TW201309563A - Direct blow molding of multi-layer bottles - Google Patents

Abstract

The present invention provides a direct blow molded multilayer bottle which is a layer of at least two layers of a layer (A) containing a polyamide resin (A) and a layer (B) containing at least one resin (B) as a main component. The polyamine resin (A) contains 25 to 50 mol% of a diamine unit containing 50 mol% or more of a specific diamine unit, and a dicarboxylic acid containing 50 mol% or more of a specific dicarboxylic acid unit. The acid unit is 25 to 50% by mole, and the specific constituent unit is 0.1 to 50% by mole.

Description

Direct blow molding of multi-layer bottles

The present invention relates to a direct blow molded multilayer 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 multilayer bottle which exhibits oxygen barrier properties. It can exhibit oxygen absorption without transition metal, can inhibit oxidative degradation of the content, and can not detract from the flavor of the content, and the strength of the oxygen barrier layer does not decrease even after long-term storage.

The present invention provides the following direct blow molded multilayer bottles.

A direct blow molding multilayer bottle comprising at least two layers of a layer (A) comprising a polyamide resin (A) and a layer (B) containing at least one resin (B) as a main component; The polyamide resin (A) contains 25 to 50 mol% of a diamine unit, and contains an aromatic diamine unit selected from the following general formula (I-1), and has the following formula (I) And the total content of at least one diamine unit in 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 mol% The above; the dicarboxylic acid unit is 25 to 50 mol%, and contains a linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) and/or an aromatic compound represented by the following general formula (II-2) The total content of the group dicarboxylic acid unit is 50% by mole or more; and the constituent unit represented by the following formula (III) is 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 multi-layer bottle of the invention can exhibit oxygen barrier property, and at the same time can exhibit oxygen absorption performance without transition metal, and with the oxygen absorption, the oxygen barrier layer is strong The degree of decline is minimal. 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 multi-layer bottle>>

The direct blow molded multilayer bottle of the present invention comprises a layer (A) of a polyamide resin (A) (hereinafter sometimes referred to as an "oxygen barrier layer"), and at least one resin (B) as a main component. A layer of at least two layers of layer (B).

The layer constitution of the direct blow molded multilayer bottle of the present invention is not particularly limited, and the number or type of the layer (A) and the layer (B) is not particularly limited. For example, it may be composed of A/B composed of one layer (A) and one layer (B), or may be B/ composed of one layer (A) and two layers (B). The three-layer structure of A/B. Further, it may be composed of five layers of B1/B2/A/B2/B1 composed of two layers (B) of one layer (A), two layers (B1) and two layers (B2). Further, the direct blow molded multilayer bottle of the present invention may optionally contain any layer such as an adhesive layer (AD), and may be, for example, 7 layers of B1/AD/B2/A/B2/AD/B1.

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. Layer (A) containing polyamine resin (A) (oxygen barrier layer)

In the present invention, the oxygen-absorbing barrier layer can exhibit oxygen-absorbing performance and oxygen barrier properties by containing a specific polyamine resin (hereinafter referred to as "polyamine resin (A)") to be described later. The polyamine resin (A) to be contained in the oxygen-absorbing barrier layer may be one type or a combination of two or more types.

In the present invention, the oxygen-absorbing barrier layer contains a polyamide resin (A) as a main resin component. In the oxygen barrier layer, a resin other than the polyamide resin (A) may be added, but it is preferably The ratio of the polyamide resin (A) to all the resins of the oxygen-absorbing barrier layer is preferably more than 95% by mass. The resin contained in the oxygen-absorbing barrier layer may be only polyamine resin (A), and the ratio of the polyamine resin (A) to all of the resins of the oxygen-absorbing barrier layer is preferably 100% by mass or less.

As described above, a resin other than the polyamine resin (A) may be added to the oxygen-absorbing barrier layer, and the additive resin may be used conventionally in order not to impair the object of the present invention, and to impart properties to the oxygen-absorbing barrier layer. Various resins. For example, from the viewpoint of imparting impact resistance, pinhole resistance, and flexibility, for example, polyolefins such as polyethylene or polypropylene, various modified products thereof, polyolefin elastomers, and polyamide-based elastomers are mentioned. Further, various thermoplastic elastomers such as a styrene-butadiene copolymer resin or a hydrogenated product thereof, a polyester elastomer, and various polyamines such as nylon 6, 66, 12, and nylon 12 are further imparted. From the viewpoint of oxygen absorption performance, a resin containing a carbon-carbon unsaturated double bond such as polybutadiene or modified polybutadiene may be mentioned. The resin to be added may be one type or a combination of two or more types. It is preferable that the ratio of the added resin to all the resins of the oxygen-absorbing barrier layer is 5% by mass or less.

In addition to the polyamine resin (A), the oxygen-absorbing barrier layer may contain additives described later (hereinafter sometimes referred to as "additive (C)") depending on the desired performance, etc., but the polyamine in the oxygen-absorbing barrier layer. The content of the resin (A) is preferably from 90% by mass to 100% by mass, and more preferably from 95% by mass to 100% by mass, from the viewpoints of moldability, oxygen absorption performance, and oxygen barrier property.

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 directly blown multilayer bottle. 10~80μm.

1-1. Polyamide resin (A) <Composition of Polyamine Resin (A)>

In the present invention, the polyamide resin (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 Mole; 25 to 50 mol% of the dicarboxylic acid unit, wherein the linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) and/or the aromatic dicarboxylic acid represented by the following general formula (II-2) The total content of the acid unit is 50% by mole or more; and the carboxylic acid unit having a hydrogen level of 3 (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 polyamide resin (A) may further contain a constituent unit other than the above, without departing from the scope of the effects of the present invention.

In the polyamine resin (A), the content of the carboxylic acid unit containing a third-order hydrogen is 0.1 to 50 mol%. When the content of the carboxylic acid unit containing the tertiary hydrogen is less than 0.1 mol%, sufficient oxygen absorbing performance cannot be exhibited. 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 polyamidamide resin (A) are lowered, especially including grade 3 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 containing the third-order hydrogen is preferably 0.2 mol% or more, more preferably 1 mol% or more, more preferably 1 mol% or more, from the viewpoint of the oxygen absorbing property or the property of the polyamidamide resin (A). 40% or less, more preferably 30% by mole or less.

The polyamine resin (A) has a diamine unit content of 25 to 50 mol%, preferably 30 to 50 mol% from the viewpoint of oxygen absorption performance or polymer properties. Similarly, in the polyamide resin (A), the content of the dicarboxylic acid unit is from 25 to 50 mol%, preferably from 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 polyamide resin (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 resin (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, to make crystallinity In the low case, the cis isomer content ratio of the bis(aminomethyl)cyclohexane is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% 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 polyamide resin (A) is preferably improved in transparency or color tone or easy to form a general-purpose thermoplastic resin, in addition to imparting excellent gas barrier properties to the polyamide resin (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 polyamide resin (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 polyamide resin (A).

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

Examples of the compound 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, The polyether-based diamine having an ether bond represented by Jeffamine or Elastamine (all trade names) manufactured by Huntsman Co., Ltd. is not limited thereto. These may be used alone or in combination of two or more.

[dicarboxylic acid unit]

The dicarboxylic acid unit in the polyamide resin (A) contains the straightness represented by the above formula (II-1) from the viewpoints of the reactivity at the time of polymerization, the crystallinity of the polyamide resin (A), and the moldability. 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 polyamide resin (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 thereto. 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 polyamide resin (A) has the excellent gas barrier property of the polyamide resin (A), and the heat resistance after heat sterilization of the packaging material or the packaging container is considered. 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 polyamide resin (A) is a linear aliphatic group from the viewpoints of the gas barrier properties of the polyamide resin (A) and the heat 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 polyamide resin (A) is a linear aliphatic dicarboxylic acid unit from the viewpoint of imparting appropriate gas barrier properties and moldability to the polyamide resin (A). Preferably, the sebacic acid unit is preferably 50 mol% or more, and the polyamidamide resin (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 polyamide resin (A), the aromatic dicarboxylic acid unit represented by the above formula (II-2) is 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 polyamide resin (A) preferably contains a group selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic 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 point of view of moderate glass transition temperature or reduction of crystallinity, when the total of the two units is 100, Mohr Preferably, it is 0/100~100/0, more preferably 0/100~60/40, more preferably 0/100~40/60, and even more preferably 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 polyamide resin (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 polyamide resin (A) and lower the crystallinity of the polyamide resin (A), a 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 polyamide resin (A) and impart flexibility to the polyamide resin (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 polyamine resin (A) has at least one amine group and carboxyl group, or two or more, from the viewpoint of polymerization of the polyamide resin (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 polyamine resin (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 polyamide resin (A) can exhibit excellent oxygen absorption performance even without a transition metal.

In the present invention, it is not known that the polyamine resin (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), each of R, R ¹ and R ² represents 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 (with 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 alkyl group substituted with an aryl group (for example, benzyl group), an alkyl group-substituted aryl group (for example, p-tolyl group), an alkyl group-substituted aryloxy group (for example, 2-methylphenoxy group) Etc., but not limited to these.

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-membered aralkyl group such as a benzylidene group) and an extended 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 resin (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, a methyl group, an ethyl group, an isopropyl group, a 2-methylpropyl group, and a benzyl group are more preferable.

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 resin has a low molecular weight and a high copolymerization ratio per 1 g of the polyamide resin (A), the polyamine resin (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, when the polyamidamide resin (A) requires flexibility or the like, the diamine unit may be in addition to the dicarboxylic acid unit and the third-order hydrogen-containing carboxylic acid unit. Further, it contains the ω-amino carboxylic acid unit represented by the following formula (X).

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

The content of the aforementioned 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 constituent units of the polyamidamide resin (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 resin (A)]

The relative viscosity is used for the degree of polymerization of the polyamide resin (A). The ideal relative viscosity of the polyamide resin (A) is preferably from 1.8 to 4.2, more preferably from 1.9 to 4.0, still more preferably from 2.0 to 3.8, from the viewpoints of strength, appearance, and moldability of the molded article.

In the relative viscosity referred to herein, 1 g of the polyamide resin (A) was dissolved in 100 mL of 96% sulfuric acid, and the dropping time (t) measured by a Cannon-Fenske type viscometer at 25 ° C was measured. 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 polyamide resin (A) and the oxidative degradation of the polyamide resin (A) due to oxygen absorption can be controlled by changing the terminal amine group concentration of the polyamide resin (A). In the present invention, the concentration of the terminal amine group of the polyamide resin (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 Polyamide Resin (A)>

The polyamidamide resin (A) can constitute the aforementioned carboxylic acid having a hydrogen level of 3, by forming a diamine component which can constitute the diamine unit, a dicarboxylic acid component which can constitute the dicarboxylic acid unit, and the like. The carboxylic acid component containing three-stage hydrogen in the unit and, if necessary, the ω-amino carboxylic acid component constituting the ω-amino carboxylic acid unit are produced by polycondensation, and the degree of polymerization can be controlled by adjusting 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 polyamide resin (A) may be adjusted to be shifted by 1.

The polycondensation method of the polyamide resin (A) is, for example, a reaction extrusion method, a pressurized salt method, a normal pressure dropping method, a pressurized dropping method, or the like, but is not limited thereto. Further, when the reaction temperature is as low as possible, the yellowing or gelation of the polyamide resin (A) can be suppressed, and the polyamide resin (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 resin (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 polyamine resin (A)), and a carboxylic acid component containing a third-order hydrogen, which are melt-kneaded by an extruder and reacted. 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 resin (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. Slowly return the inside of the tank to normal pressure, and simultaneously raise the temperature to about 10 ° C of the melting point of the polyamide resin (A) and hold it, then slowly reduce the pressure to -0.02 MPaG, and continue to polycondensate at this temperature. After reaching a certain stirring torque, the inside of the tank is pressurized with nitrogen to about 0.3 MPaG. The polyamine resin (A) is recovered.

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 polyamidamide resin (A) having a carboxylic acid unit containing a tertiary hydrogen in a total amount of 15 mol% or more in all constituent units of the polyamide resin (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. Resin (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 polyamide resin (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 polyamide resin (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 polyamide resin (A) + 10 ° C and maintained, and then slowly decompressed to - 0.02 MPaG while maintaining this temperature to continue the polycondensation reaction. The polyamidamide resin (A) was recovered by applying a certain stirring torque to the inside of the tank under nitrogen pressure to about 0.3 MPaG.

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 polyamidamide resin (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 polyamide resin (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, thereby allowing the polycondensation reaction to proceed smoothly, and obtaining a polymer having excellent properties. Indoleamine resin (A). 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 resin (A) having a low yellowness is obtained.

[Steps to increase the degree of polymerization]

The polyamine resin (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 polyamide resin (A), in the above-described apparatus, the rotary drum type heating device is obtained from the viewpoint of being capable of shrinking the inside of the system and facilitating the removal of oxygen which is a cause of coloring. It is better.

[Compound containing phosphorus atom, alkali metal compound]

In the polycondensation of the polyamide resin (A), it is preferred to add a compound containing a phosphorus atom from the viewpoint of promoting the oximation 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 , sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, phenylphosphonic acid Phosphonic acid compound such as ethyl ester, sodium ethylphosphonate or potassium ethylphosphonate; phosphinic acid, sodium phosphinate, lithium phosphinate, potassium phosphinate, magnesium phosphinate, calcium phosphinate, phenyl a phosphinic acid compound such as phosphinic acid, sodium phenylphosphinate, potassium phenylphosphinate, lithium phenylphosphinate or ethyl phenylphosphinate; phosphorous acid, sodium hydrogen phosphite, sodium phosphite, A phosphorous acid compound such as lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite or pyrophosphoric acid.

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 compound containing a phosphorus atom is preferably 0.1 to 1000 ppm, more preferably 1 to 600 ppm, still more preferably 5 to 400 ppm, in terms of the phosphorus atom concentration in the polyamide resin (A). When it is 0.1 ppm or more, the polyamide resin (A) is not easily colored during polymerization, and transparency is improved. When it is 1000 ppm or less, the polyamide resin (A) is less likely to gel, and it is also possible to reduce the fact that a fish eye which is thought 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 of the polyamine resin (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 resin (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 polyamide resin (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, better 1.0/0.1~1.0/1.2, and more preferably 1.0/0.2~1.0/1.1.

1-2. Additives (C)

The oxygen-absorbing barrier layer of the present invention may further contain an additive (C) as needed in addition to the above-mentioned polyamine resin (A). The additive (C) may be used alone or in combination of two or more. The content of the additive (C) in the oxygen-absorbing barrier layer 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 bis-amine compound and/or a diester compound to the polyamide resin (A) 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 obtained from an aliphatic dicarboxylic acid mainly composed of stearic acid and a diamine mainly composed of ethylenediamine. Compound.

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.

More preferably, it is a diester compound obtained from an aliphatic dicarboxylic acid mainly composed of octacosanoic 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 oxygen-absorbing barrier layer. %. By adding 0.005% by mass or more and using a crystallization nucleating agent to the oxygen-absorbing barrier layer, 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 oxygen-absorbing barrier layer, the haze value of the molded article obtained by molding the polyamide resin (A) of the present invention can be kept low.

[layered citrate]

In the present invention, the oxygen-absorbing barrier layer may also contain a layered niobate. By adding the layered niobate, it is possible to impart not only oxygen barrier properties to the multilayer 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. Etc. 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; a triethylalkylammonium salt such as a salt, a triethyltetradecyl ammonium salt, a triethylhexadecyl ammonium salt or a triethyl octadecyl ammonium salt; a tributyl dodecyl ammonium salt, a tributyl fourteen a tributylalkylammonium salt such as a quaternary ammonium salt, a tributylhexadecyl ammonium salt or a tributyl octadecyl ammonium salt; dimethyldi-dodecyl ammonium salt, dimethyl di-tetradecyl ammonium a dimethyldialkylammonium salt such as a salt, a dimethyldi-hexadecyl ammonium salt, a dimethyl di-octadecyl ammonium salt, a dimethyl di-tallow ammonium salt; a dimethyl di-deca a dimethyldienyl ammonium salt such as an octadecyl ammonium salt or a dimethyl di-octadecadienyl ammonium salt; diethyl di-dodecyl ammonium salt or diethyl di-tetradecyl ammonium salt , diethyl di-hexadecyl ammonium salt, diethyl dialkyl ammonium salt such as diethyl di-octadecyl ammonium; dibutyl two - ten Dibutyldialkylammonium salt such as alkalium salt, dibutyldi-tetradecylammonium salt, dibutyldi-hexadecyl ammonium salt, dibutyldi-octadecyl ammonium salt; methylbenzyl group Methylbenzyldialkylammonium salt such as di-hexadecyl ammonium salt; dibenzyldialkylammonium salt such as dibenzyldi-hexadecyl ammonium salt; tri-dodecylmethylammonium salt, tri- a trialkylmethylammonium salt such as tetradecylmethylammonium salt or tri-octadecylmethylammonium salt; a trialkylethylammonium salt such as tri-dodecylethylammonium salt; tri-dodecylbutyrate a trialkylbutylammonium salt such as a quaternary ammonium salt; 4-amino-n-butyric acid, 6-amino-n-hexanoic acid, 8-aminooctanoic acid, 10-amino decanoic acid, 12-aminododecanoic acid An ω-amino acid such as 14-aminotetradecanoic acid, 16-aminohexadecanoic acid or 18-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. Base double (PAG) ammonium salt, diethyl bis (PAG) ammonium salt, two Butyl bis(PAG) ammonium salt, methyl alkyl bis(PAG) ammonium salt, ethyl alkyl bis(PAG) ammonium salt, butyl alkyl 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 dodeca, tetradecyl, hexadecyl, octadecyl, quaternary, etc. An alkyl group having 12 or more carbon atoms, and PAG means a polyalkylene glycol residue, preferably a polyethylene glycol residue having a carbon number of 20 or less or a polypropylene glycol residue, etc.) and at least one alkylene glycol The fourth-grade ammonium salt of the 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 oxygen-absorbing barrier layer in an amount of 0.5 to 8% by mass, more preferably 1 to 6% by mass, still more preferably 2 to 5% by mass. 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 polyamide resin (A). Oxidation reaction promoter, such as iron, cobalt, nickel, etc. Or a low-grade inorganic or organic acid salt of a Group I metal such as silver, a Group IV metal such as tin, titanium or zirconium, a Group V of vanadium, a Group VI of chromium, a Group VI of manganese, or a Group VII metal such as manganese. Or the 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, in terms of the atomic concentration of the oxygen in the oxygen-absorbing barrier layer.

[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 by imparting oxygen absorbing performance to the oxygen absorbing barrier layer in addition to the oxygen absorbing property of the polyamide resin (A). 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 oxygen absorbing barrier layer.

[Anti-gelation. Reduce the silver point of the agent]

In the present invention, it is preferred to add one or more kinds of carboxylates selected from sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate, and the like to the oxygen barrier layer. The class is better. 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 polyamide resin (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 oxygen barrier layer. When it is 400 ppm or more, thermal deterioration of the polyamide resin (A) can be suppressed and gelation can be prevented. Moreover, if it is 10000 ppm or less, the polyamide resin (A) will not be emitted. Poor shape, no coloring or whitening. If a carboxylate which is a basic substance exists in the molten polyamine resin (A), it is presumed that the modification of the polyamide resin (A) due to heat is slowed down, and it is suppressed that it 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 oxygen-absorbing barrier layer. Therefore, the particle size 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 the polyamide resin (A), but from the viewpoints of workability or reduction of acetic acid odor, a masterbatch composed of polyamine resin (A) and sodium acetate is preferably used. The polyamide resin (A) is preferably subjected to dry mixing for forming. 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 polyamide resin (A).

[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 oxygen barrier layer from the viewpoint of controlling oxygen absorption performance or suppressing deterioration of mechanical properties. ~3 mass%, more preferably 0.01-1 mass%.

[Other additives]

In the oxygen barrier layer, a lubricant, a matting agent, a heat stabilizer, a weathering stabilizer, a UV absorber, a plasticizer, a flame retardant, an antistatic agent, a coloring preventive agent, or the like may be added depending on the intended use or performance. An additive such as a nucleating agent. These additives may be added as needed within a range that does not impair the effects of the present invention.

2. Layer (B) with resin (B) as its main component

In the present invention, the layer (B) is a layer containing the resin (B) as a main component. Here, the "main component" is the layer (B), and the resin (B) content is 70% by mass or more, preferably 80% by mass or more, and more preferably 90 to 100% by mass. The layer (B) may contain the above-mentioned additive (C) in addition to the resin (B) in accordance with the required properties and the like.

The direct blow molded multilayer bottle of the present invention may have a plurality of layers (B), and the majority of the layers (B) may be identical or different from each other. The thickness of the layer (B) can be appropriately determined depending on the application, and is preferably from 5 to 200 μm, more preferably from 10 to 150 μm, even more preferably from 20 to 2, from the viewpoint of ensuring various physical properties such as flexibility required for directly blowing a multilayer bottle. 100 μm.

2-1. Resin (B)

In the present invention, the resin (B) can be any resin and is not particularly limited. As the resin (B), for example, a thermoplastic resin, specifically, for example, a polyolefin, a polyester, a polyamide, an ethylene-vinyl alcohol copolymer, and a plant-derived resin can be used. 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 the oxygen absorbing effect, a resin having high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymer is more preferable.

[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-(meth)acrylic acid copolymer, etc. Ethylene-α,β-unsaturated carboxylic acid ester copolymer, ethylene-α,β-unsaturated carboxylic acid ester copolymer, ethylene-α,β-unsaturated carboxylic acid copolymer Other ethylene copolymers such as an ion crosslinked product and an ethylene-vinyl acetate copolymer; and the like, such as a graft modified polyolefin which is graft-modified with an acid anhydride such as maleic anhydride or the like.

[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, pimelic acid, suberic acid, sebacic acid, sebacic acid, decanedicarboxylic acid, and dodecanedicarboxylic acid. Acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3 a saturated aliphatic dicarboxylic acid exemplified by cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid or the like or the ester formability thereof An unsaturated aliphatic dicarboxylic acid exemplified as a derivative, fumaric acid, maleic acid, itaconic acid or the like, or an ester-forming derivative thereof, phthalic acid, isophthalic acid, terephthalic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'- Biphenyldicarboxylic acid, 4,4'-biphenylfluorene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylate An aromatic dicarboxylic acid exemplified by an acid, a hydrazine dicarboxylic acid or the like, or an ester-forming derivative thereof, 5-sodium sulfoisophthalic acid, 2-sodium sulfophthalic acid, 5-lithium sulfo Isophthalic acid, 2-lithium a metal sulfonate-containing aromatic dicarboxylic acid or a lower alkane exemplified by a base of terephthalic acid, 5-potassium sulfoisophthalic acid or 2-potassium sulfophthalic acid Ester derivatives and the like.

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-hydroxyethoxyphenyl)fluorene, bis(p-hydroxyphenyl) Ether, bis(p-hydroxyphenyl)fluorene, bis(p-hydroxyphenyl)methane, 1,2-bis(p-hydroxyphenyl)ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol An aromatic diol exemplified by 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 containing ethylene terephthalate unit 70. More than 5% by mole of linear polyester, more preferably 80% by mole of ethylene terephthalate unit, more preferably 90 parts of ethylene terephthalate unit More than 100% linear polyester.

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 a linear polyester containing 70% by mole or more of a propylene terephthalate unit, and a linear polyester containing 70% by mole or more of a propylene glycol naphthalate unit. a linear polyester containing 70 mol% or more of 1,4-cyclohexane terephthalic acid dimethanol ester unit, or a linear polyester containing 70 mol% or more of a butylene naphthalate unit, or A linear polyester of 70 mol% or more of a butylene naphthalate diester 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" does not mean "polyamide resin (A)") of the present invention, for example, a unit derived from a meglumine or an aminocarboxylic acid is mainly composed. a polyamine of a unit, or an aliphatic polyamine which has a unit derived from an aliphatic diamine and an aliphatic dicarboxylic acid as a main constituent unit, and a unit derived from an aliphatic diamine and an aromatic dicarboxylic acid as a main component a part of the aromatic polyamine which is a constituent unit, a part of the aromatic polyamine which is a main constituent unit derived from an aromatic diamine and an aliphatic dicarboxylic acid, and the like, and a monomer other than the main constituent unit, if necessary Unit copolymerization.

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 (polyamine MXD12), poly1,3-bis (aminomethyl) Cyclohexanehexanediamine (polyamine BAC6), poly-p-xylylenediamine (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]

Various conventionally known resins may be added as the resin (B) insofar as the object of the present invention is not impaired. For example, from the viewpoint of imparting impact resistance, pinhole resistance, flexibility, adhesion, and squeezing properties, for example, polyolefin such as polyethylene or polypropylene, or various modified materials thereof, and poly Various thermoplastic elastomers represented by an olefin-based elastomer, a polyamine-based elastomer, a styrene-butadiene copolymer resin or a hydrogenated product thereof, a polyester-based elastomer, or the like, nylon 6, 66, 12, and nylon 12 Examples of various polyamines and the like include a resin containing a carbon-carbon unsaturated double bond such as polybutadiene or modified polybutadiene from the viewpoint of further imparting oxygen absorption performance.

3. Any layer 3-1. Welding layer

In the present invention, the direct blown multilayer bottle contains a layer of the oxygen-absorbing barrier layer and the resin (B) as a main component, and may further contain a weld layer on the surface of the directly blown multilayer bottle (one-side surface or both side surfaces). .

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 obtained by polymerization using a metallocene catalyst. Olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methyl a pentene polymer, a polybutene polymer, a polyolefin resin such as a polyvinyl acetate resin, a poly(meth)acrylic resin, a polyvinyl chloride resin, or a polyethylene or a polypropylene; An acid-modified polyolefin resin obtained by modifying an unsaturated carboxylic acid such as methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid, etc., may be used singly or in combination of two or more kinds. material. 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. Ethylene-α. The olefin copolymer 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 melt-blown layer is provided on both surfaces of the direct-blowed multi-layer bottle, the configuration of the two weld layers may be different from each other, and it is preferable that the thermoplastic resin having 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 fusion layer in the present invention is preferably from 5 to 200 μm, more preferably from the viewpoint of exhibiting practical welding strength while ensuring the processability of directly blow molding a multi-layer bottle. It is 10 to 150 μm, and more preferably 15 to 100 μm.

3-2. Adhesive layer

In the present invention, the direct blow molded multilayer bottle may further contain an adhesive layer in addition to the oxygen-absorbing barrier layer and the layer containing the resin (B) as a main component. In a direct blow molding multi-layer bottle, in the case where a practical interlayer adhesion strength is not obtained between two adjacent layers (for example, an oxygen barrier layer and a fusion 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 directly blowing the multilayer bottle.

3-3. 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.

3-4. Any other layer

In the present invention, the multi-layer bottle is directly blow molded, and any layer other than the above may be further contained in accordance with the desired properties. 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.

4. Method for directly blowing a multi-layer bottle

The method for producing the direct blow molded multilayer bottle of the present invention is not particularly limited and can be produced by any method. For example, a multi-layer direct blow molding device composed of a plurality of extruders and a cylindrical mold 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. When it is not cooled, it is blown 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, a tube, or a groove.

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 multilayer 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. An electrodeposited film of an inorganic or inorganic oxide can mask dissolution of acetaldehyde or formaldehyde from a direct blown multilayer 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 adsorption of various low molecular organic compounds having a taste. 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 multilayer 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, before and after the storage of the objects to be preserved, the directly blown multilayer bottle or the preserved material may be sterilized by a form suitable for the object to be stored. 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, regarding the unit constituting the copolymer, The unit derived from m-xylylenediamine is referred to as "MXDA", and the unit derived from 1,3-bis(aminomethyl)cyclohexane is referred to as "1,3BAC", and the unit derived from hexamethylenediamine. The unit 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-A The unit of the amine acid is called "DL-Leu", and the unit of ε-caprolactam is 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".

The α-amino acid content, relative viscosity, terminal amine group concentration, glass transition temperature and melting point of the polyamide resin 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 polyamide resin was quantified using ¹ H-NMR (400 MHz, manufactured by JEOL Ltd., trade name: JNM-AL400, measurement mode: NON ( ¹ H)). Specifically, a solution of 5% by mass of a polyamide resin was prepared using formic acid-d as a solvent, and ¹ H-NMR measurement was carried out.

(2) Relative viscosity

1 g of the granular sample was finely dissolved and dissolved in 100 ml of 96% sulfuric acid at 20 to 30 ° C. 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 resin, 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 a 30mmφ twin-axis extruder with a T-die (manufactured by the Institute of Plastics Engineering) to make the cylinder of the melting point of the polyamide resin +20 °C. The T-die temperature was formed from a polyamide resin to form an unstretched single-layer film having a thickness of about 100 μm.

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.

Production Example 1 (Manufacture of Polyamide Resin 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, 13,000 g (88.96 mol) of adipic acid (made by Asahi Kasei Chemicals Co., Ltd.), 880-56 g (9.88 mol) of DL-alanine (made by Musashino Chemical Research Institute Co., Ltd.), and 11.7 g of sodium hypophosphite. (0.11 mol) and sodium acetate 6.06 g (0.074 mol), and after sufficiently replacing with nitrogen, the inside of the reaction container was sealed, and the inside of the container was kept at 0.4 MPa, and the temperature was raised to 170 ° C under stirring. After reaching 170 ° C, 12082.2 g (88.71 mol) of m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which was 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 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 (polyamide resin 1).

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

Manufacturing Example 2 (Manufacture of Polyamide 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).

Manufacturing Example 3 (Manufacture of Polyamide Resin 3)

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 = 41.1:41.3:17.6 (mol%). /DL-Ala copolymer (polyamide resin 3).

Manufacturing 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)

Replace α-amino acid with DL-leucine (Ningbo Haishuo Bio-technology), and the addition ratio of each monomer was set to m-xylylenediamine: adipic acid: DL-leucine = 44.3: 44.6: 11.1 (mol%), and other examples. 1 was carried out in the same manner to obtain an MXDA/AA/DL-Leu copolymer (polyamide resin 5).

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)

The diamine component is replaced by a mixture of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and m-xylylenediamine, and the addition ratio of each monomer is set to Meta-xylene diamine: 1,3-bis(aminomethyl)cyclohexane: adipic acid: DL-alanine = In the same manner as in Production Example 1, except that 33.2:11.1:44.6:11.1 (mol%), MXDA/1,3BAC/AA/DL-Ala copolymer (polyamide resin 8) was obtained.

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).

Table 1 shows the monomer composition of the polyamine resin 1 to 10, 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 20 and Comparative Examples 1 to 12, a direct blown multilayer bottle was produced using the above polyamine resins 1 to 10.

Example 1

Extrusion of polyamine resin at 250 ° C from the first extruder using a multi-layer direct blow molding device equipped with 3 extruders, cylinder molds, and molds. Extrusion at 230 ° C from the second extruder Polypropylene (made by Japan Polypropylene Co., Ltd., trade name: Novatec, grade: FY6), extruded adhesive resin at 220 ° C from the third extruder (Mitsui Chemical Co., Ltd., trade name: Admer, grade) :QB515), blow molding in a mold, manufacturing a layer of polypropylene/adhesive resin layer/polyamide resin layer/adhesive tree from the outer layer Three layers of a five-layer structure of a grease layer/polypropylene layer having a capacity of 200 cc. Further, the thickness of each layer was set to 300/10/60/10/300 (μm).

Example 2~9

As described in Table 2, a direct blown multilayer bottle was produced in the same manner as in Example 1 except that the polyamide resin 2 was replaced with the polyimide resin 2 to 9.

Example 10~20

A direct blow molded multilayer bottle was produced in the same manner as in Example 1 except that the polyamine resin and the layer constitution described in Table 2 were replaced.

Further, in Examples 18 to 20, PET was manufactured by Toyobo Co., Ltd., trade name: IP560, and adhesive resin was manufactured by Mitsubishi Chemical Corporation, trade names: MODIC-AP and F534A.

Comparative Example 1~12

As shown in Table 2, a direct blown multilayer bottle was produced in the same manner as in Example 1 except that the polyamide resin resin 10 was used in place of the polyamide resin 1 and the layered structure described in Table 2 was used. .

Further, in Comparative Examples 2, 5, 8, and 11, cobalt (II) stearate was added so that the cobalt content was 400 ppm with respect to the polyamide resin 10.

Further, in Comparative Examples 3, 6, 9, and 12, cobalt (II) stearate was added to make the cobalt content 100 ppm with respect to the polyamide resin 10, and further, maleic acid-modified polybutadiene (Nippon Oil) was added. Chemically, the product name: M-2000-20) is contained in an amount of 3 parts by mass based on 100 parts by mass of the polyamide resin.

Further, in Comparative Examples 10 to 12, PET was manufactured by Toyobo Co., Ltd., trade name: IP560, and adhesive resin was manufactured by Mitsubishi Chemical Corporation, trade names: MODIC-AP and F534A.

For the direct blow molding multilayer bottles prepared in Examples 1 to 20 and Comparative Examples 1 to 12, the oxygen permeability, the residual rate of L-ascorbic acid, and the odor after opening were evaluated in the following manner. taste.

(1) Oxygen permeability

Oxygen permeability of direct blow molded multi-layer bottles, using oxygen permeability measuring device (MOCON Company system, type: OX-TRAN2/61), according to ASTM D3985. In Examples 1 to 17 and Comparative Examples 1 to 9, an autoclave (SR-240, trade name, manufactured by Tomy Seiko Co., Ltd.) was used for boiling at 90 ° C for 30 minutes. On the other hand, in Examples 18 to 20 and Comparative Examples 10 to 12, 150 cc of hot water at 85 ° C was first injected, and then left at room temperature for 10 minutes, after which the entire amount of water was discarded. Thereafter, 20 ml of distilled water was filled from the opening of the directly blown multilayer bottle, and the aluminum foil laminated film was heat-sealed to seal the opening. A hole was formed in the aluminum foil laminated film, and a copper tube was inserted, fixed with an epoxy resin, and then connected to an oxygen permeability measuring device, and measured under a gas atmosphere of a relative humidity of 60% at 23 °C.

(2) L-ascorbic acid residual rate

100 ml of a 10% aqueous solution of L-ascorbic acid was filled from the opening of the directly blown multilayer bottle, and the opening was sealed by heat sealing with an aluminum foil laminated film. In the examples 1 to 17 and the comparative examples 1 to 9, the autoclave (SR-240, trade name, manufactured by Tomy Seiko Co., Ltd.) was used for 121 minutes at 121 ° C for 30 minutes, and the container was heated at 23 ° C. Store in a 50% RH environment for 1 month. Further, Examples 18 to 20 and Comparative Examples 10 to 12 were not subjected to heat treatment, and were stored in an environment of 23 ° C and 50% RH for 3 months, and then the content liquid was taken out, and 10 ml of the content liquid was placed in a 100 ml-capacity high beaker. Next, 5 ml of a mixed aqueous solution of metaphosphoric acid and acetic acid and 40 ml of distilled water were added. 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.

(3) smell and taste when opening

The obtained directly blown multi-layer bottle is filled with mineral water, sealed and sealed, and stored in a thermostat at 50 ° C for 50 ° C for 1 month. After storage, the five panelists sniffed the smell in 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 taste of the mineral water changed.

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

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

Table 2 shows the results of the evaluation.

D: not treated after heat treatment at 23 ° C for 3 months

^* (6) Determined after storage for 1 month in a thermostat at 40 ° C 50% RH

The direct blow molded multilayer bottles of Examples 1 to 20 were superior in oxygen permeability and L-ascorbic acid residual ratio as compared with Comparative Examples 1, 4, 7, and 10. In Comparative Examples 2, 5, 8, and 11 in which oxygen absorption performance was imparted by using cobalt (II) stearate, delamination occurred after boiling treatment or after hot water filling, and the barrier property was deteriorated, so that the oxygen permeability was not measured. Further, cobalt (II) stearate and maleic acid-modified polybutadiene were added to Comparative Examples 3, 6, 9, and 12 of the polyimide resin layer, and the oxygen permeability was good, but the odor at the time of opening. . Poor taste.

[Industry Utilization]

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

Claims (8)

A direct blow molding multilayer bottle comprising at least two layers of a layer (A) comprising a polyamide resin (A) and a layer (B) containing at least one resin (B) as a main component; The polyamide resin (A) contains 25 to 50 mol% of a diamine unit, and contains an aromatic diamine unit selected from the following general formula (I-1), and has the following formula (I) And the total content of at least one diamine unit in 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 mol% The above; the dicarboxylic acid unit is 25 to 50 mol%, and contains a linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) and/or an aromatic compound represented by the following general formula (II-2) The total content of the group dicarboxylic acid unit is 50% by mole or more; and the constituent unit represented by the following formula (III) is 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 multilayer 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 Aryl. A direct blow molded multilayer bottle according to claim 1 or 2, wherein the diamine unit contains 50 mol% or more of m-xylylenediamine unit. The direct blow molding multilayer 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- At least one of the group consisting of dodecanedicarboxylic acid units has a total content of 50 mol% or more. The direct blow molded multilayer 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 the naphthalene dicarboxylic acid units has a total content of 50 mol% or more. The direct blow molding multilayer bottle according to any one of claims 1 to 5, wherein the polyamide resin (A) further contains 0.1 to 49.9 of all constituent units of the polyamide resin (A). a ω-amino carboxylic acid unit represented by the following general formula (X); [In the general formula (X), p represents an integer of 2 to 18]. The direct blow molded multilayer bottle according to 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 m. %the above. The direct blow molded multilayer bottle according to any one of claims 1 to 7, wherein the polyamidamide resin (A) has a relative viscosity of 1.8 or more and 4.2 or less.