diamine component and a dicarboxylic acid component (polyamide corresponding to the precursor of the polyamide compound (A)) or a polyamide composed of a diamine component, a dicarboxylic acid component and an ω-aminocarboxylic acid component (polyamide compound (A And a tertiary hydrogen-containing carboxylic acid component are melt-kneaded with an extruder and reacted. 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 compound (A) containing a small amount of a tertiary hydrogen-containing carboxylic acid unit, it is a simple method and suitable.

[Pressure salt method]
The pressurized salt method is a method of performing melt polycondensation under pressure using a 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 compound (A) + 10 ° C. and held, and then the pressure was gradually reduced to −0.02 MPaG while being kept at the same temperature. Continue polycondensation. When a certain stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound (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 compound (A) containing 15 mol% or more of tertiary hydrogen-containing carboxylic acid units in all structural units of the polyamide compound (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, the polyamide compound (A) excellent in properties can be obtained.

[Normal pressure dropping method]
In the normal pressure dropping method, a diamine component is continuously dropped into a mixture obtained by heating and melting a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and, if necessary, a ω-aminocarboxylic acid component under normal pressure. Then, polycondensation is performed 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 polyamide compound (A) to be produced.
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.

[Pressure drop method]
In the pressure drop method, first, a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and, if necessary, a ω-aminocarboxylic acid component are charged into a polycondensation can, and the components are stirred, melted and mixed. To prepare. 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 carried out while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the resulting polyamide compound (A). When the set molar ratio is reached, the dropping of the diamine component is terminated, the temperature inside the can is gradually returned to normal pressure, the temperature is raised to about the melting point of the polyamide compound (A) + 10 ° C., and then held, and further −0.02 MPaG The pressure is gradually reduced until it is maintained at the same temperature, and the polycondensation is continued. When a certain stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound (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 compound (A) containing 15 mol% or more of tertiary hydrogen-containing carboxylic acid units in the structural unit of the polyamide compound (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 compound (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. The polyamide compound (A) having a low yellowness can be obtained.

[Process of increasing the degree of polymerization]
The polyamide compound (A) produced by the 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 compound (A) is performed, a 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.

[Phosphorus atom-containing compound, alkali metal compound]
In the polycondensation of the polyamide compound (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 compound (A). If it is 0.1 ppm or more, the polyamide compound (A) is difficult to be colored during the polymerization, and the transparency becomes high. If it is 1000 ppm or less, the polyamide compound (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, and 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 compound (A). In order to prevent the polyamide compound (A) from being colored during the polycondensation, it is necessary that a sufficient amount of the phosphorus atom-containing compound is present, but in some cases, the polyamide compound (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.

1-2. Resin (B)
In the present invention, any resin can be used as the resin (B) and is not particularly limited. As the resin (B), for example, a thermoplastic resin can be used, and specific examples thereof include polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and plant-derived resin. In the present invention, the resin (B) preferably contains at least one selected from the group consisting of these resins.
Among these, a resin having high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymer is more preferable in order to effectively exhibit the oxygen absorption effect.
A conventionally well-known method can be used for mixing of the polyamide compound (A) and the resin (B), and dry mixing and melt mixing are exemplified. When the polyamide compound (A) and the resin (B) are melt-mixed to produce desired pellets and molded bodies, they can be melt-blended using an extruder or the like. The extruder may be a known extruder such as a single screw extruder or a twin screw extruder, but is not limited thereto.

[Polyolefin]
Specific examples of polyolefin include olefins such as polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene), polypropylene, polybutene-1, and poly-4-methylpentene-1. Homopolymer; Copolymer of ethylene and α-olefin such as ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cyclic olefin copolymer Ethylene-α, β-unsaturated carboxylic acid copolymer such as ethylene- (meth) acrylic acid copolymer, ethylene-α, β-unsaturated carboxylic acid such as ethylene- (meth) acrylic acid ethyl copolymer Ester copolymer, ionic cross-linked product of ethylene-α, β-unsaturated carboxylic acid copolymer, ethylene - Other ethylene copolymers such as vinyl acetate copolymer; may be mentioned graft-modified polyolefin grafted modifying these polyolefins with an acid anhydride such as maleic anhydride.

[polyester]
In the present invention, the polyester is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or a hydroxycarboxylic acid and an ester-forming derivative thereof, or a cyclic ester.

  Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3- Exemplified as cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid or the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid 1,3-na Taleenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′- Aromatic dicarboxylic acids exemplified by biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic acid, etc. or ester formation thereof Metal, exemplified by 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, etc. Sulfonate group-containing aromatic dicarboxylic acid or Such lower alkyl esters thereof derivative.

  Among the above dicarboxylic acids, the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferable in terms of the physical properties of the resulting polyester, and other dicarboxylic acids may be copolymerized as necessary. .

  As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.

  As glycols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethyl Aliphatic glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) exemplified by tylene glycol and polytetramethylene glycol ) Sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2 , 5-naphthalenediol, and aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols.

  Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component. Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like. Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.

  Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.

  Examples of ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides and the like.

  The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.

  The polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof with respect to the total acid component, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is also preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, more preferably 80 mol% or more. It is polyester to contain, More preferably, it is polyester containing 90 mol% or more.

  Examples of the naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid exemplified in the above dicarboxylic acids, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof are preferred.

  The polyester whose main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol with respect to the total glycol component, more preferably a polyester containing 80 mol% or more, more preferably Polyester containing 90 mol% or more. The alkylene glycol here may contain a substituent or an alicyclic structure in the molecular chain.

  The copolymer components other than the terephthalic acid / ethylene glycol are isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propane. It is preferably at least one selected from the group consisting of diol and 2-methyl-1,3-propanediol in order to achieve both transparency and moldability. In particular, isophthalic acid, diethylene glycol, neopentyl glycol, 1 More preferred is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.

  A preferred example of the polyester used in the present invention is a polyester whose main repeating unit is composed of ethylene terephthalate, more preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, and still more preferably an ethylene terephthalate unit. A linear polyester containing 80 mol% or more is preferable, and a linear polyester containing 90 mol% or more of ethylene terephthalate units is particularly preferable.

  Another preferred example of the polyester used in the present invention is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate, more preferably 70 mol% or more of ethylene-2,6-naphthalate unit. It is a linear polyester, more preferably a linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, and particularly preferable is a linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units. Polyester.

  Other preferable examples of the polyester used in the present invention include linear polyesters containing 70 mol% or more of propylene terephthalate units, linear polyesters containing 70 mol% or more of propylene naphthalate units, and 1,4-cyclohexanedimethylene terephthalate. A linear polyester containing 70 mol% or more of units, a linear polyester containing 70 mol% or more of butylene naphthalate units, or a linear polyester containing 70 mol% or more of butylene terephthalate units.

  In particular, the composition of the whole polyester is a combination of terephthalic acid / isophthalic acid // ethylene glycol, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol, and terephthalic acid // ethylene glycol / neopentyl glycol. This is preferable in order to satisfy both the moldability and the moldability. Needless to say, a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol may be included in the esterification (transesterification) reaction or polycondensation reaction.

  Other preferable examples of the polyester used in the present invention include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. This polyglycolic acid may be copolymerized with other components such as lactide.

[polyamide]
Polyamide used in the present invention (here, “polyamide” refers to a polyamide resin mixed with “polyamide compound (A)” of the present invention, and refers to “polyamide compound (A)” of the present invention itself. Is not a polyamide having a unit derived from a lactam or an aminocarboxylic acid as a main structural unit, an aliphatic polyamide having a unit derived from an aliphatic diamine and an aliphatic dicarboxylic acid as a main structural unit, Partially aromatic polyamides whose main constituent units are units derived from aromatic diamines and aromatic dicarboxylic acids, partially aromatic polyamides whose main constituent units are units derived from aromatic diamines and aliphatic dicarboxylic acids, etc. As necessary, monomer units other than the main structural unit may be copolymerized.

  Examples of the lactam or aminocarboxylic acid include lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid. .

  As the aliphatic diamine, an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof can be used. Furthermore, an alicyclic diamine may be used. The aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine. Specific examples of such linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples include aliphatic diamines such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine. Specific examples of the alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like.

  Moreover, as said aliphatic dicarboxylic acid, linear aliphatic dicarboxylic acid and alicyclic dicarboxylic acid are preferable, and also linear aliphatic dicarboxylic acid which has a C4-C12 alkylene group is especially preferable. Examples of such linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, dimer Examples thereof include acids and functional derivatives thereof. Examples of the alicyclic dicarboxylic acid include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.

  Examples of the aromatic diamine include metaxylylenediamine, paraxylylenediamine, para-bis (2-aminoethyl) benzene, and the like.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and functional derivatives thereof. It is done.

  Specific polyamides include polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 4, 6, polyamide 6, 6, polyamide 6, 10, polyamide 6T, polyamide 9T, polyamide 6IT, polymetaxylylene azide. Pamide (Polyamide MXD6), Isophthalic acid copolymer polymetaxylylene adipamide (Polyamide MXD6I), Polymetaxylylene sebamide (Polyamide MXD10), Polymetaxylylene decanamide (Polyamide MXD12), Poly 1,3-bis (Aminomethyl) cyclohexane adipamide (polyamide BAC6), polyparaxylylene sebacamide (polyamide PXD10) and the like. More preferable polyamides include polyamide 6, polyamide MXD6, and polyamide MXD6I.

  Further, as a copolymerization component of the polyamide, a polyether having at least one terminal amino group or a terminal carboxyl group and a number average molecular weight of 2000 to 20000, or an organic carboxylate of the polyether having the terminal amino group, or An amino salt of a polyether having a terminal carboxyl group can also be used. Specific examples include bis (aminopropyl) poly (ethylene oxide) (polyethylene glycol having a number average molecular weight of 2000 to 20000).

  The partially aromatic polyamide may contain a structural unit derived from a polybasic carboxylic acid having 3 or more bases such as trimellitic acid and pyromellitic acid within a substantially linear range.

  The polyamide is basically a conventionally known melt polycondensation method in the presence of water or a melt polycondensation method in the absence of water, or a polyamide obtained by these melt polycondensation methods. It can be manufactured by a method or the like. The melt polycondensation reaction may be performed in one step or may be performed in multiple steps. These may be comprised from a batch-type reaction apparatus, and may be comprised from the continuous-type reaction apparatus. The melt polycondensation step and the solid phase polymerization step may be operated continuously or may be operated separately.

[Ethylene-vinyl alcohol copolymer]
Although it does not specifically limit as an ethylene vinyl alcohol copolymer used by this invention, Preferably it is 15-60 mol%, More preferably, it is 20-55 mol%, More preferably, it is 29-44 mol%, The degree of saponification of the vinyl acetate component is preferably 90 mol% or more, more preferably 95 mol% or more.
Further, the ethylene vinyl alcohol copolymer has a smaller amount of an α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, and unsaturated carboxylic acid as long as the effects of the present invention are not adversely affected. Alternatively, it may contain a comonomer such as a salt, a partial alkyl ester, a complete alkyl ester, a nitrile, an amide, an anhydride, an unsaturated sulfonic acid or a salt thereof.

[Plant-derived resin]
Specific examples of the plant-derived resin include a portion overlapping with the above resin, but are not particularly limited, and examples thereof include aliphatic polyester-based biodegradable resins other than various known petroleum materials. Examples of the aliphatic polyester-based biodegradable resin include poly (α-hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES), and the like. And polyalkylene alkanoates.

[Other resins]
Various conventionally known resins may be added as the resin (B) in accordance with the performance desired to be imparted to the oxygen-absorbing barrier layer as long as the object of the present invention is not impaired. For example, from the viewpoint of imparting impact resistance, pinhole resistance, and flexibility, polyolefins such as polyethylene and polypropylene, various modified products thereof, polyolefin elastomers, polyamide elastomers, styrene-butadiene copolymer resins and hydrogens thereof. Additives processed, various thermoplastic elastomers typified by polyester elastomers, various polyamides such as nylon 6, 66, 12 and nylon 12, etc. From the viewpoint of further imparting oxygen absorption performance, polybutadiene and modified polybutadiene And carbon-carbon unsaturated double bond-containing resins.

1-3. Additive (C)
In the present invention, the resin composition for forming the oxygen absorption barrier layer may further contain an additive (C) as necessary in addition to the polyamide compound (A) and the resin (B) described above. . One type of additive (C) may be used, or a combination of two or more types may be used. The content of the additive (C) in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, although it depends on the type of additive.

[Anti-whitening agent]
In the present invention, it is preferable to add a diamide compound and / or a diester compound to the resin composition as a suppression of whitening after the 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 used in the present invention 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. In addition, when the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diamine has 10 or less carbon atoms, uniform dispersion in the oxygen-absorbing barrier layer 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.

The diester compound used in the present invention is preferably a diester compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms. 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 oxygen-absorbing barrier layer 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.

  In the present invention, the amount of the diamide compound and / or diester compound added is preferably 0.005 to 0.5% by mass, more preferably 0.05 to 0.5% by mass, and still more preferably 0 in the resin composition. .12 to 0.5% by mass. A synergistic effect of preventing whitening can be expected by adding 0.005% by mass or more to the resin composition and using it together with the crystallization nucleating agent. Moreover, it becomes possible to keep the fog value of the molded object obtained by shape | molding the said resin composition low as the addition amount is 0.5 mass% or less in a resin composition.

[Layered silicate]
In the present invention, the oxygen absorption barrier layer may contain a layered silicate. By adding a layered silicate, not only an oxygen gas barrier property but also a barrier property against a gas such as carbon dioxide gas can be imparted to the tubular container.

  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; 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.

  In this invention, what added 0.5-8 mass% of layered silicate processed with the organic swelling agent to the resin composition is used preferably, More preferably, it is 1-6 mass%, More preferably, it is 2-5. % By mass. If the amount of layered silicate added is 0.5% by mass or more, the effect of improving the gas barrier property is sufficiently obtained, and if it is 8% by mass or less, pinholes are generated due to deterioration of the flexibility of the oxygen absorption barrier layer. Such problems are unlikely to occur.

  In the oxygen absorption barrier layer, 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 in the oxygen absorption barrier layer, 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.

[Oxidation reaction accelerator]
In order to further enhance the oxygen absorption performance of the oxygen absorption barrier layer, a conventionally known oxidation reaction accelerator may be added as long as the effects of the present invention are not impaired. The oxidation reaction accelerator can enhance the oxygen absorption performance of the oxygen absorption barrier layer by promoting the oxygen absorption performance of the polyamide compound (A). Examples of the oxidation reaction accelerator include Group VIII metals such as iron, cobalt and nickel, Group I metals such as copper and silver, Group IV metals such as tin, titanium and zirconium, Group V of vanadium, Examples thereof include low-valent inorganic or organic acid salts of Group VI metals such as chromium and Group VII metals such as manganese, or complex salts of the above transition metals. Among these, a cobalt salt excellent in an oxygen reaction promoting effect or a combination of a cobalt salt and a manganese salt is preferable.
In the present invention, the addition amount of the oxygen reaction accelerator is preferably 10 to 800 ppm, more preferably 50 to 600 ppm, and still more preferably 100 to 400 ppm as a metal atom concentration in the resin composition.

[Oxygen absorber]
In order to further enhance the oxygen absorption performance of the oxygen absorption barrier layer, a conventionally known oxygen absorbent may be added within a range not impairing the effects of the present invention. The oxygen absorbent can enhance the oxygen absorption performance of the oxygen absorption barrier layer by imparting oxygen absorption performance to the oxygen absorption barrier layer separately from the oxygen absorption performance of the polyamide compound (A). Examples of the oxygen absorbent include oxidizable organic compounds typified by compounds having a carbon-carbon double bond in the molecule, such as vitamin C, vitamin E, butadiene, and isoprene.
In the present invention, the addition amount of the oxygen absorbent 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 in the resin composition. .

[Anti-gelling / Fish Eye Reducing Agent]
In the present invention, it is preferable to add one or more carboxylates selected from sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate and derivatives thereof. 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 carboxylates, it is possible to prevent gelation of the polyamide compound (A) that occurs during the molding process and to reduce fish eyes in the molded article, thereby improving the suitability of the molding process.

The addition amount of the carboxylates 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 resin composition. If it is 400 ppm or more, the thermal deterioration of the polyamide compound (A) can be suppressed, and gelation can be prevented. Moreover, if it is 10000 ppm or less, a polyamide compound (A) will not raise | generate a shaping | molding defect, and neither coloring nor whitening will occur. It is speculated that the presence of carboxylates, which are basic substances, in the molten polyamide compound (A) delays the modification of the polyamide compound (A) by heat and suppresses the formation of a gel that is considered to be the final modified product. The
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 carboxylates is not particularly limited, but when the powder and the smaller particle size are dry-mixed, it is easy to uniformly disperse in the resin composition. .2 mm or less is preferable.

[Antioxidant]
In 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-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl- 6-t-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-t-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-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-1-butylphenol), N, N′-hexamethylenebis (3,5-di-t-butyl) -4-hydroxy-hydroxycinnamad), 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, ethyl calcium bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate, 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-t-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O-cresol , Isooctyl-3- (3,5-di-t-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-tetraoxa Pyro [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 include organic phosphorus compounds such as diphosphite, tetra (tridecyl-4,4′-isopropylidene diphenyl diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite. Is alone or It can be used in a mixture of these.

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

[Other additives]
The resin composition for forming the oxygen absorption barrier layer includes a lubricant, a matting agent, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a plasticizer, a flame retardant, and a charge depending on the required application and performance. Additives such as an inhibitor, an anti-coloring agent, and a crystallization nucleating agent may be added. These additives can be added as necessary within a range not impairing the effects of the present invention.

2. Optional layer 2-1. Fusion Layer The tubular container of the present invention preferably further includes a fusion layer as the innermost layer and / or outermost layer of the tubular container in addition to the oxygen absorption barrier layer. By providing a fusion layer, it is equipped with a cylindrical multilayer body (parison) manufactured by a sleeve body and multilayer extrusion and a spout when a sleeve body is manufactured by fusing ends from a multilayer laminate. Workability can be improved, for example, at the time of welding with the container head part, and further, after filling the contents and then fusing the opening of the tubular container. In addition, depending on the type of contents, the physical properties of the container can be enhanced.
The fusing layer is a layer containing a thermoplastic resin having fusing properties. As the thermoplastic resin having fusibility, various polyolefin resins that can be melted by heat and fused to each other, and other thermoplastic resins can be used. For example, low density polyethylene, medium density polyethylene, Density polyethylene, linear (linear) low density polyethylene, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer Copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride Resins, polyolefins such as polyethylene or polypropylene Examples include acid-modified polyolefin resins modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid, and they may be used alone. Two or more kinds of materials may be mixed. Among these, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and ethylene-α · polymerized using a metallocene catalyst from the viewpoint of moldability, hygiene, odor, etc. Olefin copolymers are preferably used.
In addition, the fused layer is a lubricant, crystallization nucleating agent, anti-whitening agent, matting agent, heat stabilizer, weathering stabilizer, ultraviolet absorber, plasticizer, flame retardant, antistatic agent, coloring as long as the effect is not impaired. Additives such as inhibitors, antioxidants, impact resistance improvers and the like may be included.
In the case where a fusion layer is provided on both the innermost layer and the outermost layer of the tubular container, the configuration of both fusion layers may be the same or different from each other, but exhibits stable fusion properties. It is preferable to select a material that can be used.

  The thickness of the fusion layer in the present invention is preferably 5 to 200 μm, more preferably 10 to 150 μm, and still more preferably from the viewpoint of ensuring workability while exhibiting practical fusion strength. 15-100 μm.

2-2. Adhesive layer The tubular container of the present invention may further include an adhesive layer in addition to the oxygen-absorbing barrier layer. In a tubular container, when practical interlayer adhesive strength cannot be obtained between two adjacent layers (for example, an oxygen absorption barrier layer and a fusion layer), an adhesive layer is provided between the two layers. It is preferable.
The adhesive layer preferably contains a thermoplastic resin having adhesiveness. As the thermoplastic resin having adhesiveness, for example, an acid modification in which a polyolefin resin such as polyethylene or polypropylene is modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Examples include polyolefin resins. It is preferable to select a modified resin of the same type as the thermoplastic resin having a fusibility as the thermoplastic resin having adhesiveness.

  The thickness of the adhesive layer is preferably 2 to 100 μm, more preferably 5 to 90 μm, and still more preferably 10 to 80 μm from the viewpoint of ensuring workability while exhibiting practical adhesive strength.

2-3. Other Arbitrary Layers The tubular container of the present invention may further include an arbitrary layer other than those described above depending on the desired performance and the like. Examples of the material constituting such a layer include the above-mentioned various polyolefins, various polyamides such as nylon 6 and nylon MXD6, various polyesters such as polyethylene terephthalate and polyglycolic acid, and thermoplastics such as ethylene vinyl alcohol copolymer. The thing which mixed resin individually or is mentioned. In addition, various metal foils, resin films on which metal oxide films are deposited, and the like can also be used.

3. Manufacturing method of tube-shaped container The tube-shaped container of the present invention is manufactured after a film is produced through a T-die, or after a multilayer laminated film is manufactured by a method such as extrusion lamination, co-extrusion lamination, or dry lamination. Can be manufactured by a method of forming a sleeve body by fusing and then cutting to a desired size and forming into a pipe shape, and further joining a mouth portion provided with a pouring portion to the end portion of the pipe. Moreover, it can manufacture by conventionally well-known manufacturing methods, such as the method of joining a mouth part after manufacturing the parison which has a multilayer structure by coextrusion.
In this invention, the oxygen absorption barrier layer should just be used for at least one part of the tube-shaped container, The use location also depends on the manufacturing method of a tube-shaped container. For example, when a pipe is formed by processing the above-described film and a mouth is joined to the end of the pipe to produce a tubular container, an oxygen absorption barrier layer is provided in the film. The oxygen absorption barrier layer is provided on the body of the tubular container.

4). Use of tube-shaped container The tube-shaped container of the present invention includes, for example, seasonings such as mayonnaise, miso, mustard, wasabi, ginger, garlic, and other seasonings, jam, cream, butter, margarine, chocolate paste, etc. Various articles such as pasty foods, pharmaceuticals, cosmetics, toothpastes, hair dyes, dyes, soaps, chemicals, and various other sticky objects can be stored and stored.

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”,
A unit derived from 1,3-bis (aminomethyl) cyclohexane is referred to as “1,3BAC”,
The unit derived from hexamethylenediamine is “HMDA”,
The unit derived from adipic acid is “AA”,
The unit derived from isophthalic acid is “IPA”,
The unit derived from DL-alanine is “DL-Ala”,
The unit derived from DL-leucine is “DL-Leu”,
The unit derived from DL-valine is “DL-Val”,
A unit derived from ε-caprolactam is referred to as “ε-CL”.
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 compound obtained in Production Example were measured by the following methods. Moreover, the film was produced from the polyamide compound obtained by the manufacture example, and the oxygen absorption amount was measured with the following method.

(1) α-amino acid content
Quantification of the α-amino acid content of the polyamide compound was performed 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 a polyamide compound was prepared using formic acid-d as a solvent, and ¹ H-NMR measurement was performed.

(2) Relative Viscosity 1 g of the pellet 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 compound 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 compound is increased from the polyamide compound melting point (+ 20 ° C) to the cylinder T die temperature. 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.
In addition, for the polyamide compounds obtained in Production Examples 8 and 9, instead of the film sample, a powder sample 2g obtained by finely pulverizing a polyamide compound pellet or pulverized product with a pulverizer was used. The oxygen absorption amount was calculated in the same manner as described above.

Production Example 1 (Production of polyamide compound 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 Corporation) 13000 g (88.96 mol), DL-alanine (Musashino Chemical Laboratory Co., Ltd.) 880.56 g (9.88 mol), sodium hypophosphite 11.7 g (0. 11 mol) and 6.06 g (0.074 mol) of sodium acetate were added, and after sufficiently purging 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 Then, the mixture was cooled and pelletized with a pelletizer to obtain an MXDA / AA / DL-Ala copolymer (polyamide compound 1). In addition, the preparation composition ratio of each monomer was metaxylylenediamine: adipic acid: DL-alanine = 47.3: 47.4: 5.3 (mol%).

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

Production Example 3 (Production of polyamide compound 3)
MXDA / AA in the same manner as in Production Example 1 except that the charged composition ratio of each monomer was metaxylylenediamine: adipic acid: DL-alanine = 41.1: 41.3: 17.6 (mol%). / DL-Ala copolymer (polyamide compound 3) was obtained.

Production Example 4 (Production of polyamide compound 4)
MXDA / AA in the same manner as in Production Example 1 except that the composition ratio of each monomer was metaxylylenediamine: adipic acid: DL-alanine = 37.5: 37.5: 25.0 (mol%). / DL-Ala copolymer (polyamide compound 4) was obtained.

Production Example 5 (Production of polyamide compound 5)
The α-amino acid was changed to DL-leucine (manufactured by Ningbo Haishu Bio-technology), and the composition ratio of each monomer was changed to metaxylylenediamine: adipic acid: DL-leucine = 44.3: 44.6: 11.1. An MXDA / AA / DL-Leu copolymer (polyamide compound 5) was obtained in the same manner as in Production Example 1 except that the amount was (mol%).

Production Example 6 (Production of polyamide compound 6)
The α-amino acid was changed to DL-valine (manufactured by Sinogel Amino Acid Co., Ltd.), and the composition ratio of each monomer was changed to metaxylylenediamine: adipic acid: DL-valine = 44.3: 44.6: 11. 0.1 (mol%) was carried out in the same manner as in Production Example 1 to obtain an MXDA / AA / DL-Val copolymer (polyamide compound 6).

Production Example 7 (Production of polyamide compound 7)
The dicarboxylic acid component was changed to a mixture of isophthalic acid (manufactured by EI International Chemical Co., Ltd.) and adipic acid, and the composition ratio of each monomer was changed to metaxylylenediamine: adipic acid: isophthalic acid: DL- MXDA / AA / IPA / DL-Ala copolymer (polyamide compound 7) in the same manner as in Production Example 1 except that alanine = 44.3: 39.0: 5.6: 11.1 (mol%). Got.

Production Example 8 (Production of polyamide compound 8)
Ε-Caprolactam (manufactured by Ube Industries) was used as a comonomer, the α-amino acid was changed to DL-leucine, and the composition ratio of each monomer was changed to metaxylylenediamine: adipic acid: DL-leucine: ε- Caprolactam = 41.0: 41.3: 11.8: 5.9 (mol%), and the same as in Production Example 1 except that stirring was stopped when a predetermined torque was reached without further depressurization operation Thus, an MXDA / AA / DL-Leu / ε-CL copolymer (polyamide compound 8) was obtained.

Production Example 9 (Production of polyamide compound 9)
The diamine component was changed to a mixture of 1,3-bis (aminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine, and the charge composition ratio of each monomer was changed to metaxylylenediamine: 1,3- When bis (aminomethyl) cyclohexane: adipic acid: DL-alanine = 33.2: 11.1: 44.6: 11.1 (mol%) and when a predetermined torque is reached without further decompression operation An MXDA / 1,3BAC / AA / DL-Ala copolymer (polyamide compound 9) was obtained in the same manner as in Production Example 1 except that the stirring was stopped.

Production Example 10 (Production of polyamide compound 10)
The diamine component was changed to a mixture of hexamethylenediamine (manufactured by Showa Chemical Co., Ltd.) and metaxylylenediamine, and the composition ratio of each monomer was changed to metaxylylenediamine: hexamethylenediamine: adipic acid: DL-alanine = 33. .3: 11.1: 44.5: 11.1 (mol%) Except that it was set as the same as manufacture example 1, the MXDA / HMDA / AA / DL-Ala copolymer (polyamide compound 10) was obtained. .

Production Example 11 (Production of polyamide compound 11)
N-MXD6 was prepared in the same manner as in Production Example 1 except that DL-alanine was not added and the charged composition ratio of each monomer was metaxylylenediamine: adipic acid = 49.8: 50.2 (mol%). (Polyamide compound 11) was obtained.

Production Example 12 (Production of polyamide compound 12)
N-MXD6 was prepared in the same manner as in Production Example 1 except that DL-alanine was not added and the composition ratio of each monomer was metaxylylenediamine: adipic acid = 50.2: 49.8 (mol%). (Polyamide compound 12) was obtained.

  Table 1 shows the charged monomer composition of polyamide compounds 1 to 12, 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 compound.

Next, in Examples 1-20 and Comparative Examples 1-18, a tubular container was prepared using the polyamide compounds 1-12.
The following materials were used as the resin (B).
(1) Nylon 6 (N-6): Ube Industries, UBE nylon, grade: 1022B
(2) Nylon MXD6 (N-MXD6): The polyamide compound 11 obtained in Production Example 11 was used.
(3) Polyethylene (LDPE): manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LD LC602A
(4) Adhesive polyethylene (adhesive PE): manufactured by Mitsubishi Chemical Corporation, trade name: Modic L504
(5) Polylactic acid (PLA): Unitika Ltd., trade name: Terramac TP-4000
(6) Polyethylene terephthalate (PET): Nihon Unipet Co., Ltd. Grade: RT553C
(7) Ethylene-vinyl alcohol copolymer (EVOH): Kuraray Co., Ltd., Eval, Grade: F104B

Example 1
High-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec HD-HB431) was used from the first extruder using a four-kind five-layer multi-layer pipe extruder comprising a first to fourth extruder, a feed block, a die and a cooling device. , Hereinafter abbreviated as HDPE), adhesive polyethylene from the second extruder (Mitsubishi Chemical Co., Ltd., trade name: Modic L553, hereinafter abbreviated as adhesive PE), from the third extruder in Production Example 1 Blended pellets prepared by dry blending the produced polyamide compound 1 and N-6 at a ratio of 90:10 (mass ratio), low-density polyethylene (Nippon Polyethylene Co., Ltd., Novatec LD-YF30, hereinafter LDPE) from the fourth extruder Are abbreviated to HDPE layer (120 μm) / adhesive PE layer (30 μm) / polyamide compound in order from the inner layer side to the outer layer side. X Resin (B) 4 types and 5 layers multilayer pipe having an inner diameter of 35 mm having a constitution of blend layer (50 μm) / adhesive PE layer (30 μm) / LDPE layer (120 μm) were produced. After cutting the multilayer pipe into a length of 160 mm, a gas barrier property and a high-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec HD-HJ360) is used as one end of the pipe. Joined to obtain a tubular container. In addition, since the said tubular container is filled with the content by the below-mentioned evaluation test, the other edge part of a pipe is not closed but is the open state.

Example 2
Example 1 except that polyamide compound 2 was used instead of polyamide compound 1 in the polyamide compound × resin (B) blend layer, and the mixing ratio of polyamide compound 2 and N-6 was 80:20 (mass ratio). Similarly, a tubular container was produced.
Example 3
Example 1 except that polyamide compound 3 was used instead of polyamide compound 1 in the polyamide compound × resin (B) blend layer, and the mixing ratio of polyamide compound 3 and N-6 was 70:30 (mass ratio). Similarly, a tubular container was produced.
Example 4
Example 1 except that polyamide compound 4 was used instead of polyamide compound 1 in the polyamide compound × resin (B) blend layer, and the mixing ratio of polyamide compound 4 and N-6 was 60:40 (mass ratio). Similarly, a tubular container was produced.
Example 5
A tubular container was produced in the same manner as in Example 2 except that the polyamide compound 5 was used in place of the polyamide compound 2 in the polyamide compound × resin (B) blend layer.
Example 6
A tubular container was prepared in the same manner as in Example 2 except that polyamide compound 6 was used instead of polyamide compound 2 in the polyamide compound × resin (B) blend layer.
Example 7
A tubular container was prepared in the same manner as in Example 2 except that polyamide compound 7 was used instead of polyamide compound 2 in the polyamide compound × resin (B) blend layer.
Example 8
A tubular container was prepared in the same manner as in Example 2 except that the polyamide compound 10 was used in place of the polyamide compound 2 in the polyamide compound × resin (B) blend layer.

Comparative Example 1
Instead of the polyamide compound × resin (B) blend layer, a tube-like container was produced in the same manner as in Example 1 except that the polyamide compound 1 was not mixed and a resin (B) layer consisting only of N-6 was provided.
Comparative Example 2
A tubular container was prepared in the same manner as in Example 1 except that the polyamide compound 11 was used in place of the polyamide compound 1 in the polyamide compound × resin (B) blend layer.
Comparative Example 3
A tubular container was prepared in the same manner as in Example 2 except that the polyamide compound 11 was used in place of the polyamide compound 2 in the polyamide compound × resin (B) blend layer.
Comparative Example 4
A tubular container was prepared in the same manner as in Example 3 except that the polyamide compound 11 was used in place of the polyamide compound 3 in the polyamide compound × resin (B) blend layer.
Comparative Example 5
A tubular container was produced in the same manner as in Example 4 except that the polyamide compound 11 was used in place of the polyamide compound 4 in the polyamide compound × resin (B) blend layer.

Example 9
Other than using N-MXD6 (polyamide compound 11) instead of N-6 in the polyamide compound × resin (B) blend layer, and setting the mixing ratio of polyamide compound 1 and N-MXD6 to 30:70 (mass ratio) Produced a tubular container in the same manner as in Example 1.
Example 10
A tubular container was produced in the same manner as in Example 9 except that polyamide compound 2 was used instead of polyamide compound 1 in the polyamide compound × resin (B) blend layer.
Example 11
Example 9 except that polyamide compound 3 was used instead of polyamide compound 1 in the polyamide compound × resin (B) blend layer, and the mixing ratio of polyamide compound 3 and N-MXD6 was 20:80 (mass ratio). Similarly, a tubular container was produced.
Example 12
A tubular container was produced in the same manner as in Example 11 except that the polyamide compound 4 was used in place of the polyamide compound 3 in the polyamide compound × resin (B) blend layer.
Example 13
A tubular container was prepared in the same manner as in Example 9 except that polyamide compound 8 was used instead of polyamide compound 1 in the polyamide compound × resin (B) blend layer.
Example 14
A tubular container was produced in the same manner as in Example 9 except that the polyamide compound 9 was used in place of the polyamide compound 1 in the polyamide compound × resin (B) blend layer.

Comparative Example 6
Instead of the polyamide compound × resin (B) blend layer, a tubular container was produced in the same manner as in Example 9 except that the polyamide (1) was not mixed and a resin (B) layer consisting only of N-MXD6 was provided.

Example 15
A tubular container was produced in the same manner as in Example 2 except that PET was used instead of N-6 in the polyamide compound × resin (B) blend layer.
Example 16
A tubular container was produced in the same manner as in Example 15 except that the mixing ratio of the polyamide compound 2 and PET was 70:30 (mass ratio).

Comparative Example 7
Instead of the polyamide compound × resin (B) blend layer, a tube-shaped container was produced in the same manner as in Example 15 except that the polyamide compound 2 was not mixed and a resin (B) layer consisting only of PET was provided.
Comparative Example 8
A tubular container was prepared in the same manner as in Example 15 except that the polyamide compound 11 was used in place of the polyamide compound 2 in the polyamide compound × resin (B) blend layer.
Comparative Example 9
A tubular container was produced in the same manner as in Example 16 except that the polyamide compound 11 was used in place of the polyamide compound 2 in the polyamide compound × resin (B) blend layer.

Example 17
A tube similar to Example 3 except that EVOH was used instead of N-6 in the polyamide compound × resin (B) blend layer, and the mixing ratio of polyamide compound 3 and EVOH was 10:90 (mass ratio). A container was prepared.
Example 18
A tubular container was prepared in the same manner as in Example 17 except that the mixing ratio of the polyamide compound 3 and EVOH was 20:80 (mass ratio).

Comparative Example 10
Instead of the polyamide compound × resin (B) blend layer, a tubular container was produced in the same manner as in Example 17 except that the polyamide (3) was not mixed and a resin (B) layer consisting only of EVOH was provided.
Comparative Example 11
A tubular container was produced in the same manner as in Example 17 except that the polyamide compound 11 was used in place of the polyamide compound 3 in the polyamide compound × resin (B) blend layer.
Comparative Example 12
A tubular container was produced in the same manner as in Example 18 except that the polyamide compound 11 was used in place of the polyamide compound 3 in the polyamide compound × resin (B) blend layer.

Comparative Example 13
Instead of the blend pellet obtained by dry-mixing polyamide compound 1 and N-6 at a ratio of 90:10 (mass ratio) to the polyamide compound × resin (B) blend layer, polyamide compound 11, N-6 and cobalt stearate (II ) Was used in the same manner as in Example 1 except that blend pellets obtained by dry mixing at a ratio of 80: 20: 0.12 (mass ratio) were used.

Comparative Example 14
Instead of the blend pellet obtained by dry-mixing polyamide compound 1 and N-6 at a ratio of 90:10 (mass ratio) to the polyamide compound × resin (B) blend layer, polyamide compound 12, N-6 and cobalt stearate (II ) And maleic acid-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name: M-2000-20) in a dry blend ratio of 80: 20: 0.12: 2.4 (mass ratio). A tubular container was produced in the same manner as in Example 1 except that it was used.

Comparative Example 15
Dry blend of 40 parts by mass of granular oxygen absorbent coated with 3 parts by mass of calcium chloride and 100 parts by mass of LDPE with respect to 100 parts by mass of reduced iron powder having an average particle size of 30 μm, followed by extrusion with a 35 mm twin screw extruder, After cooling with a net belt with a blower, LDPE containing oxygen absorbent was obtained through a pelletizer.
Using 5 types and 6 layers of multi-layer pipe extruder comprising a first to fifth extruder, a feed block, a die and a cooling device, HDPE from the first extruder, LDPE containing the oxygen absorbent from the second extruder, Adhesive PE from the third extruder, blend pellet obtained by dry-mixing the polyamide compound 11 and N-6 obtained in Production Example 11 from the fourth extruder at a ratio of 80:20 (mass ratio), fifth extrusion LDPE was extruded from the machine, and in order from the inner layer side to the outer layer side, HDPE layer (60 μm) / LDPE layer containing oxygen absorbent (60 μm) / adhesive PE layer (30 μm) / polyamide compound × resin (B) blend layer ( 50 types) / adhesive PE layer (30 μm) / LDPE layer (120 μm) having a configuration of 5 types and 6 layers multilayer pipes with an inner diameter of 35 mm were manufactured. After cutting the multilayer pipe into a length of 160 mm, a gas barrier property and a high-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec HD-HJ360) is used as one end of the pipe. Joined to obtain a tubular container. In addition, since the said tubular container is filled with the content by the below-mentioned evaluation test, the other edge part of a pipe is not closed but is the open state.

Comparative Example 16
A tubular container was prepared in the same manner as in Comparative Example 13 except that the resin (B) was changed from N-6 to PET.

Comparative Example 17
Polyamide compound × resin (B) blend layer is blended with polyamide compound 11, N-6, cobalt stearate (II) and maleic acid-modified polybutadiene in a ratio of 80: 20: 0.12: 2.4 (mass ratio). Instead of using blended pellets, EVOH, cobalt stearate (II), and maleic acid-modified polybutadiene were mixed at a ratio of 100: 0.12: 2.4 (mass ratio). A tubular container was produced in the same manner as in Comparative Example 14.

Comparative Example 18
A tubular container was produced in the same manner as in Comparative Example 15 except that the resin (B) was changed from N-6 to PET.

Using the tubular containers prepared in Examples 1 to 18 and Comparative Examples 1 to 18, the oxidative deterioration suppressing effect, flavor retention, and strength maintenance were evaluated as follows.
(1) Oxidation degradation inhibitory effect (L-ascorbic acid residual rate)
The tip hole of the mouth provided in the tube-shaped container was sealed with an aluminum foil laminated film, and the cap was closed. Next, 100 ml of a 10% aqueous solution of L-ascorbic acid was filled from the opening of the tubular container, and the opening was sealed by heat sealing. After storing this container in an environment of 25 ° C. and 50% RH for 3 months, the content solution is taken out, 10 ml of the content solution is put into a 100 ml capacity tall beaker, and then 5 ml of a mixed aqueous solution of metaphosphoric acid and acetic acid and 40 ml of distilled water. Was added. Subsequently, 0.05 mol / l iodine solution was used as a titrant, and titration was performed by an inflection point detection method using a potentiometric titration apparatus. The L-ascorbic acid residual rate was determined from the result. In addition, if the residual rate of L-ascorbic acid is high, it means that it is excellent in the effect which suppresses the oxidative degradation of the content.
(2) Flavor retention After opening and sealing the opening of the tube-shaped container, 100 ml of distilled water is filled from the tip hole of the mouth provided in the tube-shaped container, and the tip of the mouth is filled with an aluminum foil laminated film The hole was sealed and the cap was closed. After storing this container in an environment of 25 ° C. and 50% RH for one month, the aluminum foil laminated film was peeled off to investigate the odor of the head space in the container.
A sample in which no odor was recognized was marked with ◯, and a sample in which odor was recognized was marked with ×.
(3) Strength maintenance The distilled water is extracted from the container after storing the distilled water for one month in the flavor retention test, and the container is squeezed by hand 50 times. investigated.
The case where no delamination was observed was marked with ◯, and the case where delamination was observed was marked with x.
Table 2 shows the evaluation results.

As for the tube-shaped containers of Examples 1-18, the evaluation results of flavor retention and strength maintenance were all good, and the flavor retention and strength maintenance were excellent.
Moreover, the tube-shaped container (Examples 1-8) which provided the layer which blended polyamide compound 1-7, 10 which has an oxygen absorption function to N-6 (Examples 1-8) provided the layer which consists only of N-6 Compared with (Comparative Example 1) and a tubular container (Comparative Examples 2 to 5) provided with a layer obtained by blending N-6 with a polyamide compound 11 having no oxygen absorption function, the L-ascorbic acid residual rate is high. It was excellent in the effect of suppressing oxidative deterioration. Similarly, the tubular containers of Examples 9-14 are compared with the tubular containers of Comparative Example 6, and the tubular containers of Examples 15-16 are compared with the tubular containers of Comparative Examples 7-9. The tubular containers of Examples 17 to 18 had a higher L-ascorbic acid residual rate than the tubular containers of Comparative Examples 10 to 12, and were excellent in terms of the effect of suppressing oxidative degradation.

Although the tube-shaped container of Comparative Example 13 was excellent in the oxidation deterioration suppressing effect and the flavor retention, the polyamide layer was destroyed and delamination occurred in the container's manual test, and the appearance of the container deteriorated. Although the polyamide compound 11 and the transition metal compound (cobalt stearate (II)) coexisted to express oxygen absorption performance, the polyamide compound 11 was oxidized and decomposed at the same time, and the polyamide compound × resin (B) blend layer was deteriorated in strength. it is conceivable that.
Although the tubular container of Comparative Example 14 was excellent in the oxidative deterioration suppressing effect and strength maintenance, an unpleasant odor was observed at the time of opening, and the flavor retention was poor. Since the polyamide compound 12 has a high terminal amino group concentration and is substantially difficult to oxidize, the polyamide compound × resin (B) blend layer is not greatly deteriorated in strength and coexists with maleic acid-modified polybutadiene and cobalt stearate. Although the oxygen absorption performance was exhibited in this case, it is considered that a bad odor was generated due to the generation of low molecular weight compounds accompanying the oxidative degradation of polybutadiene.
Although the tube-shaped container of Comparative Example 15 was excellent in the oxidation deterioration suppressing effect and strength maintenance, an iron odor was observed at the time of opening. Although the polyamide compound × resin (B) blend layer expresses oxygen barrier performance and the oxygen absorbent-containing LDPE expresses oxygen absorption performance, iron powder is used as the oxygen absorbent, which is attributed to the iron powder. This is probably because an iron odor occurred.
Moreover, even if it changed resin (B) of Comparative Examples 13-15 into another material (Comparative Examples 16-18), it turned out that the problem is not solved.

Example 19
Polyamide obtained in Production Example 4 from HDPE from the first extruder and HDPE from the second extruder, using 5 types and 6 layers multi-layer pipe extrusion equipment consisting of 1st to 5th extruder, feed block, die and cooling device Blend pellets (compacted with polyamide compound × resin (B) blend layer α) obtained by dry-mixing Compound 4, LDPE, and adhesive PE at a ratio of 70:20:10 (mass ratio), adhesive PE from the third extruder , Blend pellet obtained by dry-mixing the polyamide compound 11 obtained in Production Example 11 from the fourth extruder and N-6 at a ratio of 80:20 (mass ratio) (becomes a polyamide compound × resin (B) blend layer β) The LDPE was extruded from the fifth extruder, and the HDPE layer (60 μm) / adhesive PE layer (30 μm) / polyamide compound × resin (B) blend layer α (60 μm) in this order from the inner layer side to the outer layer side. / Polyamide compound × resin (B) blend layer beta (50 [mu] m) / adhesive PE layer (30 [mu] m) / LDPE layer were prepared five 6-layered pipe having an inner diameter of 35mm having the configuration of (120 [mu] m). After cutting the multilayer pipe into a length of 160 mm, a gas barrier property and a high-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec HD-HJ360) is used as one end of the pipe. Joined to obtain a tubular container. In addition, since the said tubular container is filled with the content by the below-mentioned evaluation test, the other edge part of a pipe is not closed but is the open state.

Example 20
Instead of the blend pellet obtained by dry-mixing the polyamide compound 4, the LDPE, and the adhesive PE at a ratio of 70:20:10 (mass ratio) to the polyamide compound × resin (B) blend layer α, the polyamide compound 4 and PLA are 70: A tubular container was produced in the same manner as in Example 19 except that blend pellets comprising 30 (mass ratio) were used.

  About the tube-shaped container produced in the said Example 19 and 20, the oxidation degradation inhibitory effect, flavor retainability, and strength maintenance property were evaluated with the evaluation method similar to the above-mentioned evaluation method. The evaluation results of Examples 19 and 20 are shown in Table 3 together with the evaluation results of Comparative Example 3 described above.

  Polyamide compound x resin (B) blend layer α using polyolefin (Example 19) or plant-derived resin (Example 20) as resin (B) is applied to the tube-like container of Comparative Example 3 having no oxygen absorption function. By laminating, the L-ascorbic acid residual rate could be maintained high. It has been confirmed that the tubular container exhibits the oxygen absorbing function even when a polyolefin or a plant-derived resin is used as the resin (B) blended with the polyamide compound having an oxygen absorbing function.

  The tubular container of the present invention can be suitably used as a packaging material.

Claims (10)

A tubular container including a layer formed from a resin composition containing a polyamide compound (A) and a resin (B),
The polyamide compound (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 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%,
The tubular container containing 0.1-50 mol% of structural units represented by the following general formula (III).

[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 tubular container 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.   The tubular container according to claim 1 or 2, 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 tube-shaped container in any one of.   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. The tubular container according to crab. The polyamide compound (A) further contains an ω-aminocarboxylic acid unit represented by the following general formula (X) in an amount of 0.1 to 49.9 mol% in all the structural units of the polyamide compound (A). Item 6. The tubular container according to any one of Items 1 to 5.

[In said general formula (X), p represents the integer of 2-18. ]   The tubular container according to claim 6, wherein the ω-aminocarboxylic acid unit contains 50 mol% or more of a total of 6-aminohexanoic acid units and / or 12-aminododecanoic acid units.   The said resin composition contains at least 1 sort (s) chosen from the group which consists of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and plant-derived resin as said resin (B), Any one of Claims 1-7 The tubular container according to crab. The relative viscosity of the polyamide compound (A) is 1.8 or more and 4.2 or less, and the mass ratio of the polyamide compound (A) / the resin (B) is 5/95 to 95/5. Item 9. A tubular container according to any one of Items 1 to 8. The relative viscosity of the polyamide compound (A) is 1.01 or more and less than 1.8, and the mass ratio of the polyamide compound (A) / the resin (B) is 5/95 to 50/50, Item 9. A tubular container according to any one of Items 1 to 8.