TW201311819A - Direct blow molding bottle - Google Patents

Abstract

The present invention provides a direct blow bottle comprising a layer formed of a polyamine compound (A) and a resin composition containing the resin (B), the polyamine compound (A) comprising: a specific diamine unit 50 More than 25% by mole of the diamine unit of mol% or more, 25 to 50 mol% of the dicarboxylic acid unit of 50 mol% or more of the specific dicarboxylic acid unit, and 0.1 to 50 mol% of the specific constituent unit.

Description

Direct blow molding bottle

The present invention relates to a direct blow molded bottle having oxygen barrier properties and oxygen absorbing properties.

Polyamine obtained by polycondensation reaction of xylene diamine and aliphatic dicarboxylic acid, for example, polyamidamine (hereinafter referred to as nylon MXD6) obtained from meta-xylene diamine and adipic acid, has high strength, It has a high modulus of elasticity and exhibits low penetrability for gaseous substances such as oxygen, carbon dioxide, odor and flavor components, and is therefore widely used as a gas barrier material in the field of packaging materials. Compared with other gas barrier resins, nylon MXD6 has good thermal stability during melting, so it can be coextruded with thermoplastic resins such as polyethylene terephthalate (hereinafter referred to as PET), nylon 6 and polypropylene. Forming or total injection molding. Therefore, nylon MXD6 is actively utilized as a gas barrier layer constituting a multilayer structure.

In recent years, a small amount of a transition metal compound is added to nylon MXD6 and mixed, and an oxygen absorbing function is imparted to the nylon MXD6, and is utilized as an oxygen barrier material constituting a container or a packaging material, whereby the nylon MXD6 is absorbed and penetrated from the outside of the container. Oxygen, and the method of absorbing the oxygen remaining in the inside of the container by the nylon MXD6 to improve the preservation of the contents of the container made of the conventional oxygen barrier thermoplastic resin has been gradually put into practical use (refer to, for example, a patent). Documents 1 and 2).

On the other hand, in order to remove oxygen in the container, an oxygen absorbing agent has been used from the past. For example, Patent Literatures 3 and 4 describe an oxygen-absorbing multilayer body and an oxygen-absorbing film obtained by dispersing an oxygen-absorbing agent such as iron powder in a resin. Patent Document 5 describes a product comprising an oxygen-swept layer containing an ethylenically unsaturated compound such as polybutadiene and a transition metal catalyst such as cobalt; and an oxygen blocking layer such as polyamine.

Further, Patent Document 6 discloses a multilayer bottle obtained by directly blowing and molding a polyester resin layer as an oxygen barrier material and a polyglycolic acid layer.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-341747

Patent Document 2: Japanese Patent No. 2991437

Patent Document 3: Japanese Patent Laid-Open No. 2-72851

Patent Document 4: Japanese Patent Laid-Open No. Hei 4-90848

Patent Document 5: Japanese Patent Laid-Open No. Hei 5-115776

Patent Document 6: Japanese Laid-Open Patent Publication No. 2003-266527

An oxygen-absorbing multilayer body and a container obtained by dispersing an oxygen-absorbing agent such as iron powder in a resin may be opaque by coloring the resin by an oxygen-absorbing agent such as iron powder, and thus may be used in a field in which packaging requiring transparency is required. Limitations on the use.

On the other hand, the resin composition containing a transition metal such as cobalt has an advantage that it can be applied to a packaging container requiring transparency, but the resin composition is not colored by the transition metal catalyst. Further, these resin compositions absorb oxygen due to the transition metal catalyst, causing oxidation of the resin. Specifically, in nylon MXD6, it is considered that the hydrogen atom of the methylene chain adjacent to the aryl group of the polyamine resin is removed due to the transition metal atom, thereby generating a radical, due to aerobics for the aforementioned radical The addition of molecules leads to the generation of peroxidic free radicals, and the removal of hydrogen atoms by peroxidation radicals. Due to such a machine rotation, the resin is oxidized by oxygen absorption, so that decomposition products are generated and a bad odor is generated for the contents of the container, or the color tone or strength of the container is deteriorated due to oxidative degradation of the resin. .

The object of the present invention is to provide a bottle which exhibits oxygen barrier properties, exhibits oxygen-absorbing properties without a transition metal, inhibits oxidative degradation of contents, and can detract from flavor of the contents, even if stored for a long period of time. The strength of the oxygen barrier layer does not decrease.

The present invention provides the following direct blow molded bottles.

A direct blow bottle comprising a layer formed of a resin composition containing a polyamine compound (A) and a resin (B); the polyamine compound (A) comprises: a diamine unit of 25 to 50 mol% And an alicyclic diamine unit selected from the group consisting of aromatic diamine units represented by the following formula (I-1), represented by the following formula (I-2), and the following formula (I) -3) The total content of at least one diamine unit in the group consisting of linear aliphatic diamine units is 50 mol% or more; the dicarboxylic acid unit is 25 to 50 mol%, wherein The linear aliphatic dicarboxylic acid unit represented by the formula (II-1) and/or the aromatic dicarboxylic acid unit represented by the following formula (II-2) has a total content of 50 mol% or more; (III) represents a constituent unit of 0.1 to 50% by mole;

[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 extension An aryl group; in the formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group].

The direct blow molding bottle of the invention can exhibit oxygen barrier property, and can exhibit oxygen absorption performance without transition metal, and the strength of the oxygen barrier layer decreases with oxygen absorption. small. Therefore, the direct blow molded multilayer bottle of the present invention is excellent in the function of suppressing oxidative degradation of the content, and has almost no odor or a substance which causes a change in flavor, and is excellent in flavor retainability.

(Formation of the invention) <<Direct blow molding bottle>>

The direct blow molded bottle of the present invention contains at least a bottle formed of a resin composition containing a polyamine compound (A) and a resin (B) (hereinafter sometimes referred to as an "oxygen barrier layer"). The bottle of the present invention may be a single layer bottle, and may also be a multi-layer bottle further comprising any layer as needed.

In the case where the direct blow molded bottle of the present invention is a multilayer bottle, the layer constitution thereof is not particularly limited, and the number or kind of layers is not particularly limited. For example, when the oxygen-absorbing barrier layer is a layer (X) and the other resin layer is a layer (Y), it may be composed of a layer (X) of one layer and a layer (Y) of one layer (Y), and Y. The /X structure may be composed of three layers of Y/X/Y composed of a layer (X) of one layer and a layer (Y) of two layers. Further, it may be composed of five layers of Y1/Y2/X/Y2/Y1 composed of two layers (Y) of one layer (X) and two layers (Y1) of the layer (Y1) and the layer (Y2). Further, the direct blow bottle of the present invention may contain any layer such as an adhesive layer (AD) as needed, and may be, for example, a 7-layer structure of Y1/AD/Y2/X/Y2/AD/Y1.

Further, in the case of a multilayer structure, the position of the oxygen-absorbing barrier layer is close to the inner layer, and since the moisture of the content of the triggering agent is increased, the oxygen absorption rate is increased, and oxygen is started earlier. Furthermore, by providing a high-barrier resin layer on the outer side of the oxygen-absorbing barrier layer, the oxygen-absorbing barrier layer can block oxygen from the outside of the container, and at the same time, can absorb the oxygen remaining in the container with good efficiency.

1. A layer formed of a resin composition containing a polyamine compound (A) and a resin (B) (oxygen barrier layer)

In the present invention, the oxygen-absorbing barrier layer is formed of a resin composition, and the resin composition is also contained in addition to a conventionally known resin (hereinafter sometimes referred to as "resin (B)"). The specific polyamine compound (hereinafter sometimes referred to as "polyamine compound (A)") exhibits oxygen absorption performance and oxygen barrier performance.

In the present invention, the polyamine compound (A) contained in the resin composition may be one type or a combination of two or more types. In addition, the resin (B) contained in the resin composition may be one type or a combination of two or more types.

In the resin composition used in the present invention, the desired ratio of the mass ratio of the polyamine compound (A) to the resin (B) varies depending on the relative viscosity of the polyamide compound (A).

When the relative viscosity of the polyamine compound (A) is 1.8 or more and 4.2 or less, the mass ratio of the polyamine compound (A) / resin (B) is preferably selected from the range of 5/95 to 95/5. From the viewpoint of the oxygen absorption performance and the oxygen barrier property, the content of the polyamidamine compound (A) is preferably 10 parts by mass or more, and 30 parts by mass based on 100 parts by mass of the total of the polyamide compound (A) and the resin (B). More than the above.

When the relative viscosity of the polyamine compound (A) is 1.01 or more and less than 1.8, it is preferable to contain a large amount of the resin (B) from the viewpoint of moldability, and the mass ratio of the polyamine compound (A) / resin (B) It is better to choose from the range of 5/95~50/50. From the viewpoint of the oxygen absorption performance and the oxygen barrier property, the content of the polyamidamine compound (A) is preferably 10 parts by mass or more, and 30 parts by mass based on 100 parts by mass of the total of the polyamide compound (A) and the resin (B). More than the above.

In addition to the polyamine compound (A) and the resin (B), the resin composition to be used in the present invention may contain an additive (hereinafter sometimes referred to as "additive (C)") depending on the desired performance and the like. The content of the polyamine compound (A) and the resin (B) in the resin composition is preferably from 90% by mass to 100% by mass, from the viewpoints of moldability, oxygen absorption performance, and oxygen barrier property. 95 The quality %~100% by mass is better.

The thickness of the oxygen-absorbing barrier layer is preferably from 2 to 100 μm, more preferably from 5 to 90 μm, from the viewpoint of improving oxygen absorption performance and oxygen barrier property while ensuring processability of the direct blow bottle. It is 10~80μm.

1-1. Polyamine compound (A) <Composition of Polyamine Compound (A)>

In the present invention, the polyamidamine compound (A) comprises: 25 to 50 mol% of a diamine unit, which is selected from the group consisting of aromatic diamine units represented by the following formula (I-1), and having the following formula ( The total content of at least one diamine unit of the group consisting of the alicyclic diamine unit represented by the following formula (I-3) and the linear aliphatic diamine unit represented by the following formula (I-3) is 50 More than 5% by mole; a dicarboxylic acid unit of 25 to 50 mol%, wherein the linear aliphatic dicarboxylic acid unit represented by the following formula (II-1) and/or represented by the following formula (II-2) The total content of the aromatic dicarboxylic acid unit is 50% by mole or more; and the carboxylic acid unit containing a tertiary hydrogen (preferably, the constituent unit represented by the following formula (III)) is 0.1 to 50 mol%.

[In the above formula (I-3), m represents an integer of 2 to 18. In the above formula (II-1), n represents an integer of 2 to 18. In the above formula (II-2), Ar represents an exoaryl group. In the above formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ]

The total amount of the diamine unit, the dicarboxylic acid unit, and the third-order hydrogen-containing carboxylic acid unit is not more than 100 mol%. The polyamine compound (A) may further contain a constituent unit other than the above, without departing from the effects of the present invention.

In the polyamine compound (A), the content of the carboxylic acid unit having a hydrogen level of 3 is 0.1 to 50 mol%. When the content of the carboxylic acid unit containing 3-grade hydrogen is less than 0.1 mol%, sufficient expression cannot be exhibited. Oxygen absorption performance. On the other hand, if the content of the carboxylic acid unit containing the third-order hydrogen exceeds 50 mol% and the hydrogen content of the third-order is too large, the physical properties such as gas barrier properties and mechanical properties of the polyamidamine compound (A) are lowered, especially including the third-order. In the case where the carboxylic acid of hydrogen is an amino acid, since the peptide bond is continuous, not only the heat resistance is insufficient, but also a ring composed of a dimer of an amino acid occurs, which hinders polymerization. The content of the carboxylic acid unit having a hydrogen level of 3 is preferably 0.2 mol% or more, more preferably 1 mol% or more, and more preferably from the viewpoint of oxygen absorbing property or the property of the polyamidamine compound (A). 40% or less, more preferably 30% by mole or less.

The content of the diamine unit in the polyamine compound (A) is 25 to 50 mol%, and is preferably 30 to 50 mol% from the viewpoint of oxygen absorption performance or polymer property. Similarly, in the polyamine compound (A), the content of the dicarboxylic acid unit is 25 to 50 mol%, preferably 30 to 50 mol%.

The ratio of the content of the diamine unit to the dicarboxylic acid unit is preferably the same amount from the viewpoint of the polymerization reaction, and the content of the dicarboxylic acid unit is more preferably ± 2 mol% of the content of the diamine unit. When the content of the dicarboxylic acid unit exceeds ±2 mol% of the content of the diamine unit, the degree of polymerization of the polyamine compound (A) is not easily improved. Therefore, it takes a lot of time to increase the degree of polymerization, and thermal deterioration is likely to occur.

[diamine unit]

a diamine unit in the polyamine compound (A), which comprises an aromatic diamine unit represented by the above formula (I-1), an alicyclic diamine represented by the above formula (I-2) The unit and the diamine unit having a total content of at least one of the diamine units in the group consisting of the linear aliphatic diamine units represented by the above formula (I-3) is preferably 50 mol% or more, and the content is preferably It is 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and further preferably 100 mol% or less.

Examples of the compound which can constitute the aromatic diamine unit represented by the above formula (I-1) include o-xylenediamine, m-xylenediamine, and p-xylylenediamine. These may be used alone or in combination of two or more.

The compound which can constitute the alicyclic diamine unit represented by the above formula (I-2) includes 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane. A bis(aminomethyl)cyclohexane such as an alkane. These may be used alone or in combination of two or more.

The bis(aminomethyl)cyclohexane has a structural isomer, and by increasing the cis isomer ratio, the crystallinity is high, and good formability can be obtained. On the other hand, if the cis isomer ratio is low, the crystallinity is low, and a transparent one can be obtained. Therefore, in order to increase the crystallinity, the cis isomer content ratio in the bis(aminomethyl)cyclohexane group is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90% or more. On the other hand, in the case where the crystallinity is low, the cis isomer content ratio of the bis(aminomethyl)cyclohexane is preferably 50 mol% or less, more preferably 40 mol% or less, and still more. Good for 30% or less.

In the above formula (I-3), m represents an integer of from 2 to 18, preferably from 3 to 16, more preferably from 4 to 14, still more preferably from 6 to 12.

Examples of the compound which can constitute the linear aliphatic diamine unit represented by the above formula (I-3) include ethylenediamine, 1,3-propanediamine, tetramethylenediamine, and pentamethylenediamine. Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecyldiamine, dodecamethylenediamine Aliphatic diamines, but are not limited to these. Among these, hexamethylenediamine is preferred. These may be used alone or in combination of two or more.

The diamine unit in the polyamine compound (A) is preferably one which is excellent in transparency or color tone, or which is easy to form a general-purpose thermoplastic resin, in addition to the excellent gas barrier property of the polyamine compound (A). It is preferable to contain the aromatic diamine unit represented by the above formula (I-1) and/or the alicyclic diamine unit represented by the above formula (I-2), and to impart moderate crystallinity to the polyamine compound (A). From the viewpoint of the nature, the linear aliphatic diamine unit represented by the above formula (I-3) is preferred. In particular, the aromatic diamine unit represented by the above formula (I-1) is preferred from the viewpoint of oxygen absorption performance or properties of the polyamidamine compound (A).

a diamine unit in the polyamine compound (A), in addition to exhibiting the polyamine compound (A) In addition to the excellent gas barrier properties, from the viewpoint of easy molding of a general-purpose thermoplastic resin, it is preferably 50 mol% or more of m-xylylenediamine unit, and the content is preferably 70 mol% or more, more preferably 80. More than or equal to 5% by mole, more preferably 90% by mole or more, and preferably 100% by mole or less.

Examples of the compound which can constitute a diamine unit other than the diamine unit represented by any one of the above formulas (I-1) to (I-3) include aromatic diamines such as p-phenylenediamine and 1,3-two. An alicyclic diamine such as aminocyclohexane or 1,4-diaminocyclohexane, N-methylethylenediamine, 2-methyl-1,5-pentanediamine, 1-amino-3 - an aliphatic diamine such as aminomethyl-3,5,5-trimethylcyclohexane, a polyether-based diamine having an ether bond represented by Jeffamine or Elastamine (all trade name) manufactured by Huntsman Co., Ltd., But not limited to these. These may be used alone or in combination of two or more.

[dicarboxylic acid unit]

The dicarboxylic acid unit in the polyamine compound (A) contains the straightness represented by the above formula (II-1) from the viewpoints of the reactivity at the time of polymerization, and the crystallinity and formability of the polyamide compound (A). The content of the chain aliphatic dicarboxylic acid unit and/or the aromatic dicarboxylic acid unit represented by the above formula (II-2) is 50 mol% or more based on the total amount of the dicarboxylic acid units, and the content is more than Preferably, it is 70% by mole or more, more preferably 80% by mole or more, still more preferably 90% by mole or more, and more preferably 100% by mole or less.

The linear aliphatic dicarboxylic acid unit represented by the above formula (II-1) can impart a glass transition temperature or crystallinity to the polyamidamine compound (A), and can be imparted as a packaging material or a packaging container. The viewpoint of softness is preferred.

In the above formula (II-1), n represents an integer of 2 to 18, preferably 3 to 16, more preferably 4 to 12, still more preferably 4 to 8.

Examples of the compound which can constitute the linear aliphatic dicarboxylic acid unit represented by the above formula (II-1) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and cerium. Acid, 1,10-nonanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, etc. But not limited to these. These may be used alone or in combination of two or more.

The type of the linear aliphatic dicarboxylic acid unit represented by the above formula (II-1) can be appropriately determined depending on the intended use. The linear aliphatic dicarboxylic acid unit in the polyamine compound (A) is not only excellent in gas barrier properties to the polyamine compound (A), but also heat resistant from heat preservation after packaging materials or packaging containers. Preferably, the linear aliphatic dicarboxylic acid unit contains at least one selected from the group consisting of adipic acid units, sebacic acid units, and 1,12-dodecanedicarboxylic acid units in a total of 50 moles. More preferably, the content of the ear is more than 70% by mole, more preferably 80% by mole or more, still more preferably 90% by mole or more, and preferably 100% by mole or less.

The linear aliphatic dicarboxylic acid unit in the polyamine compound (A) is a linear aliphatic group from the viewpoints of gas barrier properties of the polyamine compound (A) and thermal properties such as a suitable glass transition temperature or melting point. The dicarboxylic acid unit preferably contains 50 mol% or more of the adipic acid unit. Further, the linear aliphatic dicarboxylic acid unit in the polyamine compound (A) is a linear aliphatic dicarboxylic acid unit from the viewpoint of imparting appropriate gas barrier properties and moldability to the polyamine compound (A). Preferably, the azelaic acid unit is preferably 50% by mole or more, and the polyamidamine compound (A) is used in applications requiring low water absorption, weather resistance, and heat resistance, and is preferably in a linear aliphatic dicarboxylic acid unit. It is preferable to contain 50 mol% or more of the 1,12-dodecanedicarboxylic acid unit.

In addition to the gas barrier property to the polyamine compound (A), the aromatic dicarboxylic acid unit represented by the above formula (II-2) is more preferable from the viewpoint of facilitating the moldability of the packaging material or the packaging container. good.

In the above formula (II-2), Ar represents an exoaryl group. The above-mentioned aryl group is preferably a carbon number of 6 to 30, more preferably a carbon number of 6 to 15 exoaryl group, for example, a phenyl group, a naphthyl group or the like.

The compound which can constitute the aromatic dicarboxylic acid unit represented by the above formula (II-2), for example, terephthalic acid, isophthalic acid or 2,6-naphthalene dicarboxylic acid, is not limited thereto. These may be used alone or in combination of two or more.

The type of the aromatic dicarboxylic acid unit represented by the above formula (II-2) can be appropriately determined depending on the intended use. The aromatic dicarboxylic acid unit in the polyamine compound (A) preferably contains a group selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalene dicarboxylic acid unit. At least one kind is preferably 50 mol% or more in total of the aromatic dicarboxylic acid unit, and the content is more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90. More than or equal to 100% by mole, more preferably 100% by mole or less. Further, among these, the aromatic dicarboxylic acid unit preferably contains isophthalic acid and/or terephthalic acid. The content ratio of the isophthalic acid unit to the terephthalic acid unit (isophthalic acid unit/terephthalic acid unit) is not particularly limited and may be appropriately determined depending on the intended use. For example, from the viewpoint of shifting temperature or decreasing crystallinity of a moderate glass, when the total of the two units is 100, the molar ratio is preferably 0/100 to 100/0, more preferably 0/100 to 60/40, and further Good is 0/100~40/60, and even better is 0/100~30/70.

The ratio of the linear aliphatic dicarboxylic acid unit to the aromatic dicarboxylic acid unit in the dicarboxylic acid unit in the polyamine compound (A) (linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid) Unit) is not particularly limited and may be appropriately determined depending on the purpose. For example, in order to increase the glass transition temperature of the polyamine compound (A) and lower the crystallinity of the polyamine compound (A), the linear aliphatic dicarboxylic acid unit/aromatic dicarboxylic acid unit, when two units are When the total is 100, the molar ratio is preferably 0/100 to 60/40, more preferably 0/100 to 40/60, and even more preferably 0/100 to 30/70. Further, when the purpose is to lower the glass transition temperature of the polyamine compound (A) and impart flexibility to the polyamine compound (A), the linear aliphatic dicarboxylic acid unit/aromatic dicarboxylic acid unit, when two When the total of the units is 100, the molar ratio is preferably 40/60 to 100/0, more preferably 60/40 to 100/0, and even more preferably 70/30 to 100/0.

Examples of the compound which can constitute a dicarboxylic acid unit other than the dicarboxylic acid unit represented by the above formula (II-1) or (II-2) include oxalic acid, malonic acid, fumaric acid, maleic acid, and 1,3. a dicarboxylic acid such as benzene diacetic acid or 1,4-benzene diacetic acid, but is not limited thereto.

[Carboxylic acid unit containing 3-stage hydrogen]

In the present invention, the carboxylic acid unit containing a tertiary hydrogen in the polyamidamine compound (A) has at least one amine group and carboxyl group, or two or more from the viewpoint of polymerization of the polyamidamine compound (A). Carboxyl group. Specific examples thereof include constituent units represented by any one of the following formula (III), (IV) or (V).

[In the above formulae (III) to (V), R, R ¹ and R ² each represent a substituent, and each of A ¹ to A ³ represents a single bond or a divalent linking group. However, the case where A ¹ and A ² in the above formula (IV) are simultaneously a single bond is not included]

In the present invention, the polyamidamine compound (A) contains a carboxylic acid unit containing a hydrogen atom of three stages. By containing such a carboxylic acid unit containing a tertiary hydrogen as a copolymerization component, the polyamidamine compound (A) can exhibit excellent oxygen absorption performance even without a transition metal.

In the present invention, it is not known that the polyamine compound (A) having a carboxylic acid unit having a hydrogen atom of three stages exhibits good oxygen absorption performance, but it is presumed as follows. A compound capable of constituting a carboxylic acid unit containing a hydrogen atom of 3, since an electron attracting group and an electron donating group are bonded to the same carbon atom, it is considered that the energy of the unpaired electron existing on the carbon atom is in terms of energy. A phenomenon known as the Captodative effect, which is stabilized, produces very stable free radicals. That is, the carboxyl group is an electron attracting group, and the carbon bonded to the adjacent third-order hydrogen becomes electron-deficient (δ ⁺ ), so the third-order hydrogen also becomes electron-deficient (δ ⁺ ), which dissociates into protons. And form free radicals. In the presence of oxygen and water, it is believed that oxygen will exhibit oxygen absorbing properties due to the reaction of oxygen with the free radicals. Moreover, it is judged that the higher the humidity and the high temperature environment, the higher the reactivity.

In the above formulae (III) to (v), R, R ¹ and R ² each represent a substituent. In the present invention, R, R ¹ and R ² represent a substituent such as a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom) or an alkyl group (having 1 to 15, preferably 1 to 6 carbons). a linear, branched or cyclic alkyl group of an atom, for example: methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl , an alkenyl group (linear, branched or cyclic alkenyl group having 2 to 10, preferably 2 to 6 carbon atoms, for example, vinyl, allyl), alkynyl (having 2 to 10, An alkynyl group of 2 to 6 carbon atoms, for example, an ethynyl group, a propargyl group, an aryl group (an aryl group having 6 to 16, preferably 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group or a heterocyclic group (having 1 to 12, preferably 2 to 6 by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound of a 5-membered ring or a 6-membered ring) a valence group of a carbon atom, such as 1-pyrazolyl, 1-imidazolyl, 2-furyl, cyano, hydroxy, nitro, alkoxy (having 1 to 10, preferably 1 to 6) a linear, branched or cyclic alkoxy group of one carbon atom, for example: methoxy, ethoxy), aryloxy (having 6 to 12, preferably an aryloxy group of 6 to 8 carbon atoms, for example, a phenoxy group, a fluorenyl group (methanyl group, having 2 to 10, preferably 2 to 6 carbon atoms) An alkylcarbonyl group, or an arylcarbonyl group having 7 to 12, preferably 7 to 9 carbon atoms, for example, an ethyl group, a trimethylethyl group, a benzhydryl group, an amine group (an amine group, having 1 to 10, preferably an alkylamine group of 1 to 6 carbon atoms, an anilino group having 6 to 12, preferably 6 to 8 carbon atoms, or 1 to 12, preferably 2~ a heterocyclic amine group of 6 carbon atoms, for example, an amine group, a methylamino group, an anilino group, a fluorenyl group, an alkylthio group (an alkylthio group having 1 to 10, preferably 1 to 6 carbon atoms, For example: methylthio, ethylthio), arylthio (arylthio having 6 to 12, preferably 6 to 8 carbon atoms, such as phenylthio), heterocyclic thio (Heterocyclic thio group having 2 to 10, preferably 2 to 6 carbon atoms, such as 2-benzothiazolylthio), quinone imine (having 2 to 10, preferably 4 to 8) A quinone imine group of a carbon atom, for example, N-succinimide group, N-phthalimido group, and the like.

Those having a hydrogen atom among the functional groups may be further substituted with the above groups, for example, an alkyl group substituted with a hydroxyl group (for example, a hydroxyethyl group), an alkyl group substituted with an alkoxy group (for example, a methoxyethyl group). , an aryl-substituted alkyl group (for example, benzyl group), an alkyl-substituted aryl group (example) For example, p-tolyl), an alkyl-substituted aryloxy group (for example, 2-methylphenoxy), and the like, but not limited thereto.

Further, when the functional group is further substituted, the carbon number does not include the carbon number of the further substituent. For example, a benzyl group, which is regarded as a carbon number 1 alkyl group substituted by a phenyl group, is not regarded as a carbon number 7 alkyl group substituted with a phenyl group. For the description of the following carbon numbers, the same explanation will be given unless otherwise specified.

In the above formulae (IV) and (V), each of A ¹ to A ³ represents a single bond or a divalent linking group. However, the case where both A ¹ and A ² in the above formula (IV) are single bonds is not included. a divalent linking group, for example, a linear, branched or cyclic alkyl group (having a carbon number of 1 to 12, preferably an alkylene group having a carbon number of 1 to 4, such as a methylene group or an ethyl group), An aralkyl group (having a carbon number of 7 to 30, preferably a 7 to 13 carbon atom, such as a benzylidene group), and an aryl group (having a carbon number of 6 to 30, preferably a carbon number of 6 to 15) An aryl group, for example, a phenyl group). These may further have a substituent, and examples of the substituent include the above-described functional groups which are substituents represented by R, R ¹ and R ² . For example, an alkyl group-substituted aryl group (for example, xylylene group), etc., but is not limited thereto.

In the present invention, it is preferred that the polyamine compound (A) contains at least one of the constituent units represented by any one of the above formula (III), (IV) or (V). Among these, a carboxylic acid unit having a 3-stage hydrogen in α carbon (a carbon atom adjacent to a carboxyl group) is more preferable from the viewpoints of raw material availability or oxygen absorption enhancement, and the constituent unit represented by the above formula (III) Especially good.

In the above formula (III), R is as defined above, but wherein a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are more preferred, and the substituted or unsubstituted carbon number is 1 to 6 The alkyl group and the substituted or unsubstituted aryl group having 6 to 10 carbon atoms are more preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group.

Desirable specific examples of R, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, 1-methylpropyl, 2-methylpropyl, hydroxymethyl, 1 - hydroxyethyl, decylmethyl, sulfanylethyl, phenyl, naphthyl, benzyl, 4-hydroxybenzyl, etc., but not limited thereto. Among these, methyl, ethyl, isopropyl, 2-methylpropane The base and the benzyl group are more preferred.

Examples of the compound which can constitute the structural unit represented by the above formula (III) include alanine, 2-aminobutyric acid, valine acid, n-decylamine, leucine, orthraenic acid, and third amine. Acid, isoleucine, serine, threonine, cysteine, methionine, 2-phenylglycine, phenylalanine, tyrosine, histidine, tryptophan, An α-amino acid such as lysine, but is not limited thereto.

Further, a compound which can constitute a constituent unit represented by the above formula (IV), for example, a β-amino acid such as 3-aminobutyric acid, which can constitute a constituent unit represented by the above formula (V), such as methyl propyl group Dicarboxylic acids such as diacid, methyl succinic acid, malic acid, tartaric acid, etc., but are not limited thereto.

These may be any of the D body, the L body, and the racemate, or may be an allo-body. Further, these may be used alone or in combination of two or more.

Among these, from the viewpoints of raw material availability and oxygen absorption, it is particularly preferable that the α-carbon has α-amino acid having three-stage hydrogen. Further, among the α-amino acids, alanine is preferred from the viewpoints of ease of supply, low cost, ease of polymerization, and low yellowness (YI) of the polymer. Since the alanine has a low molecular weight and a high copolymerization ratio per 1 g of the polyamidamine compound (A), the polyamine compound (A) has a good oxygen absorption performance per 1 g.

Further, the purity of the compound which can constitute the carboxylic acid unit containing the third-order hydrogen is preferably 95% or more from the viewpoint of the influence on the polymerization such as the delay of the polymerization rate or the influence on the quality surface such as the yellowness of the polymer. More preferably, it is 98.5% or more, and more preferably 99% or more. Further, the sulfate ion or ammonium ion contained as an impurity is preferably 500 ppm or less, more preferably 200 ppm or less, still more preferably 50 ppm or less.

[ω-amino carboxylic acid unit]

In the present invention, the polyamine compound (A), when the polyamine compound (A) requires flexibility or the like, the diamine unit, in addition to the above-mentioned dicarboxylic acid unit and the aforementioned 3-stage hydrogen-containing carboxylic acid In addition to the element, the ω-amino carboxylic acid unit represented by the following formula (X) may be further contained.

[In the above formula (X), p represents an integer of 2 to 18. ]

The content of the ω-amino carboxylic acid unit is preferably from 0.1 to 49.9 mol%, more preferably from 3 to 40 mol%, still more preferably 5, based on all the constituent units of the polyamine compound (A). ~35 moles %. However, the total amount of the above diamine unit, dicarboxylic acid unit, carboxylic acid unit containing 3-stage hydrogen, and ω-amino carboxylic acid unit is not more than 100 mol%.

In the above formula (X), p represents an integer of from 2 to 18, preferably from 3 to 16, more preferably from 4 to 14, still more preferably from 5 to 12.

The compound which can constitute the ω-amino carboxylic acid unit represented by the above formula (X), for example, an ω-amino carboxylic acid having 5 to 19 carbon atoms or a decylamine having 5 to 19 carbon atoms. Omega-amino carboxylic acid having 5 to 19 carbon atoms, such as 6-aminocaproic acid and 12-aminododecanoic acid, etc., decylamine having a carbon number of 5 to 19, such as ε-caprolactam and laurel Guanamine, but not limited to this. These may be used alone or in combination of two or more.

The ω-amino carboxylic acid unit preferably contains a 6-aminohexanoic acid unit and/or a 12-aminododecanoic acid unit in an amount of 50 mol% or more in the ω-amino carboxylic acid unit. More preferably, it is 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and further preferably 100 mol% or less.

[Polymerization degree of polyamine compound (A)]

The relative viscosity is used for the degree of polymerization of the polyamine compound (A). The relative viscosity of the polyamine compound (A) is not particularly limited, but is preferably from 1.01 to 4.2, from the viewpoint of strength, appearance, and moldability of the molded article.

As described above, the desired ratio of the mass ratio of the polyamine compound (A) / the resin (B) varies depending on the relative viscosity of the polyamine compound (A), and the relative viscosity of the polyamide compound (A) is 1.8. In the case of 4.2 or less, the mass ratio of the polyamine compound (A)/resin (B) is preferably selected from the range of 5/95 to 95/5, and the relative viscosity of the polyamine compound (A) is 1.01 or less. In the case of 1.8, the mass ratio of the polyamine compound (A) / resin (B) is preferably selected from the range of 5/95 to 50/50.

In the relative viscosity referred to herein, 1 g of the polyamidamine compound (A) was dissolved in 100 mL of 96% sulfuric acid, and the dropping time (t) measured at 25 ° C using a Cannon-Fenske type viscosity meter was measured in the same manner. The ratio of the drop time (t ₀ ) of 96% sulfuric acid itself is expressed in the following formula.

Relative viscosity = t / t ₀

[terminal amino group concentration]

The oxygen absorption rate of the polyamine compound (A) and the oxidative degradation of the polyamine compound (A) due to oxygen absorption can be controlled by changing the terminal amine group concentration of the polyamine compound (A). In the present invention, the concentration of the terminal amine group of the polyamido compound (A) is preferably from 5 to 150 μeq/g, more preferably from 10 to 100 μeq/g, from the viewpoint of the balance between the oxygen absorption rate and the oxidative degradation. More preferably, it is 15 to 80 μeq/g.

<Method for Producing Polyamine Compound (A)>

The polyamine compound (A) can be composed of a diamine component which can constitute the diamine unit, a dicarboxylic acid component which can constitute the dicarboxylic acid unit, and a carboxylic acid unit which can constitute the tertiary hydrogen-containing unit. The carboxylic acid component of the hydrogen group and, if necessary, the ω-amino carboxylic acid component constituting the ω-amino carboxylic acid unit are produced by polycondensation, and the polymerization degree can be controlled by adjusting the polycondensation conditions and the like. A small amount of a unit amine or a unit carboxylic acid may also be added as a molecular weight regulator during the polycondensation. Further, in order to suppress the polycondensation reaction to have a desired degree of polymerization, the ratio (mol ratio) of the diamine component and the carboxylic acid component constituting the polyamine compound (A) may be adjusted to deviate from 1.

Polycondensation method of polyamine compound (A) such as reaction extrusion method, pressurized salt method, often The pressure drop addition method, the pressure drop method, and the like are not limited thereto. Further, when the reaction temperature is as low as possible, the yellowing or gelation of the polyamine compound (A) can be suppressed, and the polyamine compound (A) having a stable property can be obtained.

[Reaction extrusion method]

The reaction extrusion method is a polyamine (a polyamine which is a precursor of a polyamine compound (A)) or a diamine component, and a dicarboxylic acid component and ω, which are composed of a diamine component and a dicarboxylic acid component. - a polydecylamine composed of an aminocarboxylic acid component (a polyamine corresponding to the precursor of the polyamidamine compound (A)), and a carboxylic acid component containing a tertiary hydrogen compound, which are melt-kneaded and reacted by an extruder method. A method in which a carboxylic acid component containing a hydrogen atom of 3 is introduced into a skeleton of polyamine by a guanamine exchange reaction, and in order to sufficiently react, a screw suitable for reaction extrusion and a double shaft having a large L/D ratio are preferably used. The extruder is preferred. In the case of producing a polyamine compound (A) containing a small amount of a carboxylic acid unit containing a tertiary hydrogen, a simple method is preferred.

[pressurized salt method]

The pressurized salt method is a method in which a nylon salt is used as a raw material to carry out melt polycondensation under pressure. Specifically, a solution of a nylon salt composed of a diamine component, a dicarboxylic acid component, a carboxylic acid component containing a third-order hydrogen, and optionally an ω-amino carboxylic acid component is prepared, and then the aqueous solution is concentrated, followed by The temperature was raised under pressure, and polycondensation was carried out while removing the condensed water. The inside of the tank was slowly returned to normal pressure, and simultaneously heated to a temperature of about 10 ° C of the polyamine compound (A) and maintained, and then slowly depressurized to -0.02 MPaG, and the temperature was continued to continue polycondensation. Upon reaching a certain stirring torque, the inside of the tank was pressurized with nitrogen to about 0.3 MPaG to recover the polyamine compound (A).

The pressurized salt method is useful when a volatile component is used as a monomer, and is an ideal polycondensation method when the copolymerization ratio of the carboxylic acid component containing a tertiary hydrogen is high. In particular, it is preferred to produce a polyamine compound (A) having a carboxylic acid unit containing a third-order hydrogen in an amount of 15 mol% or more in all constituent units of the polyamine compound (A). By using the pressurized salt method, it is possible to prevent the carboxylic acid component containing the third-order hydrogen from being evacuated, and to suppress the polycondensation of the carboxylic acid component containing the third-order hydrogen, and to carry out the polycondensation reaction smoothly, thereby obtaining a polyamine having excellent properties. Compound (A).

[Atmospheric pressure drop method]

The normal pressure dropping method is a method in which a dicarboxylic acid component, a carboxylic acid component containing a third-order hydrogen, and optionally an ω-amino carboxylic acid component are heated and melted under normal pressure, and continuously added dropwise The amine component is subjected to polycondensation while removing the condensed water. Further, the polycondensation reaction is carried out while raising the temperature of the reaction system so that the reaction temperature is not lower than the melting point of the produced polyamine compound (A).

In the normal pressure dropping method, if the water for dissolving the salt is not used as compared with the above-mentioned pressurized salt method, the yield per unit batch is large, and it is not necessary to vaporize and condense the raw material components, and the reaction rate decreases little. Process time can be shortened.

[Pressure drop method]

In the pressurized dropping method, first, a dicarboxylic acid component, a carboxylic acid component containing three hydrogen atoms, and optionally an ω-amino carboxylic acid component are added to a polycondensation tank, and the components are stirred and melt-mixed to obtain a mixture. Next, the diamine component is continuously added dropwise to the mixture while the inside of the can is preferably pressurized to about 0.3 to 0.4 MPaG, and polycondensation is carried out while removing the condensation water. At this time, the polycondensation reaction is carried out while raising the temperature of the reaction system so that the reaction temperature is not lower than the melting point of the produced polyamine compound (A). When the molar ratio is reached, the dropping of the diamine component is completed, and the inside of the tank is slowly returned to normal pressure, and the temperature is raised to the melting point of the polyamine compound (A) + 10 ° C and maintained, and then slowly decompressed to - 0.02 MPaG while maintaining this temperature to continue the polycondensation reaction. Upon reaching a certain stirring torque, the inside of the tank was pressurized with nitrogen to about 0.3 MPaG to recover the polyamine compound (A).

The pressurized dropping method is useful in the case of using a volatile component as a monomer as in the case of the pressurized salt method, and is an ideal polycondensation method when the copolymerization ratio of the carboxylic acid component containing the tertiary hydrogen is high. In particular, it is preferred to produce a polyamine compound (A) having a carboxylic acid unit containing a tertiary hydrogen in a total amount of 15 mol% or more of all the constituent units of the polyamine compound (A). By using the pressurized dropping method, it is possible to prevent the carboxylic acid component containing the third-order hydrogen from being evaporated, and further, it is possible to suppress the polycondensation of the carboxylic acid component containing the third-order hydrogen, and the polycondensation reaction can be smoothly performed. A polyamine compound (A) excellent in properties can be obtained. Further, in the pressurized dropping method, since the water for dissolving the salt is not used as compared with the pressurized salt method, the yield per unit lot is large, and the reaction time can be shortened as in the normal pressure dropping method, so that the gel can be suppressed. The polyamine compound (A) having a low yellowness is obtained.

[Steps to increase the degree of polymerization]

The polyamine compound (A) produced by the above polycondensation method may be used as it is or may be subjected to a step for increasing the degree of polymerization. The step of increasing the degree of polymerization can be exemplified by reaction extrusion or solid phase polymerization carried out in an extruder. For the heating device used for solid phase polymerization, it is preferred to use a continuous heating and drying device or a rotary drum type heating device called a tumble dryer, a cone dryer, a rotary dryer, etc., and a conical type (Nauta) mixer. A conical heating device having a rotating blade inside is not limited thereto, and a known method and device can be used. In particular, in the case of the solid phase polymerization of the polyamine compound (A), in the above-described apparatus, the rotary drum type heating device is obtained from the viewpoint of being able to shrink the inside of the system and easily remove the oxygen which is the cause of coloring. It is better.

[Compound containing phosphorus atom, alkali metal compound]

In the polycondensation of the polyamine compound (A), it is preferred to add a compound containing a phosphorus atom from the viewpoint of promoting the amidation reaction.

a compound containing a phosphorus atom, for example, a phosphinic acid compound such as dimethylphosphinic acid or phenylmethylphosphinic acid; hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, hypophosphorous acid a diphosphorous acid compound such as magnesium, calcium hypophosphite or ethyl hypophosphite; phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid a phosphonic acid compound such as sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphinate, diethyl phenylphosphonate, sodium ethylphosphonate or potassium ethylphosphonate; phosphinic acid, phosphinic acid Sodium, lithium phosphinate, potassium phosphinate, magnesium phosphinate, calcium phosphinate, phenylphosphinic acid, sodium phenylphosphinate, potassium phenylphosphinate, lithium phenylphosphinate, benzene A phosphinic acid compound such as ethyl phosphinate; phosphorous acid, sodium hydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite Phosphite, pyrophosphoric acid, etc. Things and so on.

Among these, a metal hypophosphite such as sodium hypophosphite, potassium hypophosphite or lithium hypophosphite is preferred because it has a high effect of promoting the amidation reaction and is excellent in coloring prevention effect, especially hypophosphorous acid. Sodium is preferred. Further, the compound containing a phosphorus atom which can be used in the present invention is not limited to these compounds.

The amount of the phosphorus atom-containing compound to be added is preferably from 0.1 to 1,000 ppm, more preferably from 1 to 600 ppm, still more preferably from 5 to 400 ppm, in terms of the phosphorus atom concentration in the polyamine compound (A). When it is 0.1 ppm or more, the polyamine compound (A) is not easily colored during polymerization, and transparency is improved. When it is 1000 ppm or less, the polyamine compound (A) is less likely to gel, and it is also possible to reduce the fact that a fish eye which is considered to be caused by a compound containing a phosphorus atom is mixed into a molded article, and the appearance of the molded article is good.

Further, in the polycondensation system of the polyamine compound (A), it is preferred to use an alkali metal compound in combination with a compound containing a phosphorus atom. In order to prevent the polyamine compound (A) from being colored in the polycondensation, a sufficient amount of a compound containing a phosphorus atom is required, but depending on the case, there may be a tendency to cause gelation of the polyamine compound (A), so in order to adjust The rate of the amidation reaction is also preferably a coexisting alkali metal compound.

The alkali metal compound is preferably an alkali metal hydroxide or an alkali metal acetate, an alkali metal carbonate, an alkali metal alkoxide or the like. The alkali metal compound which can be used in the present invention, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, barium hydroxide, lithium acetate, sodium acetate, potassium acetate, barium acetate, barium acetate, sodium methoxide , sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium carbonate, etc., but are not limited to the use of such compounds. Further, the ratio of the phosphorus atom-containing compound to the alkali metal compound (mol ratio) is preferably a compound containing a phosphorus atom/alkali metal compound = 1.0/0.05 to 1.0 from the viewpoint of controlling the polymerization rate or reducing the yellowness. The range of /1.5 is better, more preferably 1.0/0.1 to 1.0/1.2, and even more preferably 1.0/0.2 to 1.0/1.1.

1-2. Resin (B)

In the present invention, the resin (B) can be any resin and is not particularly limited. Resin (B), For example, a thermoplastic resin can be used, specifically, for example, a polyolefin, a polyester, a polyamide, an ethylene-vinyl alcohol copolymer, and a resin of a plant origin. In the present invention, it is preferred that the resin (B) contains at least one selected from the group consisting of such resins.

Among these, in order to effectively exhibit an oxygen absorbing effect, a resin having high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymer is more preferable.

The mixing of the polyamine compound (A) and the resin (B) can be carried out by a conventionally known method such as dry mixing or melt mixing. When the polyamine compound (A) and the resin (B) are melt-mixed to produce a desired pellet or a molded body, it can be melt-blended by using an extruder or the like. As the extruder, a known extruder such as a uniaxial extruder or a twin-shaft extruder can be used, but is not limited thereto.

[Polyolefin]

Specific examples of the polyolefin include polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene), polypropylene, polybutene-1, and poly Olefin homopolymer of -4-methylpentene-1; ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cyclic olefin copolymer a copolymer of ethylene and an α-olefin; an ethylene-α,β-unsaturated carboxylic acid copolymer such as an ethylene-(meth)acrylic acid copolymer; an ethylene-α,β such as an ethylene-ethyl (meth)acrylate copolymer; - an unsaturated carboxylic acid ester copolymer, an ionomer of an ethylene-α,β-unsaturated carboxylic acid copolymer, an ethylene copolymer such as an ethylene-vinyl acetate copolymer; the polyolefin is passed through Malay A graft-modified polyolefin obtained by graft-modifying an acid anhydride such as an acid anhydride.

[Polyester]

In the present invention, the polyester means one or more selected from the group consisting of polycarboxylic acids containing a dicarboxylic acid and ester-forming derivatives thereof, and one selected from the group consisting of polyols containing a diol or Two or more constituents, or those composed of a hydroxycarboxylic acid and such an ester-forming derivative, or a cyclic ester.

Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and gem Acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornium a saturated aliphatic dicarboxylic acid exemplified by an alkanedicarboxylic acid, a dimer acid or the like, or an ester-forming derivative thereof, an unsaturated aliphatic dicarboxylic acid exemplified by fumaric acid, maleic acid, itaconic acid or the like Or such ester-forming derivatives, phthalic acid, isophthalic acid, terephthalic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylfluorene dicarboxylic acid, 4,4'-biphenyl An aromatic dicarboxylic acid exemplified as an ether dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid or a quinone dicarboxylic acid, or an ester-forming derivative thereof, 5-sodium sulfoisophthalic acid, 2-sodium sulfophthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfophthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfophthalate It shows the metal-containing sulfonates (sulfonate) an aromatic dicarboxylic acid or a lower alkyl ester of such a derivative of the group.

Among the above dicarboxylic acids, in particular, when terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid is used, it is preferred from the viewpoint of physical properties of the obtained polyester, and other dicarboxylic acids may be copolymerized as needed. .

Polycarboxylic acids other than such dicarboxylic acids, such as ethane tricarboxylic acid, propane tricarboxylic acid, butane tetracarboxylic acid, pyromellitic acid, trimellitic acid, symmetrical trimellitic acid, 3, 4, 3' 4'-biphenyltetracarboxylic acid, and ester-forming derivatives thereof.

Glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3- Butylene glycol, 1,4-butanediol, 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, Aliphatic diol, hydrogen exemplified by 1,10-decethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. Bismuth, 4,4'-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)benzene, 1,4-bis(β-hydroxyethoxyl) Phenyl, bis(p-hydroxyphenyl)ether, bis(p-hydroxyphenyl)anthracene, bis(p-hydroxyphenyl)methane, 1,2-bis(p-hydroxyphenyl)ethane, bisphenol A An aromatic diol exemplified by bisphenol C, 2,5-naphthalenediol, or a diol obtained by adding oxyethylene to the diol.

Among the above diols, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferably used as a main component. Polyhydric alcohols other than the diols are, for example, trimethylolethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, hexanetriol, and the like. Hydroxycarboxylic acid, such as lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, 4-hydroxycyclohexanecarboxylic acid, Or such ester-forming derivatives and the like.

Cyclic esters such as ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycosides, lactide and the like.

An ester-forming derivative of a polyvalent carboxylic acid or a hydroxycarboxylic acid, for example, such an alkyl ester, hydrazine chloride, an acid anhydride or the like.

The polyester used in the present invention, the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalene dicarboxylic acid or an ester-forming derivative thereof, and the main diol component is alkylene glycol. Polyester is preferred.

The polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester having a total content of terephthalic acid or an ester-forming derivative of 70 mol% or more based on the total acid component. Preferably, it is preferably a polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more. The polyester having a main acid component of naphthalene dicarboxylic acid or an ester-forming derivative thereof is preferably a polyester having a naphthalene dicarboxylic acid or an ester-forming derivative in a total amount of 70 mol% or more, more preferably It is a polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more.

The naphthalene dicarboxylic acid or an ester-forming derivative thereof used in the present invention is preferably 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid or 1,5-naphthalene dicarboxylic acid exemplified as the above dicarboxylic acid. Acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, or such ester-forming derivatives are preferred.

The main diol component is a polyester of an alkylene glycol, preferably a polyester having a total alkylene glycol content of 70 mol% or more, more preferably 80 mol%, based on the total diol component. The above polyester is more preferably a polyester containing 90 mol% or more. The alkylene glycol referred to herein may also have a substituent or an alicyclic structure in the molecular chain.

The copolymerization component other than the above terephthalic acid/ethylene glycol is selected from the group consisting of isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, and 1,4-cyclohexane. When at least one of the group consisting of alkane dimethanol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propanediol is preferred in terms of both transparency and formability, especially It is more preferably at least one selected from the group consisting of isophthalic acid, diethylene glycol, neopentyl glycol, and 1,4-cyclohexane dimethanol.

A preferred example of the polyester used in the present invention is a polyester composed mainly of repeating units of ethylene terephthalate, more preferably a linear form containing 70% by mole of ethylene terephthalate unit. The polyester is more preferably a linear polyester containing 80% by mole or more of ethylene terephthalate unit, and more preferably a linear polyester containing more than 90% by weight of ethylene terephthalate unit. .

Further, another preferred example of the polyester used in the present invention is that the main repeating unit is a polyester composed of ethylene-2,6-naphthalate, and more preferably contains ethylene 2,6-naphthalate unit 70. More than 5% of the linear polyester, more preferably a linear polyester containing more than 80% by mole of 2,6-naphthalenedicarboxylate unit, and particularly preferably containing 2,6-naphthalenedicarboxylic acid The ester unit has 90% or more linear polyester.

Further, another preferred example of the polyester used in the present invention is propylene glycol terephthalate. The linear unit polyester having 70% or more of the ester unit, the linear polyester containing 70% by mole or more of the propylene glycol naphthalate unit, and the 70 mole containing the 1,4-cyclohexane terephthalate unit The linear polyester of % or more, the linear polyester containing 70% by mole or more of the butylene naphthalate unit, or the linear polyester containing 70% by mole of the butylene dicarboxylate unit.

In particular, the composition of the whole polyester is a combination of terephthalic acid/isophthalic acid//ethylene glycol, a combination of terephthalic acid//ethylene glycol/1,4-cyclohexanedimethanol, and benzene. When a combination of dicarboxylic acid//ethylene glycol/neopentyl glycol is used, it is preferable from the viewpoint of achieving both transparency and formability. Further, it is a matter of course that a small amount (5 mol% or less) of diethylene glycol which is produced by dimerization of ethylene glycol in the esterification (transesterification) reaction or the polycondensation reaction is not to be said.

Further, another preferred example of the polyester used in the present invention is, for example, a polycondensation of a glycolic acid or a methyl glycolate or a polyglycolic acid obtained by ring-opening polycondensation of a glycoside. The polyglycolic acid can also be copolymerized with other components such as lactide.

[polyamide]

The polyamine used in the present invention (herein, "polyamine" means a polyamine resin mixed with the "polyamine compound (A)" of the present invention, and does not mean the "polyamine compound (A) of the present invention. "self", for example, polyamine which is a main constituent unit derived from a mesalamine or an aminocarboxylic acid, or an aliphatic group which is a main constituent unit derived from an aliphatic diamine and an aliphatic dicarboxylic acid. Polyamide, a partially aromatic polyamine which is a main constituent unit derived from an aliphatic diamine and an aromatic dicarboxylic acid, and a unit derived from an aromatic diamine and an aliphatic dicarboxylic acid as a main constituent unit A part of the aromatic polyamine or the like may be copolymerized with monomer units other than the main constituent unit as needed.

As the intrinsic amine or aminocarboxylic acid, an amine carboxylic acid such as ε-caprolactam or laurylamine, an aminocarboxylic acid such as aminocaproic acid or aminoundecanoic acid, or an amine group can be used. An aromatic aminocarboxylic acid such as benzoic acid or the like.

As the aliphatic diamine, an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof can be used. Further, it may be an alicyclic diamine. The aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine. Specific examples of such a linear aliphatic diamine include ethylenediamine, 1-methylethylenediamine, 1,3-propanediamine, tetramethylenediamine, and pentamethylenediamine. Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecyldiamine, dodecamethylenediamine Such as aliphatic diamines. Further, specific examples of the alicyclic diamine include cyclohexane diamine, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane.

Further, the aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, and more preferably a linear aliphatic having a carbon number of 4 to 12 alkyl groups. carboxylic acid. Such a linear aliphatic dicarboxylic acid such as adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, ten Alkanedioic acid, dodecanedioic acid, dimer acid, and such functional derivatives. An alicyclic dicarboxylic acid such as an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid or hexahydroisophthalic acid.

Further, the aromatic diamine is, for example, m-xylylenediamine, p-xylylenediamine or p-bis(2-aminoethyl)benzene.

Further, the aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenyl oxygen Ethylene dicarboxylic acid and its functional derivatives and the like.

Specific polyamines, such as polyamine 4, polyamine 6, polyamine 10, polyamine 11, polyamide 12, polyamine 4, 6, polyamine 6,6, polyamine 6 , 10, polyamine 6T, polyamine 9T, polyamine 6IT, poly-m-xylene hexamethylenediamine (polyamine MXD6), isophthalic acid copolymerization of poly-m-xylene hexamethylenediamine ( Polyamide MXD6I), polymethylene xylene decylamine (polyamide MXD10), polymethylene xylene decylamine (polyamide) MXD12), poly1,3-bis(aminomethyl)cyclohexanehexanediamine (polyamine BAC6), polyparaxylylenediamine (polyamine PXD10), and the like. More desirable polyamines, such as polyamide 6, polyamine MXD6, polyamine MXD6I.

Further, as the copolymerization component of the polyamine, an organic carboxylate having a polyether having a number average molecular weight of at least one terminal amine group or terminal carboxyl group of from 2,000 to 20,000 or a polyether having a terminal amino group may be used. Or the aforementioned amine salt of a polyether having a terminal carboxyl group. Specific examples are, for example, bis(aminopropyl)poly(oxyethylene) (polyethylene glycol having a number average molecular weight of from 2,000 to 20,000).

In addition, the partially aromatic polyamine may contain a constituent unit derived from a trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid in a substantially linear range.

The polyamine can be basically subjected to a melt polycondensation method in the presence of water or a melt polycondensation method in the absence of water, or a method of further solid phase polymerization of the polyamine obtained by the melt polycondensation method. Manufacturing. The melt polycondensation reaction can be carried out in one stage or in multiple stages. These may be constituted by a batch reactor or a continuous reactor. Further, the melt polycondensation step and the solid phase polymerization step may be continuously operated or divided.

[ethylene-vinyl alcohol copolymer]

The ethylene vinyl alcohol copolymer used in the present invention is not particularly limited, and preferably has an ethylene content of 15 to 60 mol%, more preferably 20 to 55 mol%, more preferably 29 to 44 mol%, and a vinyl acetate component. The degree of saponification is preferably 90 mol% or more, and more preferably 95 mol% or more.

Further, in the ethylene vinyl alcohol copolymer, a small amount of propylene such as propylene, isobutylene, α-octene, α-dodecene or α-octadecene may be further contained in a range which does not adversely affect the effects of the present invention. A comonomer such as an olefin, an unsaturated carboxylic acid or a salt thereof, a partial alkyl ester, a fully alkyl ester, a nitrile, a guanamine, an acid anhydride, an unsaturated sulfonic acid or a salt thereof.

[Plant-derived resin]

In the case of the plant-derived resin, the resin is a compound which is a raw material, and is not particularly limited, and an aliphatic polyester-based biodegradable resin which is known as a raw material other than petroleum is known. Aliphatic polyester-based biodegradable resin, for example, poly(α-hydroxy acid) such as polyglycolic acid (PGA) or polylactic acid (PLA); polybutylene succinate (PBS), polysuccinic acid An alkyl ester (PES) or the like, a polyalkylene alkanoate or the like.

[Other resins]

In the range which does not impair the object of the present invention, various conventionally known resins may be added as the resin (B) in response to the performance imparted to the oxygen barrier layer. For example, from the viewpoint of imparting impact resistance, pinhole resistance, flexibility, and adhesion, for example, polyolefin such as polyethylene or polypropylene, various modified products thereof, polyolefin elastomer, and polyfluorene Various thermoplastic elastomers such as an amine-based elastomer, a styrene-butadiene copolymer resin or a hydrogenated product thereof, a polyester-based elastomer, and various polyamines such as nylon 6, 66, 12, and nylon 12, From the viewpoint of further imparting oxygen absorbing performance, a resin containing a carbon-carbon unsaturated double bond such as polybutadiene or modified polybutadiene may be mentioned.

1-3. Additives (C)

The resin composition for an oxygen-absorbing barrier layer of the present invention may further contain an additive (C) as needed in addition to the polyamine compound (A) and the resin (B). The additive (C) may be used alone or in combination of two or more. The content of the additive (C) in the resin composition depends on the type of the additive, but is preferably 10% by mass or less, more preferably 5% by mass or less.

[Alkylation inhibitor]

In the present invention, it is preferred to add a diammonium compound and/or a diester compound to the resin composition to suppress whitening after hot water treatment or after a long period of time. The diamine compound and the diester compound are effective for suppressing whitening due to precipitation of the oligomer. The diamine compound and the diester compound may be used singly or in combination.

The diamine compound which can be used in the present invention is preferably a diamine compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms. When the carbon number of the aliphatic dicarboxylic acid is 8 or more and the carbon number of the diamine is 2 or more, the whitening prevention effect can be expected. When the carbon number of the aliphatic dicarboxylic acid is 30 or less and the carbon number of the diamine is 10 or less, 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. The diamine compound may be used alone or in combination of two or more.

The aforementioned aliphatic dicarboxylic acid, for example, stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), octadecanoic acid (C28), triacontanic acid (C30), etc. . The above diamine is, for example, ethylenediamine, butanediamine, hexamethylenediamine, xylenediamine, bis(aminomethyl)cyclohexane or the like. It is preferred that the diamine compound obtained by combining the above is preferable.

a diammonium compound obtained from a diamine having 8 to 30 carbon atoms and a diamine mainly composed of ethylenediamine, or an aliphatic dicarboxylic acid composed mainly of octadecanoic acid and a carbon number 2~ The diamine compound obtained from the diamine of 10 is preferably a diamine compound obtained from an aliphatic dicarboxylic acid mainly composed of stearic acid and a diamine mainly composed of ethylenediamine.

The diester compound which can be 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 carbon number of the aliphatic dicarboxylic acid is 8 or more and the carbon number of the diol is 2 or more, the whitening prevention effect can be expected. Further, when the carbon number of the aliphatic dicarboxylic acid is 30 or less and the carbon number of the diol is 10 or less, the uniform dispersion in the oxygen-absorbing barrier layer is good. The aliphatic dicarboxylic acid may also have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred. The diester compound may be used alone or in combination of two or more.

The above aliphatic dicarboxylic acid, for example, stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), octadecanoic acid (C28), triacontanic acid (C30) and the like. The aforementioned diol is, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, xylene glycol, cyclohexane dimethanol or the like. The diester compound obtained by combining these is preferable. Yu Jia is mainly composed of twenty A diester compound obtained from a diol composed of an octamoic acid and a diol mainly composed of ethylene glycol and/or 1,3-butylene glycol.

In the present invention, the amount of the diamine compound and/or the diester compound to be added is preferably 0.005 to 0.5% by mass, more preferably 0.05 to 0.5% by mass, still more preferably 0.12 to 0.5% by mass in the resin composition. . By adding 0.005% by mass or more of the resin composition and using a nucleating nucleating agent in combination, a synergistic effect of preventing whitening can be expected. In addition, when the amount of addition is 0.5% by mass or less in the resin composition, the haze value of the molded article obtained by molding the resin composition can be kept low.

[layered citrate]

In the present invention, the oxygen-absorbing barrier layer may also contain a layered niobate. By adding a layered niobate, it is possible to impart not only oxygen barrier properties to the film but also barrier properties against gases such as carbon dioxide.

The layered niobate is a 2-octahedral or 3-octahedral layered niobate having a charge density of 0.25 to 0.6, and a 2-octahedral type such as montmorillonite or aluminum montmorillonite, 3 - Octahedral type, for example, lithium bentonite, magnesium saponite, and the like. Among these, Monte Rock is preferred.

The layered niobate is preferably such that an organic swelling agent such as a polymer compound or an organic compound is previously brought into contact with the layered niobate to broaden the interlayer of the layered niobate. As the organic swelling agent, a quaternary ammonium salt can be preferably used, but it is more preferred to use a quaternary ammonium salt having at least one of an alkyl group or an alkenyl group having 12 or more carbon atoms.

Specific examples of the organic swelling agent are, for example, trimethyldodecyl ammonium salt, trimethyltetradecyl ammonium salt, trimethylhexadecyl ammonium salt, trimethyl octadecyl ammonium salt, trimethyl group a trimethylalkylammonium salt such as a decyl ammonium salt; a trimethylalkenyl ammonium salt such as a trimethyloctadecyl ammonium salt or a trimethyl octadecyl ammonium salt; or a triethyldodecylammonium salt; Salt, triethyltetradecyl ammonium salt, three Triethylalkylammonium salt such as ethylhexadecyl ammonium salt, triethyl octadecyl ammonium salt; tributyl dodecyl ammonium salt, tributyl tetradecyl ammonium salt, tributyl hexadecyl ammonium salt a tributylalkylammonium salt such as tributyloctadecyl ammonium salt; dimethyldi-dodecyl ammonium salt, dimethyl di-tetradecyl ammonium salt, dimethyl di-hexadecyl ammonium salt a dimethyldialkylammonium salt such as dimethyldi-octadecyl ammonium salt or dimethyl ditallow ammonium salt; dimethyl di-octadecyl ammonium salt, dimethyl di-n-ten a dimethyldienyl ammonium salt such as an octadecyl ammonium salt; diethyl di-dodecyl ammonium salt, diethyl di-tetradecyl ammonium salt, diethyl di-hexadecyl ammonium salt, Diethyldialkylammonium salt such as diethyldi-octadecyl ammonium; dibutyldi-dodecyl ammonium salt, dibutyldi-tetradecyl ammonium salt, dibutyl di-hexadecyl ammonium Dibutyl dialkyl ammonium salt such as salt, dibutyl di-octadecyl ammonium salt; methylbenzyl dialkyl ammonium salt such as methylbenzyl di-hexadecyl ammonium salt; dibenzyl di-ten Dibenzyldialkylammonium salt such as hexamethylammonium salt; trioxane such as tri-dodecylmethylammonium salt, tri-tetradecylmethylammonium salt or tri-octadecylmethylammonium salt a methylaminoammonium salt; a trialkylethylammonium salt such as a tri-dodecylethylammonium salt; a trialkylbutylammonium salt such as a tri-dodecylbutylammonium salt; and a 4-amino-n-butyric acid; , 6-amino-n-hexanoic acid, 8-aminooctanoic acid, 10-amino decanoic acid, 12-aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, 18 An ω-amino acid such as amino octadecanoic acid. Further, an ammonium salt containing a hydroxyl group and/or an ether group, wherein a methyl dialkyl (PAG) ammonium salt, an ethyl dialkyl (PAG) ammonium salt, a butyl dialkyl (PAG) ammonium salt, and a methyl group are used. 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, Butylalkyl bis(PAG) ammonium salt, methyl tris(PAG) ammonium salt, ethyl tris(PAG) ammonium salt, butyl tris(PAG) ammonium salt, tetra (PAG) ammonium salt (only alkyl group represents ten a dialkyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a hexyl group or the like having an alkyl group having 12 or more carbon atoms, and a PAG represents a polyalkylene glycol residue, preferably a polyethylene having a carbon number of 20 or less. An alcohol salt or a polypropylene glycol residue or the like, which contains at least one alkyl ester of an alkylene glycol residue, can also be used as an organic swelling agent. Among them, trimethyldodecyl ammonium salt, trimethyltetradecyl ammonium salt, trimethylhexadecyl ammonium salt, trimethyl octadecyl ammonium salt, dimethyl di-dodecylammonium salt, two Methyl di-tetradecyl ammonium salt, dimethyl di-hexadecyl ammonium salt, dimethyl di-octadecyl ammonium salt, and dimethyl ditallow ammonium salt are preferred. Further, these organic swelling agents may be used singly or as a mixture of a plurality of types.

In the present invention, the layered niobate treated with the organic swelling agent is preferably added in an amount of from 0.5 to 8% by mass, more preferably from 1 to 6% by mass, even more preferably from 2 to 5% by mass, based on the resin composition. When the amount of the layered niobate added is 0.5% by mass or more, sufficient gas barrier properties can be improved, and if it is 8% by mass or less, problems such as pinholes due to deterioration of flexibility of the oxygen barrier layer are less likely to occur. .

In the oxygen-absorbing barrier layer, the layered niobate is preferably not partially agglomerated but is preferably uniformly dispersed. The uniform dispersion as used herein means that the layered niobate is separated in a flat plate shape in the oxygen-absorbing barrier layer, and 50% or more of these 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 plate. The larger the distance, the better the dispersion state, the good appearance such as transparency, and the improvement of the barrier properties of gases such as oxygen and carbon dioxide.

[oxidation reaction accelerator]

In order to further improve the oxygen absorbing performance of the oxygen-absorbing barrier layer, a conventionally known oxidation reaction accelerator may be added without departing from the effects of the present invention. The oxidation reaction promoter can improve the oxygen absorption performance of the oxygen barrier layer by promoting the oxygen absorption property of the polyamine compound (A). Oxidation reaction promoters, such as metals such as iron, cobalt, nickel, etc., Group VIII metals, Group I metals such as copper or silver, Group IV metals such as tin, titanium, zirconium, Group V of vanadium, Group VI of chromium, etc. A low-grade inorganic or organic acid salt of a metal of Group VII such as manganese or a wrong salt of the above transition metal. Among these, a cobalt salt having an excellent oxygen reaction promoting effect or a combination of a cobalt salt and a manganese salt is preferred.

In the present invention, the amount of the oxygen reaction accelerator added is preferably from 10 to 800 ppm, more preferably from 50 to 600 ppm, still more preferably from 100 to 400 ppm, based on the metal atomic concentration.

[Oxygen absorber]

In order to increase the oxygen absorbing performance of the oxygen absorbing barrier layer, a conventionally known oxygen absorbing agent may be added without departing from the effects of the present invention. The oxygen absorbing agent can improve the oxygen absorbing performance of the oxygen absorbing barrier layer in addition to the oxygen absorbing property of the polyamidamine compound (A). Oxygen absorption properties of the oxygen barrier layer. An oxygen-absorbing agent, such as an oxidizing organic compound represented by a compound having a carbon-carbon double bond in a molecule such as vitamin C or vitamin E, butadiene or isoprene.

In the present invention, the amount of the oxygen absorbing agent to be added is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, still more preferably 0.5 to 3% by mass in the resin composition.

[Anti-gelation ‧ reduction of silver spots]

In the present invention, it is preferred to add one or more kinds of carboxylic acids selected from sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate, and the like to the oxygen-absorbing barrier layer. Salts are preferred. Here, the derivative is, for example, a 12-hydroxystearic acid metal salt such as calcium 12-hydroxystearate, magnesium 12-hydroxystearate or sodium 12-hydroxystearate. By adding the above-mentioned carboxylate, it is possible to prevent gelation of the polyamine compound (A) which occurs during the molding process or to reduce silver spots in the molded body, and the molding processability is improved.

The amount of the carboxylate to be added is preferably from 400 to 10,000 ppm, more preferably from 800 to 5,000 ppm, still more preferably from 1,000 to 3,000 ppm, in terms of the concentration in the resin composition. When it is 400 ppm or more, thermal deterioration of the polyamine compound (A) can be suppressed and gelation can be prevented. Moreover, when it is 10000 ppm or less, the polyamine compound (A) does not cause a molding failure, and there is no coloring or whitening. If a carboxylate which is a basic substance exists in the molten polyamine compound (A), it is presumed that the modification of the polyamine compound (A) due to heat is slowed down, and the inhibition is considered to be final. Gel formation of the modified material.

Further, the carboxylate is excellent in handleability, and the stearic acid metal salt is inexpensive, and has an effect as a lubricant, and is preferable because it can make the molding process more stable. In addition, the shape of the carboxylate is not particularly limited, and in the case where the powder is small and the particle diameter is small, it is easy to uniformly disperse in the resin composition. Therefore, the particle diameter is preferably 0.2 mm or less.

Further, in terms of a formulation which is more effective in preventing gelation, reducing silver spots, and preventing coking, it is preferred to use sodium acetate having a high concentration of metal salt per 1 g. When sodium acetate is used, it can be formed by dry mixing with polyamine compound (A) and resin (B), but From the viewpoints of workability or reduction of acetic acid odor, it is preferred to dry-mix a masterbatch composed of a polyamine compound (A) and a resin (B) with sodium acetate with a polyamide compound (A) and a resin (B). Preferably. The sodium acetate used in the master batch is preferably 0.2 mm or less, more preferably 0.1 mm or less, in order to facilitate uniform dispersion in the resin composition.

[Antioxidants]

In the present invention, it is preferred to add an antioxidant from the viewpoint of controlling oxygen absorption performance or suppressing deterioration of mechanical properties. The antioxidant is, for example, a copper-based antioxidant, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like, and a hindered phenol-based antioxidant or a phosphorus-based antioxidant is preferable.

Specific examples of the hindered phenol-based antioxidant, for example, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate, 4,4'-butylene Bis(3-methyl-6-tert-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-three , pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-sulfan-di-extended ethyl bis[3-(3,5-di Tributyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2-sulfanyl (4 -Methyl-6-1-butylphenol), N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydroxycinnamoamine), 3,5-di Tributyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-paran (3,5-di-butyl-4-hydroxybenzyl Benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl sulfonate ethyl ester, gins-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanuric acid Ester, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), 2,2'-methylene - bis-(4-ethyl-6-tert-butylphenol), 4,4'-thiobis-(3-methyl-6-tert-butylphenol), octylated diphenylamine, 2,4 - bis[(octylthio)methyl]-O-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'------ Base double (3- -6-tert-butylphenol, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoid Oxy]ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,1,3-parade (2-methyl-4-hydroxy-5-third Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-glucosin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis[3,3' - bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]diol, 1,3,5-gin (3',5'-di-t-butyl-4'-hydroxyl Benzyl)-second-three -2,4,6-(1H,3H,5H)trione, d-α-tocopherol, and the like. These may be used alone or in combination. A commercially available product of a hindered phenol compound is, for example, Irganox 1010 or Irganox 1098 (all trade names) manufactured by BASF Corporation.

Specific examples of phosphorus-based antioxidants, such as triphenyl phosphite, tri-octadecyl phosphite, tridecyl phosphite, tridecyl phenyl phosphite, diphenylisodecyl phosphite, bis (2) ,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, ginseng (2,4- Di-t-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, tetrakis(trisyl-4,4'-isopropylidenediphenyldiphosphite, 2,2- An organic phosphorus compound such as methylenebis(4,6-di-t-butylphenyl)octylphosphite. These may be used singly or as a mixture.

The content of the antioxidant is not particularly limited as long as it does not impair the various properties of the composition, but it is preferably 0.001 in the resin composition from the viewpoint of controlling oxygen absorption performance or suppressing deterioration of mechanical properties. 3% by mass, more preferably 0.01 to 1% by mass.

[Other additives]

A resin composition for forming an oxygen-absorbing barrier layer may be added with a lubricant, a matting agent, a heat-resistant stabilizer, a weathering stabilizer, a UV absorber, a plasticizer, a flame retardant, and an anti-corrosion agent depending on the intended use or performance. Additives such as an electrostatic agent, a coloring preventive agent, and a crystallization nucleating agent. These additives may be added as needed within a range that does not impair the effects of the present invention.

2. Any layer 2-1. Welding layer

In the present invention, the direct blow molding bottle can be directly blow molded in addition to the oxygen absorbing barrier layer. The surface of the bottle (one side surface or both side surfaces) further contains a weld layer.

The thermoplastic resin having the weldability may be a polyolefin resin which is melted by heat and can be welded to each other, or other thermoplastic resin, for example, low density polyethylene, medium density polyethylene, high density polyethylene, and linear chain. Shape (linear) low density polyethylene, ethylene-α‧ olefin copolymer obtained by polymerization using a metallocene catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-acrylic acid copolymer, Ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyvinyl acetate resin, poly(meth)acrylic acid Polyolefin resins such as resins, polyvinyl chloride resins, polyethylene or polypropylene are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Further, the acid-modified polyolefin resin or the like may be used alone or in combination of two or more kinds. Among these, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, and metallocene are preferably used from the viewpoints of moldability, hygiene, taste, and the like. The ethylene-α‧ olefin copolymer obtained by polymerization of a catalyst is preferred.

Moreover, the weld layer may also contain a slip agent, a crystallization nucleating agent, a whitening preventive agent, a matting agent, a heat stabilizer, a weathering stabilizer, a UV absorber, a plasticizer, a flame retardant, etc., insofar as the effect thereof is not impaired. Additives such as antistatic agents, coloring inhibitors, antioxidants, and impact-resistant materials.

Further, in the case where the welded layer is provided on both sides of the direct blown bottle, the composition of the two welded layers may be different from each other, and it is preferable that the thermoplastic resin which is the main component is stable when it is the same.

Further, the outer welded layer may have a frost-like appearance by blending different types of resins.

The thickness of the weld layer in the present invention is preferably from 5 to 200 μm, more preferably from 10 to 150 μm, and even more preferably from 15 to 5, from the viewpoint of exhibiting practical weld strength and ensuring the processability of the direct blow bottle. 100 μm.

2-2. Adhesive layer

In the present invention, the direct blow bottle may contain an adhesive layer in addition to the oxygen absorbing barrier layer. In a direct blow molded bottle, in the case where a practical interlayer adhesive strength is not obtained between two adjacent layers (for example, an oxygen-absorbing barrier layer and a welded layer), it is preferable to provide an adhesive layer between the two layers.

The adhesive layer preferably contains an adhesive thermoplastic resin. Adhesive thermoplastic resin, for example, 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 or itaconic acid. An acid-modified polyolefin resin. It is preferable to select a resin which is the same kind as the thermoplastic resin having a weldability as a thermoplastic resin having adhesiveness.

The thickness of the adhesive layer is preferably from 2 to 100 μm, more preferably from 5 to 90 μm, even more preferably from 10 to 80 μm, from the viewpoint of exerting practical adhesive strength and ensuring the processability of the direct blow bottle.

2-3. recycling layer

A layer made of a recycled resin may be added between the inner layer or the outer layer and the intermediate layer from the viewpoint of recyclability. The scrap resin generated at the time of molding is pulverized and used as a recycled resin, which not only reduces the manufacturing cost but also is important from the viewpoint of efficient use of resources. In the case of using a regenerated resin, it is preferable to arrange it from the strength surface to the outer layer which is more than the oxygen-absorbing barrier layer.

2-4. Any other layer

In the present invention, the direct blow bottle can further contain any layer other than the above depending on the desired performance. Other materials constituting any of the layers having various properties include various kinds of polyamines such as polyolefins, nylon 6 or nylon MXD6, polyethylene terephthalate, polyglycolic acid, and the like. Various thermoplastic resins such as polyesters and ethylene vinyl alcohol copolymers are used alone or in combination.

3. Method for manufacturing direct blow molding bottle

The method for producing the direct blow bottle of the present invention is not particularly limited, and it can be produced by any method. For example, a direct blow molding device composed of a plurality of extruders and a cylindrical die is used to form a cylindrical blow molding bad material composed of a material of a polyamide resin (A) and another resin (B) such as polyolefin. The blow molding bad material is extruded into a tubular shape, and the blow molding bad material is clamped by a mold whose temperature is adjusted to about 10° C. to 80° C., and the lower part of the bad material is formed by kneading and blow molding, and at the same time, the welding is performed yet. At the time of cooling, blowing is performed by high-pressure air or the like, and the blow molding bad material is swollen and formed into a shape of a container such as a bottle shape, a tubular shape, or a groove shape.

Here, the direct blow molding apparatus to be used is not particularly limited, and may be a device composed of a single cylindrical mold and a single mold, a device equipped with a plurality of cylindrical molds and a plurality of molds, or a rotary direct blow molding device.

Further, it is also possible to use an in-mold labeling method in which an in-mold label is inserted in a mold in advance and a label is attached to the surface of the container. Moreover, although it is an in-mold labeling method, it is preferable to perform flame treatment or corona treatment before labeling the attachment in the case of attaching the label. Furthermore, sandblasting can be applied to the mold to give a frosty appearance.

The direct blow molded bottle of the present invention may also be coated with an inorganic or inorganic oxide vapor deposited film or an amorphous carbon film.

Examples of the inorganic substance or inorganic oxide include aluminum or aluminum oxide, cerium oxide, and the like. The vapor-deposited film of inorganic or inorganic oxide can mask the elution of acetaldehyde or formaldehyde from the direct blow bottle. The method for forming the vapor deposition film is not particularly limited, and examples thereof include a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion implantation method, or a chemical vapor deposition method such as PECVD. The thickness of the vapor deposited film is preferably from 5 to 500 nm, more preferably from 5 to 200 nm, from the viewpoints of gas barrier properties, light blocking properties, and bending resistance.

The amorphous carbon film is a diamond-like carbon film and is a hard carbon film also called an i carbon film or a hydrogenated amorphous carbon film. In the method of forming the film, a method in which the inside of the hollow molded body is evacuated by exhaust gas, a carbon source gas is supplied thereto, and energy for generating plasma is supplied to plasma the carbon source gas is thereby exemplified. An amorphous carbon film can be formed on the inner surface of the container. The amorphous carbon film can significantly reduce the penetration of low molecular inorganic gases such as oxygen or carbon dioxide gas, and can also suppress the absorption of various low molecular organic compounds having a taste. Attached. The thickness of the amorphous carbon film is preferably from 50 to 5,000 nm from the viewpoints of the adsorption suppressing effect of the low molecular organic compound, the effect of improving the gas barrier property, the adhesion to the plastic, the durability, and the transparency.

The direct blow molded bottle of the present invention is excellent in oxygen absorption performance and oxygen barrier property, and excellent in flavor retention of contents, and is therefore suitable for packaging of various articles.

The preserved items include beverages such as milk, dairy products, juices, coffee, teas, and alcoholic beverages; liquid seasonings such as sauces, soy sauces, and sauces, soups, stews, curries, prepared foods for infants, and caregivers. Conditioned foods such as foods; paste-like foods such as jams and mayonnaise; aquatic products such as squid and fish, cheese processed products such as cheese and cream; processed meat products such as meat, salami, sausage, ham, etc. ; carrots, potatoes and other vegetables; eggs; noodles; rice before conditioning, processed rice, rice porridge and other processed rice products; powder seasonings, coffee powder, milk powder for infants, powdered dietary food, Dried vegetables, pancakes and other dry foods; pesticides, pesticides and other chemicals; pharmaceuticals; cosmetics; pet food; shampoo, moisturizing, detergents and other miscellaneous goods;

Further, the direct blow bottle or the preserved product may be sterilized by a form suitable for the object to be stored before and after the storage of the object to be preserved. Examples of the sterilization method include hot water treatment at 100 ° C or lower, pressurized hot water treatment at 100 ° C or higher, ultra-high temperature heat treatment at 130 ° C or higher, electromagnetic sterilization such as ultraviolet rays, microwaves, and gamma rays, and oxyethylene (ethylene). Gas treatment such as oxide), sterilization of chemicals such as hydrogen peroxide or hypochlorous acid, and the like.

Example

The invention will be described in more detail below by way of examples, but the invention is not limited to the examples.

Further, in the following examples, the unit constituting the copolymer is referred to as "MXDA" and the unit derived from 1,3-bis(aminomethyl)cyclohexane is referred to as "unit". 1,3BAC", the unit from hexamethylenediamine is called "HMDA", The unit that uses its own diacid is called "AA", the unit derived from isophthalic acid is called "IPA", the unit from DL-alanine is called "DL-Ala", and the unit from DL-leucine is called "DL-Leu" and a unit derived from ε-caprolactam are called "ε-CL".

Further, polymethylene xylene hexamethylenediamine is called "N-MXD6", polypropylene is called "PP", polyethylene terephthalate is called "PET", and adhesive layer is called "AD". The ethylene-vinyl alcohol copolymer is referred to as "EVOH".

Manufacturing example

The α-amino acid content, relative viscosity, terminal amine group concentration, glass transition temperature and melting point of the polyamine compound obtained in the production example were measured by the following methods. Further, a film was produced from the polyamide resin obtained in the production example, and the oxygen absorption amount thereof was measured by the following method.

(1) α-amino acid content rate

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

(2) Relative viscosity

1 g of the polyamine compound was dissolved in 100 ml of 96% sulfuric acid at 20 to 30 ° C with stirring. After completely dissolving, 5 ml of the solution was quickly taken to a Cannon-Fenske type viscometer, and after standing for 10 minutes in a constant temperature crucible at 25 ° C, the dropping time (t) was measured. Further, the dropping time (t ₀ ) of 96% sulfuric acid itself was also measured in the same manner. From t and t ₀ , the relative viscosity is calculated in the following formula.

Relative viscosity = t / t ₀

(3) terminal amine group concentration [NH ₂ ]

Finely known as polyamine compound, dissolved in phenol / ethanol = 4 / 1 volume solution at 20 ~ 30 ° C, completely dissolved, while stirring, while washing the inner wall of the container with methanol 5ml, with 0.01mol / L hydrochloric acid aqueous solution And titration, the terminal amine group concentration [NH ₂ ] was obtained.

(4) Glass transition temperature and melting point

Using a differential scanning calorimeter (Shimadzu Corporation (trade name), trade name: DSC-60), DSC measurement (differential scanning calorimetry) was carried out under a nitrogen gas flow rate at a temperature increase rate of 10 ° C /min to determine the glass transition temperature (Tg). ) and melting point (Tm).

(5) oxygen uptake

Use 30mm with T mode Biaxial extruder (manufactured by Institute of Plastics and Engineering), with a cylinder ‧ T-die temperature (melting point of polyamine resin + 20 ° C), forming a thickness of about 100 μm from polyamine resin without extension Single layer film forming.

Two pieces of test pieces of 10 cm × 10 cm cut out from the produced non-extended single-layer film were placed together with a cotton piece containing 10 ml of water into a 25-cm × 18 cm 3-way sealed bag composed of an aluminum foil laminated film to make the inside of the bag The air was sealed in a manner of 400 ml. The humidity inside the bag is 100% RH (relative humidity). After storage at 40 ° C for 7 days, after storage for 14 days, and after storage for 28 days, the oxygen concentration in the bag was measured by an oxygen concentration meter (manufactured by Toray Engineering Co., Ltd., trade name: LC-700F), and the oxygen concentration was calculated from the oxygen concentration. Oxygen intake.

Further, in the polyamine compound obtained in Production Examples 11 to 14, the film sample was replaced with a powder sample 2 g obtained by finely pulverizing a pellet or a pulverized material of a polyamine compound into a wrapping paper. The oxygen uptake was calculated in the same manner as described above.

Production Example 1 (Production of Polyamine Compound 1)

In a pressure-resistant reaction vessel equipped with a mixer, a condenser, a condenser, a pressure regulator, a thermometer, a drip tank and a pump, an aspirator, a nitrogen inlet pipe, a bottom exhaust valve, and a wire drawing die, 13000g (88.96mol), DL-alanine (available from Asahi Kasei Chemicals Co., Ltd.) 880.56g (9.88mol), sodium phosphite 11.7g (0.11mol), sodium acetate 6.06g (0.074mol), after fully replacing with nitrogen, the inside of the reaction container is sealed, keeping the inside of the container at 0.4MPa The temperature was raised to 170 ° C with stirring. After reaching 170 ° C, 12082.2 g (88.71 mol) of m-xylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) stored in the dropping tank was added dropwise to the molten raw material in the reaction vessel, and the inside of the holding vessel was kept in the holding vessel. In the state of 0.4 MPa, the generated condensation water was removed from the outside of the system and the temperature was continuously raised to 240 ° C in the reaction vessel. After the dropwise addition of m-xylylenediamine was completed, the inside of the reaction vessel was gradually returned to normal pressure, and then, the inside of the reaction vessel was depressurized to 80 kPa using an aspirator to remove the condensed water. Observe the stirring torque of the mixer under reduced pressure. When the predetermined torque is reached, the stirring is stopped, the reaction tank is pressurized with nitrogen, the bottom valve is opened, and the polymer is pulled out from the drawing die to form a strand. After the shape, it was cooled and pelletized by a granulator. Next, the pellets were placed in a stainless steel rotary drum type heating device and rotated at 5 rpm. Nitrogen substitution was carried out sufficiently, and the temperature inside the reaction system was raised from room temperature to 140 ° C under a small nitrogen flow. When the temperature in the reaction system reached 140 ° C, the pressure was reduced to 1 torr or less, and the temperature in the system was raised to 180 ° C in 110 minutes. When the temperature in the system reached 180 ° C, solid phase polymerization was continued for 180 minutes at the same temperature. After completion of the reaction, the pressure was reduced, and the temperature inside the system was lowered under a nitrogen stream. The pellet was taken out at 60 ° C to obtain MXDA/AA/DL-Ala copolymer (polyamine compound 1).

Further, the additive composition ratio of each monomer was m-xylylenediamine: adipic acid: DL-alanine = 47.3: 47.4: 5.3 (mol%).

Production Example 2 (Production of Polyamine Resin 2)

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

Production Example 3 (Manufacture of Polyamide Resin 3)

In the same manner as in Production Example 1, except that the addition ratio of the respective monomers was changed to m-xylylenediamine: adipic acid: DL-alanine = 41.1: 41.3: 17.6 (mol%). MXDA/AA/DL-Ala copolymer (polyamide resin 3).

Production Example 4 (Manufacture of Polyamide Resin 4)

MXDA/AA was obtained in the same manner as in Production Example 1 except that the addition ratio of the respective monomers was changed to m-xylylenediamine: adipic acid: DL-alanine = 33.3:33.4:33.3 (mol%). /DL-Ala copolymer (polyamide resin 4).

Production Example 5 (Manufacture of Polyamide Resin 5)

The α-amino acid was replaced with DL-leucine (manufactured by Ningbo Haishuo Bio-technology), and the addition ratio of each monomer was set to m-xylylenediamine: adipic acid: DL-leucine = In the same manner as in Production Example 1, except that 44.3: 44.6: 11.1 (mol%), MXDA/AA/DL-Leu copolymer (polyamide resin 5) was obtained.

Production Example 6 (Manufacture of Polyamide Resin 6)

The dicarboxylic acid component was replaced with a mixture of isophthalic acid (manufactured by AG International Chemical Co., Ltd.) and adipic acid, and the addition ratio of each monomer was set to m-xylylenediamine: adipic acid: MXDA/AA/IPA/DL-Ala copolymer (polyamide resin 6) was obtained in the same manner as in Production Example 1 except that phthalic acid: DL-alanine = 44.3:39.0:5.6:11.1 (mol%). .

Production Example 7 (Manufacture of Polyamide Resin 7)

ε-Caprolactam (manufactured by Ube Industries, Ltd.) was used as a comonomer, and α-amino acid was replaced with DL-leucine, and the addition ratio of each monomer was set to m-xylene. Diamine: adipic acid: DL-leucine: ε-caprolactam = 41.0: 41.3: 11.8: 5.9 (mol%), except that the same procedure as in Production Example 1 was carried out, and MXDA/AA/DL-Leu was obtained. / ε-CL copolymer (polyamide resin 7).

Production Example 8 (Manufacture of Polyamide Resin 8)

Replace the diamine component with 1,3-bis(aminomethyl)cyclohexane (Mitsubishi Gas Chemicals) And a mixture of m-xylylenediamine, and the addition ratio of each monomer is set to m-xylylenediamine: 1,3-bis(aminomethyl)cyclohexane: adipic acid: DL MXDA/1,3BAC/AA/DL-Ala copolymer (polyamide resin 8) was obtained in the same manner as in Production Example 1 except that aglycine = 33.2:11.1:44.6:11.1 (mol%).

Production Example 9 (Manufacture of Polyamide Resin 9)

The diamine component is replaced by a mixture of hexamethylenediamine (manufactured by Showa Chemical Co., Ltd.) and m-xylylenediamine, and the addition ratio of each monomer is set to m-xylylenediamine: six Methyldiamine: adipic acid: DL-alanine = 33.3: 11.1: 44.5: 11.1 (mol%), except that the same procedure as in Production Example 1 was carried out, and MXDA/HMDA/AA/DL-Ala copolymer (poly) was obtained. Indoleamine 9).

Production Example 10 (Manufacture of Polyamide Resin 10)

N- was obtained in the same manner as in Production Example 1 except that DL-alanine was not added, and the addition ratio of each monomer was changed to m-xylylenediamine: adipic acid = 49.8: 50.2 (mol%). MXD6 (polyamide resin 10).

Production Example 11 (Production of Polyamine Compound 11)

The MXDA/AA/DL-Ala copolymer (polyamide compound 11) was obtained in the same manner as in Production Example 1 except that the solid phase polymerization was not carried out.

Further, the additive composition ratio of each monomer was m-xylylenediamine: adipic acid: DL-alanine = 47.2: 47.4: 5.3 (mol%).

Production Example 12 (Production of Polyamine Compound 12)

The MXDA/AA/DL-Ala copolymer (polyamide compound 12) was obtained in the same manner as in Production Example 2 except that the solid phase polymerization was not carried out.

Further, the additive composition ratio of each monomer was: m-xylylenediamine: adipic acid: DL-alanine = 44.4: 44.5: 11.1 (mol%).

Production Example 13 (Production of Polyamine Compound 13)

The MXDA/AA/DL-Ala copolymer (polyamide compound 13) was obtained in the same manner as in Production Example 4 except that the solid phase polymerization was not carried out.

Further, the additive composition ratio of each monomer was: m-xylylenediamine: adipic acid: DL-alanine = 33.3: 33.4: 33.3 (mol%).

Production Example 14 (Production of Polyamine Compound 14)

The MXDA/AA/IPA/DL-Ala copolymer (polyamide compound 14) was obtained in the same manner as in Production Example 6 except that the solid phase polymerization was not carried out.

Further, the additive composition ratio of each monomer was: m-xylylenediamine: adipic acid: isophthalic acid: DL-alanine = 44.3: 38.9: 5.6: 11.1 (mol%).

Table 1 shows the monomer composition of the polyamidamide compounds 1 to 14, and the α-amino acid content, relative viscosity, terminal amine group concentration, glass transition temperature, melting point, and oxygen absorption amount of the obtained polyamide resin. The measurement results.

Next, in Examples 1 to 27 and Comparative Examples 1 to 14, a direct blow bottle was produced using the above polyamine compounds 1 to 14.

Example 1

Using a multi-layer direct blow molding apparatus equipped with three extruders, a cylinder mold, and a mold, the polyamine compound 1 is extruded at 260 ° C from the first extruder to N-MXD6 (Mitsubishi Gas Chemical Co., Ltd., Product name: MX nylon, grade: K7007C) Blended pellets obtained by dry mixing in a ratio of 30:70 (mass ratio), extruded from 230 ° C at the second extruder (Japanese polypropylene) ), the product name: Novatec, grade: FY6), extruded from the third extruder at 220 ° C adhesive resin (Mitsui Chemical Co., Ltd., trade name: Admer, grade: QB515), and blown with a mold Plastic molding, manufacturing of a polypropylene layer/adhesive resin layer/polyamido compound 1×N-MXD6 mixed layer/adhesive resin layer/polypropylene layer from the outer layer in a capacity of 200 cc bottle. also, The thickness of each layer was set to 300/10/60/10/300 (μm).

Example 2~10

A bottle was prepared in the same manner as in Example 1 except that the mixing ratio of the polyamine compound and the polyamine compound × resin (B) mixed layer shown in Table 2 was changed.

Example 11~27

A bottle was prepared in the same manner as in Example 1 except that the mixing ratio and the layer constitution of the polyamine compound, the resin (B), and the polyamine compound × resin (B) mixed layer described in Table 2 were changed.

Further, in Examples 14, 18, 19, and 26, PET was manufactured by Toyobo Co., Ltd., trade name: IP560, and adhesive resin was manufactured by Mitsubishi Chemical Co., Ltd., trade names: MODIC-AP, F534A.

Comparative example 1~14

A direct blow bottle was produced in the same manner as in Example 1 except that the mixing ratio and the layer constitution of the polyamine compound, the resin (B), and the polyamine compound × resin (B) mixed layer described in Table 2 were changed. .

Further, in Comparative Examples 2, 5 and 8, cobalt (II) stearate was added so that the cobalt content was 400 ppm with respect to the polyamine compound 10.

Further, in Comparative Examples 3, 6, and 9, cobalt (II) stearate was added so that the cobalt content became 100 ppm with respect to the polyamine compound 10, and maleic acid-modified polybutadiene was added (Nippon Petrochemical Co., Ltd.) The product name: M-2000-20) is 3 parts by mass based on 100 parts by mass of the polyamine compound 10.

Further, in Comparative Examples 13 to 14, PET was manufactured by Toyobo Co., Ltd., trade name: IP560, and adhesive resin was manufactured by Mitsubishi Chemical Co., Ltd., and trade names: MODIC-AP and F534A.

The direct blow molded bottles produced in Examples 1 to 27 and Comparative Examples 1 to 14 were evaluated for the residual ratio of L-ascorbic acid and the odor and taste after opening.

(1) Residual rate from L-ascorbic acid

The opening of the direct blow bottle was filled with 100 ml of a 10% aqueous solution of L-ascorbic acid, and the aluminum foil laminated film was heat-sealed to seal the opening. In Examples 1 to 13, 15 to 17, 20 to 25, and 27, and Comparative Examples 1 to 12, autoclave (SR-240, trade name, manufactured by Tomy Seiko Co., Ltd.) was used for pressure heating at 121 ° C for 30 minutes. After the treatment, the container was stored in an environment of 23 ° C and 50% RH for 1 month. Further, in Examples 14, 18, 19, and 26 and Comparative Examples 13 to 14, the heat treatment was carried out for 3 months in an environment of 23 ° C and 50% RH, and then the content liquid was taken out and placed in a high-beaker having a capacity of 100 ml. 10 ml of the content liquid was charged, followed by 5 ml of a mixed aqueous solution of metaphosphoric acid and acetic acid and 40 ml of distilled water. Next, a 0.05 mol/l iodine solution was used as a titration solution, and a potentiometric titration apparatus was used to titrate by the inflection point detection method, and the residual ratio of L-ascorbic acid was obtained from the results. Further, the higher the residual ratio of L-ascorbic acid, the more excellent the effect of suppressing oxidative degradation of the content.

(2) smell and taste when opening

The obtained direct blow molded bottle was filled with mineral water, and sealed for 1 month in a thermostat bath of 40 ° C and 50% RH. After storage, the five panelists sniffed the taste of the newly opened container and evaluated whether there was any odor.

Also, after the opening, five panelists included mineral water in the mouth to evaluate whether the mineral water had a change in taste.

○: There was no odor at all, and the taste of the mineral water did not change.

×: Although there is little but an odor, or the taste of the mineral water changes slightly.

Table 2 shows the results of the evaluation.

Layer composition ^* (1) APP/AD/polyamine compound (A) + resin (B) / AD / PP = 300/10/60/10/300 B PP / AD / MXD6 / polyamine compound (A) +Resin (B)/MXD6/AD/PP=300/10/10/40/10/10/300 C PP/AD/EVOH/Polyamine compound (A)+Resin (B)/EVOH/AD/PP =300/10/10/40/10/10/300 D PET/AD/polyamine compound (A) + resin (B) / AD / PET = 300/10/90/10/300 ^* (2) Hard Cobalt (II) succinate is added to the polyimide resin layer ^* (3) Cobalt (II) stearate and modified polybutadiene are added to the polyamide resin layer ^* (4) A, B, C : 121 ° C heat and pressure treatment for 30 minutes, measured at 23 ° C, 50% RH after one month, D: without heat treatment, after 3 months at 23 ° C measured ^* (5) at 40 ° C 50% RH The thermostat is stored for 1 month and then measured.

The direct blow molded bottles of Examples 1 to 27 were all excellent in the residual ratio of L-ascorbic acid, the odor at the time of opening, and the taste. In Comparative Examples 1, 4, 7, and 10 to 14, the residual ratio of L-ascorbic acid was low. Further, Comparative Examples 2, 5, and 8 which impart oxygen absorbing properties by using cobalt stearate (II) were subjected to delamination after boiling treatment or after hot water filling, and the barrier property was deteriorated. Therefore, the residual L-ascorbic acid could not be evaluated. rate. Further, in Comparative Examples 3, 6, and 9 in which cobalt (II) stearate and maleic acid-modified polybutadiene were added to the oxygen-absorbing barrier layer, although the residual ratio of L-ascorbic acid was good, the smell at the time of opening, Poor taste.

[Industry Utilization]

The direct blow molded bottle of the present invention is suitable as a bottle container having oxygen barrier properties and oxygen absorbing properties.

Claims (9)

A direct blow bottle comprising a layer formed of a resin composition containing a polyamine compound (A) and a resin (B); the polyamine compound (A) comprises: a diamine unit of 25 to 50 mol% And an alicyclic diamine unit selected from the group consisting of aromatic diamine units represented by the following formula (I-1), represented by the following formula (I-2), and the following formula (I) -3) The total content of at least one diamine unit in the group consisting of linear aliphatic diamine units is 50 mol% or more; the dicarboxylic acid unit is 25 to 50 mol%, wherein The linear aliphatic dicarboxylic acid unit represented by the formula (II-1) and/or the aromatic dicarboxylic acid unit represented by the following formula (II-2) has a total content of 50 mol% or more; (III) represents a constituent unit of 0.1 to 50% by mole; [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 extension An aryl group; in the formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group]. A direct blow molded bottle according to claim 1, wherein R of the formula (III) is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted carbon number of 6 to 10 base. A direct blow molded bottle according to claim 1 or 2, wherein the diamine unit contains 50 mol% or more of m-xylylenediamine unit. The direct blow molded bottle according to any one of claims 1 to 3, wherein the linear aliphatic dicarboxylic acid unit is selected from the group consisting of adipic acid units, sebacic acid units, and 1,12-ten The total content of at least one of the groups consisting of dialkyldicarboxylic acid units is 50 mol% or more. The direct blow molded bottle according to any one of claims 1 to 4, wherein the aromatic dicarboxylic acid unit is selected from the group consisting of isophthalic acid units, terephthalic acid units, and 2,6- At least one of the group consisting of naphthalene dicarboxylic acid units has a total content of 50 mol% or more. The direct blow molded bottle according to any one of claims 1 to 5, wherein the polyamine compound (A) further contains 0.1 to 49.9% of all constituent units of the polyamine compound (A). ω% of the ω-amino carboxylic acid unit represented by the following formula (X); [In the general formula (X), p represents an integer of 2 to 18]. The direct blow molded bottle of claim 6, wherein the ω-amino carboxylic acid unit contains 6-aminocaproic acid unit and/or 12-aminododecanoic acid unit in a total amount of 50% by mole. the above. The direct blow molded bottle according to any one of claims 1 to 7, wherein the polyamidamine compound (A) has a relative viscosity of 1.8 or more and 4.2 or less and the polyamine compound (A) / the resin ( B) The mass ratio is 5/95~95/5. The direct blow molded bottle according to any one of claims 1 to 7, wherein the polyamidamine compound (A) has a relative viscosity of 1.01 or more and less than 1.8 and the polyamine compound (A)/ The mass ratio of the resin (B) is 5/95 to 50/50.