TW201307052A - Tubular container - Google Patents

Abstract

This invention provides a tubular container including a layer containing polyamide resin, where the polyamide resin (A) contains 25-50 mol% of diamine units including 50 or more mol% of a specific diamine unit, and 25-50 mol% of dicarboxylic acid units including 50 or more mol% of a specific dicarboxylic acid unit, and 0.1-50 mol% of a specific structural unit.

Description

管狀容器 Tubular container

本發明係關於具有氧阻隔性能及吸氧性能之管狀容器。 The present invention relates to a tubular container having oxygen barrier properties and oxygen absorbing properties.

管狀容器使用於保存食品或醫藥品、化粧品、牙膏等衛生材料、黏著劑等化學品等多樣的物品，也可見多數形成容器之材料之構成或容器之形狀、製造方法等。該等管狀容器，為了防止內容物變質，尤其由於氧而變質，以往係使用疊層有鋁箔作為氣體阻隔層的容器。鋁箔作為能完成阻斷氧等氣體之穿透的材料為優異者，尤其已利用在醫藥品等的容器。 The tubular container is used for storing various items such as foods, chemicals such as cosmetics, toothpaste, and the like, and chemicals such as adhesives, and the like, the configuration of the material forming the container, the shape of the container, the manufacturing method, and the like. In order to prevent the deterioration of the contents, in particular, due to oxygen, the tubular containers have conventionally used a container in which an aluminum foil is laminated as a gas barrier layer. Aluminum foil is excellent as a material capable of blocking the penetration of a gas such as oxygen, and is particularly used in containers such as pharmaceuticals.

但是疊層鋁箔而得之管狀容器，於使用後的資源回收時，將疊層樹脂與鋁箔分別回收顯然為困難，且於焚燒廢棄時，會有鋁箔的灰狀殘渣造成廢棄物處理困難等問題。就解決如此的問題的手段而言，已有許多提案：將鋁箔替換為如乙烯-乙烯醇共聚物(以下有時簡稱為EVOH)或聚間亞二甲苯己二醯胺(以下有時簡稱為N-MXD6)之類的氣體阻隔性優異的熱塑性樹脂，或替換為蒸鍍有氧化鋁或氧化矽等無機氧化物之樹脂膜而成的管狀容器。 However, in the case of a tubular container obtained by laminating an aluminum foil, it is difficult to recover the laminated resin and the aluminum foil separately after the use of the resource after use, and when the incineration is discarded, there is a problem that the waste of the aluminum foil is difficult to be disposed of. . As for the means for solving such a problem, there have been many proposals for replacing an aluminum foil with, for example, an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) or polymethylene xylene hexamethylenediamine (hereinafter sometimes referred to simply as A thermoplastic resin having excellent gas barrier properties such as N-MXD6) or a tubular container obtained by vapor-depositing a resin film of an inorganic oxide such as alumina or cerium oxide.

然而，疊層有無機氧化物蒸鍍膜的容器，由於無機氧化物為玻璃質且非可撓性之薄膜，為顯然欠缺柔軟性的薄膜，因此，例如若從外部有熱或壓力等作用，會容易發生龜裂等，有氣體阻隔性大幅下降的問題。疊層有氣體阻隔性樹脂的容器雖有幾乎不會上述問題的特徵，但其氣體阻隔性能並非完美，有時會由於溫度或濕度改變而有其性能惡化的情形，雖可延長保存期間，但無法避免由於內容物氧化而造成劣化，並非能令人滿意者。 However, in a container in which an inorganic oxide deposited film is laminated, since the inorganic oxide is a glassy and non-flexible film, it is a film which is obviously lacking in flexibility, and therefore, for example, if there is heat or pressure from the outside, It is prone to cracking, etc., and there is a problem that the gas barrier property is drastically lowered. A container in which a gas barrier resin is laminated has a characteristic that the above problem is hardly obtained, but the gas barrier property is not perfect, and the performance may be deteriorated due to a change in temperature or humidity, and the storage period may be extended, but the storage period may be extended. It is unavoidable that deterioration due to oxidation of the contents is unsatisfactory.

就解決氣體阻隔性熱塑性樹脂之缺點的方法而言，近年來有人提出以下方法：設置吸氧性樹脂層作為構成管狀容器之其中一層之方法、或設置於疊層作為氣體阻隔性樹脂層或中間層之其他熱塑性樹脂層中混合吸氧性化合物而得之層之方法。例如：專利文獻1及2揭示由聚烯烴、EVOH、含過渡金屬之氧化觸媒構成之樹脂組成物及包裝材料。專利文獻3、4中，揭示疊層有以共軛二烯聚合物環化物及EVOH作為有效成分的吸氧性氣體阻隔-樹脂層的吸氧性多層管。又，專利文獻5中揭示：將由N-MXD6、低彈性係數聚醯胺、含過渡金屬等之金屬觸媒化合物構成之吸氧性聚醯胺作為氧阻隔層而疊層之多層管。再者，專利文獻6揭示：疊層有將以鐵粉作為主劑之吸氧劑分散於熱塑性樹脂而得之吸氧層的脫氧性多層管。 In order to solve the disadvantages of the gas barrier thermoplastic resin, in recent years, there has been proposed a method of providing an oxygen-absorbing resin layer as a method of forming one of the tubular containers, or providing the laminate as a gas barrier resin layer or in the middle. A method of mixing a layer obtained by mixing an oxygen-absorbing compound with another thermoplastic resin layer of a layer. For example, Patent Documents 1 and 2 disclose a resin composition composed of polyolefin, EVOH, and a transition metal-containing oxidation catalyst, and a packaging material. In Patent Documents 3 and 4, an oxygen-absorbing multilayer tube in which an oxygen-absorbing gas barrier-resin layer containing a conjugated diene polymer cyclized product and EVOH as an active component is laminated is disclosed. Further, Patent Document 5 discloses a multilayered tube in which an oxygen-absorbing polyamine which is composed of a N-MXD6, a low modulus of elasticity polyamine or a metal catalyst compound containing a transition metal or the like is used as an oxygen barrier layer. Further, Patent Document 6 discloses a deoxidizing multilayered tube in which an oxygen absorbing layer obtained by dispersing an oxygen absorbing agent containing iron powder as a main component in a thermoplastic resin is laminated.

先前技術文獻 Prior technical literature

專利文獻 Patent literature

專利文獻1：日本特開平05-156095號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 05-156095

專利文獻2：日本特開平05-170980號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 05-170980

專利文獻3：日本特開2006-335359號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-335359

專利文獻4：日本特開2006-335360號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2006-335360

專利文獻5：日本特開2004-181629號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2004-181629

專利文獻6：日本特開2002-103490號公報 Patent Document 6: JP-A-2002-103490

利用專利文獻1~4所示之樹脂組成物的管狀容器，具有阻隔氧從管狀容器外部穿透到內部的性能(氧阻隔性)，且也具有吸收在管狀容器內之頂部空間之殘存氧或溶解於內容物中之溶存氧的性能(吸氧性能)，所以抑制內容物之氧化劣化之效果優異。但是，於任 一發明均為在發揮吸氧性能的過程中，聚烯烴或共軛二烯聚合物環化物之氧化劣化會由於觸媒而劇烈進行，而產生醛或酮等成為異味的原因的低分子量有機物質。該等由於具有穿過疊層作為內層之熱塑性樹脂的性質，所以會混入容器內部之頂部空間，或視情形溶解於內容物中，而有損害內容物之風味的問題。 The tubular container using the resin composition shown in Patent Documents 1 to 4 has a property of blocking oxygen from penetrating into the interior of the tubular container (oxygen barrier property), and also has residual oxygen absorbed in the head space in the tubular container or Since the performance of dissolved oxygen (oxygen absorbing property) dissolved in the content is excellent, the effect of suppressing oxidative degradation of the content is excellent. However, Yu Ren In the invention, in the process of exerting oxygen absorbing performance, the oxidative degradation of the cyclized product of the polyolefin or the conjugated diene polymer is vigorously carried out by the catalyst, and a low molecular weight organic substance which causes odor such as aldehyde or ketone is generated. . These have the property of being a thermoplastic resin that passes through the laminate as an inner layer, so they are mixed into the head space inside the container, or dissolved in the contents as the case may be, and there is a problem of impairing the flavor of the contents.

專利文獻5揭示之多層管，亦與上述專利文獻1~4同樣係利用構成容器之熱塑性樹脂之氧化劣化而展現吸氧性能，但是N-MXD6之氧化比起上述，有異味物質之產生較少的特徵。但是，由於利用作為構造材之N-MXD6氧化劣化，故若長期利用前述多層管，隨著吸氧進行，含N-MXD6之層之強度下降會進行，該層容易發生龜裂，有氧阻隔性下降之虞。又，管狀容器，為了擠壓內容物常會以手等施加壓力，但於如此的情形，強度已下降的含有N-MXD6之層會有受破壞而產生層間剝離，造成容器之外觀惡化之虞。由於如此的顧慮，專利文獻5揭示之多層管利用於作為長期保存用容器有其限制。 In the same manner as in the above-mentioned Patent Documents 1 to 4, the multilayered tube disclosed in Patent Document 5 exhibits oxygen absorbing performance by oxidative degradation of the thermoplastic resin constituting the container, but the oxidation of N-MXD6 is less than that of the above-mentioned odorous substance. Characteristics. However, since N-MXD6 as a structural material is oxidatively degraded, if the multilayered tube is used for a long period of time, the strength of the layer containing N-MXD6 is lowered as oxygen is absorbed, and the layer is prone to cracking and aerobic barrier. The decline in sexuality. Further, in the tubular container, pressure is often applied by hand or the like in order to press the contents, but in such a case, the layer containing N-MXD6 whose strength has been lowered may be damaged to cause delamination between the layers, resulting in deterioration of the appearance of the container. Due to such a concern, the multilayered tube disclosed in Patent Document 5 is used as a container for long-term storage.

專利文獻6揭示之脫氧性多層管由於不會伴隨熱塑性樹脂之氧化劣化，所以無產生酮或醛、熱塑性樹脂層之劣化的問題，且主劑鐵粉之吸氧能力高，所以為可以與疊層有鋁箔之容器發揮同等之內容物保存性者。但是吸氧層以外必需另外設置阻隔層，所以會比起往增加使用的材料，經濟性不佳。又，由於係以金屬粉作為吸氧劑，視內容物會有其金屬味移到內容物而損及風味的問題。而且，由於在吸氧層混有多量鐵粉，故使用其之容器無透明性，其利用範圍有限制。 Since the deoxidizing multilayer tube disclosed in Patent Document 6 does not suffer from oxidative degradation of the thermoplastic resin, there is no problem of deterioration of the ketone or aldehyde or the thermoplastic resin layer, and the main agent iron powder has high oxygen absorption ability, so that it can be stacked with A container having an aluminum foil layer has the same content preservation property. However, it is necessary to additionally provide a barrier layer in addition to the oxygen absorbing layer, so that it is less economical than the materials used in the past. Further, since metal powder is used as an oxygen absorbing agent, depending on the content, the metallic taste may be shifted to the content to impair the flavor. Further, since a large amount of iron powder is mixed in the oxygen absorbing layer, the container used therein has no transparency, and its use range is limited.

本發明欲解決之課題在於提供能抑制內容物之氧化劣化的管狀容器，其係無損內容物之風味，即使長期保存也能展現吸氧性能之層之強度不下降之管狀容器。 An object of the present invention is to provide a tubular container capable of suppressing oxidative degradation of a content, which is a tubular container which does not detract from the flavor of the contents and which exhibits an insufficient oxygen-absorbing property even if it is stored for a long period of time.

本發明提供以下的管狀容器。 The present invention provides the following tubular containers.

一種管狀容器，其係包含含有聚醯胺樹脂之層；該聚醯胺樹脂包含：二胺單元25~50莫耳%，其中，含有選自於由以下列通式(I-1)表示之芳香族二胺單元、以下列通式(I-2)表示之脂環族二胺單元、及以下列通式(I-3)表示之直鏈脂肪族二胺單元構成之群組中之至少1種二胺單元總計含量為50莫耳%以上；二羧酸單元25~50莫耳%，其中，含有以下列通式(II-1)表示之直鏈脂肪族二羧酸單元及/或以下列通式(II-2)表示之芳香族二羧酸單元總計含量為50莫耳%以上；及以下列通式(III)表示之構成單元0.1~50莫耳%； A tubular container comprising a layer containing a polyamide resin; the polyamide resin comprising: 25 to 50 mol% of a diamine unit, wherein the content of the polyamine resin is selected from the group consisting of the following formula (I-1) At least one of the group consisting of an aromatic diamine unit, an alicyclic diamine unit represented by the following formula (I-2), and a linear aliphatic diamine unit represented by the following formula (I-3) a diamine unit having a total content of 50 mol% or more; a dicarboxylic acid unit of 25 to 50 mol%, wherein the linear dicarboxylic acid unit represented by the following formula (II-1) and/or The total content of the aromatic dicarboxylic acid unit represented by the following formula (II-2) is 50 mol% or more; and the constituent unit represented by the following general formula (III) is 0.1 to 50 mol%;

[該通式(I-3)中，m表示2~18之整數；該通式(II-1)中，n表示2~18之整數；該通式(II-2)中，Ar表示伸芳基；該通式(III)中，R表示取代或無取代之烷基或取代或無取代之芳基]。 [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].

本發明之管狀容器可展現氧阻隔性能，且能不含過渡金屬而展現吸氧性能，且伴隨吸氧進行之吸氧阻隔層之強度下降極小。因此內容物之氧化劣化之抑制性優異，且幾乎不發生成為異味或風味變化之原因的物質，風味保持性亦優異。又，即使長期利用，也能維持吸氧阻隔層的強度，所以不易招致龜裂或外觀惡化。 The tubular container of the present invention exhibits oxygen barrier properties and exhibits oxygen-absorbing properties without a transition metal, and the strength of the oxygen-absorbing barrier layer with oxygen absorption is extremely small. Therefore, the content is excellent in suppressing oxidative degradation, and a substance which causes odor or flavor change hardly occurs, and the flavor retaining property is also excellent. Moreover, even if it is used for a long period of time, the strength of the oxygen-absorbing barrier layer can be maintained, so that it is less likely to cause cracking or deterioration of appearance.

[實施發明之形態] [Formation of the Invention]

本發明之管狀容器至少包含含有聚醯胺樹脂之層(以下有時稱為「吸氧阻隔層」)。本發明之管狀容器，視需要也可更含有熔接層或黏著層等任意層而製成多層構造。藉由成為多層構造，可改善容器之加工性或物性，能提高容器之操作性或創意性。 The tubular container of the present invention contains at least a layer containing a polyamide resin (hereinafter sometimes referred to as an "oxygen barrier layer"). The tubular container of the present invention may further comprise any layer such as a weld layer or an adhesive layer to form a multilayer structure. By being a multilayer structure, the processability or physical properties of the container can be improved, and the operability or creativity of the container can be improved.

1.含有聚醯胺樹脂之層(吸氧阻隔層) 1. Layer containing polyamine resin (oxygen barrier layer)

本發明中，吸氧阻隔層可藉由含有後述特定聚醯胺樹脂(以下有時稱為「聚醯胺樹脂(A)」)而發揮吸氧性能及氧阻隔性能。吸氧阻隔層所含有之聚醯胺樹脂(A)可為1種，也可為2種以上的組合。 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 sometimes referred to as "polyamine resin (A)"). 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.

本發明中，吸氧阻隔層係含有聚醯胺樹脂(A)作為主要樹脂成分。吸氧阻隔層中，也可添加聚醯胺樹脂(A)以外的樹脂，但宜為聚醯胺樹脂(A)佔吸氧阻隔層的所有樹脂中之比率超過95質量%較佳。吸氧阻隔層所含之樹脂可僅有聚醯胺樹脂(A)，且聚醯胺樹脂(A)佔吸氧阻隔層的所有樹脂中之比率宜為100質量%以下為較佳。 In the present invention, the oxygen-absorbing barrier layer contains a polyamide resin (A) as a main resin component. In the oxygen-absorbing barrier layer, a resin other than the polyamide resin (A) may be added, but it is preferred that the ratio of the polyamine resin (A) to all the resins of the oxygen-absorbing barrier layer is 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.

如上述，吸氧阻隔層中也可添加聚醯胺樹脂(A)以外的樹脂，該添加樹脂可在不妨礙本發明目的之範圍，因應欲對於吸氧阻隔層賦予之性能等而使用以往公知的各種樹脂。例如：從賦予耐衝撃性、耐針孔性、柔軟性的觀點，可舉例如：聚乙烯或聚丙烯等聚烯烴或此等的各種改性物、聚烯烴系彈性體、聚醯胺系彈性體、苯乙烯-丁二烯共聚合樹脂或其氫化處理物、聚酯系彈性體等所代表之各種熱塑性彈性體、尼龍6、66、12、尼龍12等各種聚醯胺等，從進一步賦予吸氧性能之觀點，可列舉聚丁二烯或改性聚丁二烯等含碳-碳不飽和雙鍵的樹脂。添加樹脂可為1種，也可為2種以上的組合。添加樹脂佔吸氧阻隔層的所有樹脂中之比率為5質量%以下較佳。 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.

吸氧阻隔層，除了含有聚醯胺樹脂(A)以外，也可視所望之性能等而含有後述添加劑(以下有時稱為“添加劑(B)”)，但是吸氧阻隔層中之聚醯胺樹脂(A)之含量，從成型加工性或吸氧性能、氧阻隔 性能之觀點，為90質量%~100質量%較佳，95質量%~100質量%更佳。 In addition to the polyamine resin (A), the oxygen-absorbing barrier layer may contain additives described later (hereinafter sometimes referred to as "additive (B)") depending on the desired performance, etc., but the polyamine in the oxygen-absorbing barrier layer. Resin (A) content, from molding processability or oxygen absorption performance, oxygen barrier From the viewpoint of performance, it is preferably from 90% by mass to 100% by mass, more preferably from 95% by mass to 100% by mass.

吸氧阻隔層的厚度，從提高吸氧性能及氧阻隔性能且同時確保對於管狀容器要求之柔軟性等各種物性的觀點，宜為2~100μm較佳，更佳為5~90μm，又更佳為10~80μm。 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 various physical properties such as flexibility required for the tubular container. It is 10~80μm.

1-1.聚醯胺樹脂(A) 1-1. Polyamide resin (A)

<聚醯胺樹脂(A)之構成> <Composition of Polyamine Resin (A)>

本發明中，聚醯胺樹脂(A)包含：二胺單元25~50莫耳%，其中，選自於以下列通式(I-1)表示之芳香族二胺單元、以下列通式(I-2)表示之脂環族二胺單元、及以下列通式(I-3)表示之直鏈脂肪族二胺單元構成之群組中之至少1種之二胺單元之總計含量為50莫耳%以上；二羧酸單元25~50莫耳%，其中，以下列通式(II-1)表示之直鏈脂肪族二羧酸單元及/或以下列通式(II-2)表示之芳香族二羧酸單元之總計含量為50莫耳%以上；及含3級氫之羧酸單元(較佳為下列通式(III)表示之構成單元)0.1~50莫耳%。 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 5% by mole; a dicarboxylic acid unit of 25 to 50 mol%, wherein the linear aliphatic dicarboxylic acid unit represented by the following formula (II-1) and/or represented by the following formula (II-2) The total content of the aromatic dicarboxylic acid unit is 50% by mole or more; and the carboxylic acid unit containing a tertiary hydrogen (preferably, the constituent unit represented by the following formula (III)) is 0.1 to 50 mol%.

[前述通式(I-3)中，m表示2~18之整數。前述通式(II-1)中，n表示2~18之整數。前述通式(II-2)中，Ar表示伸芳基。前述通式(III) 中，R表示經取代或未經取代之烷基或經取代或未經取代之芳基。] [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. The above formula (III) Wherein R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ]

惟前述二胺單元、前述二羧酸單元、前述含3級氫之羧酸單元之合計量不超過100莫耳%。聚醯胺樹脂(A)，在不妨礙本發明效果之範圍，也可更含有前述以外之構成單元。 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.

聚醯胺樹脂(A)中，含3級氫之羧酸單元之含量為0.1~50莫耳%。含3級氫之羧酸單元之含量低於0.1莫耳%時，無法展現充分的吸氧性能。另一方面，含3級氫之羧酸單元之含量若超過50莫耳%，3級氫含量過多，所以聚醯胺樹脂(A)之氣體阻隔性或機械物性等物性下降，尤其含3級氫之羧酸為胺基酸的情形，由於胜肽鍵連續，所以不僅耐熱性不足，且會出現由胺基酸之二聚體構成的環狀物，妨礙聚合。含3級氫之羧酸單元之含量，從吸氧性能或聚醯胺樹脂(A)之性狀之觀點，較佳為0.2莫耳%以上，更佳為1莫耳%以上，又較佳為40莫耳%以下，更佳為30莫耳%以下。 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.

聚醯胺樹脂(A)中，二胺單元之含量為25~50莫耳%，從吸氧性能或聚合物性狀之觀點，較佳為30~50莫耳%。同樣，聚醯胺樹脂(A)中，二羧酸單元之含量為25~50莫耳%，較佳為30~50莫耳%。 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%.

二胺單元與二羧酸單元之含量之比例，從聚合反應之觀點，大致為同量較佳，二羧酸單元之含量為二胺單元之含量之±2莫耳%更佳。二羧酸單元之含量若超過二胺單元之含量之±2莫耳%之範圍，聚醯胺樹脂(A)之聚合度不易提高，所以為了提高聚合度需要花費許多時間，容易產生熱劣化。 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.

[二胺單元] [diamine unit]

聚醯胺樹脂(A)中之二胺單元，其中包含選自於由前述通式(I-1)表示之芳香族二胺單元、前述通式(I-2)表示之脂環族二胺單元、及前述通式(I-3)表示之直鏈脂肪族二胺單元構成的群組中之至少1種二胺單元之總計含量為50莫耳%以上之二胺單元，該含量較佳為70 莫耳%以上，更佳為80莫耳%以上，又更佳為90莫耳%以上，又，較佳為100莫耳%以下。 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 For 70 The molar percentage is more than 80%, more preferably 80% by mole or more, still more preferably 90% by mole or more, and more preferably 100% by mole or less.

能構成前述通式(I-1)表示之芳香族二胺單元之化合物，可列舉鄰亞二甲苯二胺、間亞二甲苯二胺、及對亞二甲苯二胺。此等可以單獨使用，也可組合2種以上使用。 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.

能構成前述式(I-2)表示之脂環族二胺單元之化合物，可列舉1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷等雙(胺基甲基)環己烷類。該等可以單獨使用也可組合2種以上使用。 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.

雙(胺基甲基)環己烷類具有結構異構物，藉由提高順式體比率，結晶性高，可獲得良好成型性。另一方面，若順式體比率低，結晶性低，可獲得透明者。因此欲提高結晶性的情形，宜定雙(胺基甲基)環己烷類中之順式體含有比率為70莫耳%以上較佳，更佳為80莫耳%以上，又更佳為90莫耳%以上。另一方面，欲使結晶性低的情形，定雙(胺基甲基)環己烷類之順式體含有比率為50莫耳%以下較佳，更佳為40莫耳%以下，又更佳為30莫耳%以下。 The bis(aminomethyl)cyclohexane has a structural isomer, and by increasing the cis isomer ratio, the crystallinity is high, and good moldability can be obtained. On the other hand, if the cis isomer ratio is low, the crystallinity is low, and a transparent one can be obtained. Therefore, in order to increase the crystallinity, the cis isomer content ratio in the bis(aminomethyl)cyclohexane group is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90% or more. On the other hand, in the case where the crystallinity is low, the cis isomer content ratio of the bis(aminomethyl)cyclohexane is preferably 50 mol% or less, more preferably 40 mol% or less, and still more. Good for 30% or less.

前述通式(I-3)中，m表示2~18之整數，較佳為3~16，更佳為4~14，又更佳為6~12。 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.

能構成前述通式(I-3)表示之直鏈脂肪族二胺單元之化合物，可列舉乙二胺、1,3-丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、七亞甲基二胺、八亞甲基二胺、九亞甲基二胺、十亞甲基二胺、十一亞甲基二胺、十二亞甲基二胺等脂肪族二胺，但不限於該等。該等之中，六亞甲基二胺為較佳。該等可以單獨使用也可組合2種以上使用。 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.

聚醯胺樹脂(A)中之二胺單元，除了賦予聚醯胺樹脂(A)優異之氣體阻隔性以外，從透明性或色調之提升，或使泛用的熱塑性樹脂 容易成型之觀點，宜含有前述通式(I-1)表示之芳香族二胺單元及/或前述通式(I-2)表示之脂環族二胺單元較佳，從對於聚醯胺樹脂(A)賦予適度結晶性之觀點，含有前述通式(I-3)表示之直鏈脂肪族二胺單元較佳。尤其，從吸氧性能或聚醯胺樹脂(A)之性狀之觀點，含有前述通式(I-1)表示之芳香族二胺單元較佳。 The diamine unit in the polyamide resin (A), in addition to imparting excellent gas barrier properties to the polyamide resin (A), enhances transparency or color tone, or makes a general-purpose thermoplastic resin From the viewpoint of easy molding, it is preferred 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), preferably from the polyamine resin. (A) From the viewpoint of imparting moderate crystallinity, it is preferred to contain a linear aliphatic diamine unit represented by the above formula (I-3). 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).

聚醯胺樹脂(A)中之二胺單元，除了使聚醯胺樹脂(A)展現優異的氣體阻隔性以外，從使泛用的熱塑性樹脂容易成型的觀點，含有間亞二甲苯二胺單元50莫耳%以上較佳，該含量較佳為70莫耳%以上，更佳為80莫耳%以上，又更佳為90莫耳%以上，且較佳為100莫耳%以下。 The diamine unit in the polyamide resin (A) contains a metaxylenediamine unit from the viewpoint of easily molding 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.

能構成前述通式(I-1)~(I-3)中任一項表示之二胺單元以外之二胺單元之化合物，可列舉對苯二胺等芳香族二胺、1,3-二胺基環己烷、1,4-二胺基環己烷等脂環族二胺、N-甲基乙二胺、2-甲基-1,5-戊二胺、1-胺基-3-胺基甲基-3,5,5-三甲基環己烷等脂肪族二胺、Huntsman公司製Jeffamine或Elastamine(均為商品名)所代表之具有醚鍵的聚醚系二胺等，但不限於該等。該等可以單獨使用也可組合2種以上使用。 Examples of the compound which can constitute a diamine unit other than the diamine unit represented by any one of the above formulas (I-1) to (I-3) include aromatic diamines such as p-phenylenediamine and 1,3-two. An alicyclic diamine such as aminocyclohexane or 1,4-diaminocyclohexane, N-methylethylenediamine, 2-methyl-1,5-pentanediamine, 1-amino-3 - an aliphatic diamine such as aminomethyl-3,5,5-trimethylcyclohexane, a polyether-based diamine having an ether bond represented by Jeffamine or Elastamine (all trade name) manufactured by Huntsman Co., Ltd., But not limited to these. These may be used alone or in combination of two or more.

[二羧酸單元] [dicarboxylic acid unit]

聚醯胺樹脂(A)中之二羧酸單元，從聚合時之反應性、及聚醯胺樹脂(A)之結晶性及成型性之觀點，包含前述通式(II-1)表示之直鏈脂肪族二羧酸單元及/或前述通式(II-2)表示之芳香族二羧酸單元之含量，以二羧酸單元之合計量計，為50莫耳%以上，且該含量較佳為70莫耳%以上，更佳為80莫耳%以上，又更佳為90莫耳%以上，又，較佳為100莫耳%以下。 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, and the crystallinity and moldability of the polyamide resin (A). The content of the chain aliphatic dicarboxylic acid unit and/or the aromatic dicarboxylic acid unit represented by the above formula (II-2) is 50 mol% or more based on the total amount of the dicarboxylic acid units, and the content is more than Preferably, it is 70% by mole or more, more preferably 80% by mole or more, still more preferably 90% by mole or more, and more preferably 100% by mole or less.

前述通式(II-1)表示之直鏈脂肪族二羧酸單元，除了可對於聚醯 胺樹脂(A)賦予適度的玻璃轉移溫度或結晶性以外，還能賦予作為包裝材料或包裝容器必要的柔軟性之觀點為較佳。 The linear aliphatic dicarboxylic acid unit represented by the above formula (II-1), except for polyfluorene It is preferable that the amine resin (A) imparts a moderate glass transition temperature or crystallinity, and also imparts flexibility required as a packaging material or a packaging container.

前述通式(II-1)中，n表示2~18之整數，較佳為3~16，更佳為4~12，又更佳為4~8。 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.

能構成前述通式(II-1)表示之直鏈脂肪族二羧酸單元之化合物，可列舉琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、1,10-癸二羧酸、1,11-十一烷二羧酸、1,12-十二烷二羧酸等，但不限於該等。該等可以單獨使用也可組合2種以上使用。 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.

前述通式(II-1)表示之直鏈脂肪族二羧酸單元之種類，可因應用途適當決定。聚醯胺樹脂(A)中之直鏈脂肪族二羧酸單元，除了能賦予聚醯胺樹脂(A)優異之氣體阻隔性以外，從保持包裝材料或包裝容器加熱殺菌後之耐熱性之觀點，宜於直鏈脂肪族二羧酸單元中含有選自於由己二酸單元、癸二酸單元、及1,12-十二烷二羧酸單元構成之群組中至少1種合計為50莫耳%以上較佳，該含量更佳為70莫耳%以上，又更佳為80莫耳%以上，尤佳為90莫耳%以上，且較佳為100莫耳%以下。 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.

聚醯胺樹脂(A)中之直鏈脂肪族二羧酸單元，從聚醯胺樹脂(A)之氣體阻隔性及適當的玻璃轉移溫度或熔點等熱的性質的觀點，在直鏈脂肪族二羧酸單元中含有己二酸單元50莫耳%以上較佳。又，聚醯胺樹脂(A)中之直鏈脂肪族二羧酸單元，從對於聚醯胺樹脂(A)賦予適度氣體阻隔性及成型加工適性之觀點，在直鏈脂肪族二羧酸單元中宜含有癸二酸單元50莫耳%以上較佳，聚醯胺樹脂(A)使用於要求低吸水性、耐候性、耐熱性之用途的情形，宜在直鏈脂肪族二羧酸單元中含有1,12-十二烷二羧酸單元50莫耳%以上較佳。 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 molding processability 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.

前述通式(II-2)表示之芳香族二羧酸單元，除了對於聚醯胺樹脂(A)進一步賦予氣體阻隔性以外，從使包裝材料或包裝容器的成型 加工性容易之觀點，為較佳。 The aromatic dicarboxylic acid unit represented by the above formula (II-2) is formed by molding a packaging material or a packaging container in addition to further imparting gas barrier properties to the polyamide resin (A). The viewpoint of easy processability is preferred.

前述通式(II-2)中，Ar表示伸芳基。前述伸芳基較佳為碳數6~30，更佳為碳數6~15之伸芳基，例如：伸苯基、伸萘基等。 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.

能構成前述通式(II-2)表示之芳香族二羧酸單元之化合物，例如對苯二甲酸、間苯二甲酸、2,6-萘二羧酸等，但不限於該等。該等可以單獨使用也可組合2種以上使用。 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.

前述通式(II-2)表示之芳香族二羧酸單元之種類可因應用途適當決定。聚醯胺樹脂(A)中之芳香族二羧酸單元，宜含有選自於由間苯二甲酸單元、對苯二甲酸單元、及2,6-萘二羧酸單元構成之群組中之至少1種，其在芳香族二羧酸單元中以合計量為50莫耳%以上較佳，該含量更佳為70莫耳%以上，又更佳為80莫耳%以上，尤佳為90莫耳%以上，又較佳為100莫耳%以下。又，該等之中，芳香族二羧酸單元中含有間苯二甲酸及/或對苯二甲酸較佳。間苯二甲酸單元與對苯二甲酸單元之含有比(間苯二甲酸單元/對苯二甲酸單元)，不特別限制，可因應用途適當決定。例如：從適度之玻璃轉移溫度或降低結晶性之觀點，當令兩單元之合計為100時，莫耳比較佳為0/100~100/0，更佳為0/100~60/40，又更佳為0/100~40/60，再更佳為0/100~30/70。 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 viewpoint of shifting temperature or decreasing crystallinity of a moderate glass, when the total of the two units is 100, the molar ratio is preferably 0/100 to 100/0, more preferably 0/100 to 60/40, and further Good is 0/100~40/60, and even better is 0/100~30/70.

聚醯胺樹脂(A)中之二羧酸單元中，前述直鏈脂肪族二羧酸單元與前述芳香族二羧酸單元之含有比(直鏈脂肪族二羧酸單元/芳香族二羧酸單元)，不特別限制，可因應用途適當決定。例如以提高聚醯胺樹脂(A)之玻璃轉移溫度並降低聚醯胺樹脂(A)之結晶性為目的時，直鏈脂肪族二羧酸單元/芳香族二羧酸單元，當令兩單元之合計為100時，莫耳比較佳為0/100~60/40，更佳為0/100~40/60，又更佳為0/100~30/70。又，當以降低聚醯胺樹脂(A)之玻璃轉移溫度並對於聚醯胺樹脂(A)賦予柔軟性為目的時，直鏈脂肪族二羧酸單元/芳香族二羧酸單元，當令兩單元之合計為100時，莫耳比較佳 為40/60~100/0，更佳為60/40~100/0，又更佳為70/30~100/0。 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 is better. It is 40/60~100/0, more preferably 60/40~100/0, and even more preferably 70/30~100/0.

能構成前述通式(II-1)或(II-2)表示之二羧酸單元以外之二羧酸單元之化合物，可列舉草酸、丙二酸、富馬酸、馬來酸、1,3-苯二乙酸、1,4-苯二乙酸等二羧酸，但不限於該等。 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.

[含3級氫之羧酸單元] [Carboxylic acid unit containing 3-stage hydrogen]

本發明中，聚醯胺樹脂(A)中之含3級氫之羧酸單元，從聚醯胺樹脂(A)之聚合之觀點，至少各具有1個胺基及羧基，或具有2個以上的羧基。具體例可列舉下列通式(III)、(IV)或(V)中任一者表示之構成單元。 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).

[前述通式(III)~(V)中，R、R¹及R²各表示取代基，A¹~A³各表示單鍵或2價之連結基。惟不包括前述通式(IV)中A¹及A²同時為單鍵的情形] [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]

本發明中，聚醯胺樹脂(A)包含含3級氫之羧酸單元。藉由含有如此的含3級氫之羧酸單元作為共聚合成分，聚醯胺樹脂(A)即使不含過渡金屬也能發揮優異的吸氧性能。 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.

本發明中，關於具有含3級氫之羧酸單元之聚醯胺樹脂(A)顯示良好吸氧性能之機轉尚未明瞭，但推測如下。能構成含3級氫之羧酸單元之化合物，由於在同一碳原子上鍵結著電子吸引性基及電子提供性基，所以據認為會因為在其碳原子上存在之不成對電子在能 量方面受安定化之稱為推拉(Captodative)效果的現象，生成非常安定的自由基。亦即，羧基為電子吸引性基，且於其相鄰之3級氫所鍵結的碳成為缺電子(δ⁺)，所以該3級氫也成為缺電子(δ⁺)，會解離成質子並形成自由基。於存在氧及水時，據認為由於氧與該自由基反應，會顯示吸氧性能。又，據判斷愈是高濕度且高溫環境，反應性愈高。 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.

前述通式(III)~(V)中，R、R¹及R²各表示取代基。本發明中，R、R¹及R²表示之取代基，例如：鹵素原子(例如：氯原子、溴原子、碘原子)、烷基(具有1~15個，較佳為1~6個碳原子之直鏈、分支或環狀烷基，例如：甲基、乙基、正丙基、異丙基、第三丁基、正辛基、2-乙基己基、環丙基、環戊基)、烯基(具有2~10個，較佳為2~6個碳原子之直鏈、分支或環狀烯基，例如：乙烯基、烯丙基)、炔基(具有2~10個，較佳為2~6個碳原子之炔基，例如：乙炔基、炔丙基)、芳基(具有6~16個，較佳為6~10個碳原子之芳基，例如：苯基、萘基)、雜環基(藉由從5員環或6員環之芳香族或非芳香族之雜環化合物去除1個氫原子而得之具有1~12個，較佳為2~6個碳原子之一價之基，例如1-吡唑基、1-咪唑基、2-呋喃基)、氰基、羥基、硝基、烷氧基(具有1~10個，較佳為1~6個碳原子之直鏈、分支或環狀烷氧基，例如：甲氧基、乙氧基)、芳氧基(具有6~12個，較佳為6~8個碳原子之芳基氧基，例如：苯氧基)、醯基(甲醯基，具有2~10個，較佳為2~6個碳原子之烷基羰基、或具有7~12個較佳為7~9個碳原子之芳基羰基，例如：乙醯基、三甲基乙醯基、苯甲醯基)、胺基(胺基、具有1~10個，較佳為1~6個碳原子之烷胺基、具有6~12個，較佳為6~8個碳原子之苯胺基、或具有1~12個，較佳為2~6個碳原子之雜環胺基，例如：胺基、甲胺基、苯胺基)、巰基、烷基硫基(具有1~10個，較佳為1~6個碳原子之烷硫基，例如：甲硫基、乙基硫基)、芳基硫基(具有6~12個，較佳為6~8個碳原子之芳基硫基，例如：苯基硫基)、雜環硫基(具有2~10個，較佳為2~6個碳原子之雜環硫基，例如2-苯并噻唑 基硫基)、醯亞胺基(具有2~10個，較佳為4~8個碳原子之醯亞胺基，例如：N-琥珀醯亞胺基、N-鄰苯二甲醯亞胺基)等。 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 (having 6 to 12, preferably an aryloxy group of 6 to 8 carbon atoms, for example, a phenoxy group, a fluorenyl group (methanyl group, having 2 to 10, preferably 2 to 6 carbon atoms) An alkylcarbonyl group, or an arylcarbonyl group having 7 to 12, preferably 7 to 9 carbon atoms, for example, an ethyl group, a trimethylethyl group, a benzhydryl group, an amine group (an amine group, having 1 to 10, preferably an alkylamine group of 1 to 6 carbon atoms, an anilino group having 6 to 12, preferably 6 to 8 carbon atoms, or 1 to 12, preferably 2~ a heterocyclic amine group of 6 carbon atoms, for example, an amine group, a methylamino group, an anilino group, a fluorenyl group, an alkylthio group (an alkylthio group having 1 to 10, preferably 1 to 6 carbon atoms, For example: methylthio, ethylthio), arylthio (arylthio having 6 to 12, preferably 6 to 8 carbon atoms, such as phenylthio), heterocyclic thio (Heterocyclic thio group having 2 to 10, preferably 2 to 6 carbon atoms, such as 2-benzothiazolylthio), quinone imine (having 2 to 10, preferably 4 to 8) A quinone imine group of a carbon atom, for example, N-succinimide group, N-phthalimido group, and the like.

該等官能基之中具有氫原子者也可進一步經上述基取代，例如：經羥基取代之烷基(例如：羥基乙基)、經烷氧基取代之烷基(例如：甲氧基乙基)、經芳基取代之烷基(例如：苄基)、經烷基取代之芳基(例如：對甲苯基)、經烷基取代之芳氧基(例如：2-甲基苯氧基)等，但不限於該等。 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.

又，官能基進一步經取代時，上述碳數不包括進一步的取代基的碳數。例如：苄基，視為經苯基取代之碳數1之烷基，不視為經苯基取代之碳數7之烷基。針對以下的碳數的記載，若無特別指明，則做同樣解釋。 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.

前述通式(IV)及(V)中，A¹~A³各表示單鍵或2價之連結基。惟不包括前述通式(IV)中A¹及A²均為單鍵的情形。2價之連結基，例如：直鏈、分支或環狀之伸烷基(碳數1~12，較佳為碳數1~4之伸烷基，例如亞甲基、伸乙基)、伸芳烷基(碳數7~30，較佳為碳數7~13之伸芳烷基，例如亞苄基)、伸芳基(碳數6~30，較佳為碳數6~15之伸芳基，例如：伸苯基)等。該等也可再具有取代基，該取代基可列舉上述例示作為R、R¹及R²表示之取代基者的官能基。例如：經烷基取代之伸芳基(例如：亞二甲苯基)等，但不限於該等。 In the above formulae (IV) and (V), each of A ¹ to A ³ represents a single bond or a divalent linking group. However, the case where both A ¹ and A ² in the above formula (IV) are single bonds is not included. a divalent linking group, for example, a linear, branched or cyclic alkyl group (having a carbon number of 1 to 12, preferably an alkylene group having a carbon number of 1 to 4, such as a methylene group or an ethyl group), An aralkyl group (having a carbon number of 7 to 30, preferably a 7 to 13 carbon atom, such as a benzylidene group), and an aryl group (having a carbon number of 6 to 30, preferably a carbon number of 6 to 15) An aryl group, for example, a phenyl group). These may further have a substituent, and examples of the substituent include the above-described functional groups which are substituents represented by R, R ¹ and R ² . For example, an alkyl group-substituted aryl group (for example, xylylene group), etc., but is not limited thereto.

本發明中，聚醯胺樹脂(A)宜含有前述通式(III)、(IV)或(V)任一者表示之構成單元中之至少1種較佳。該等之中，從原料取得性或提高吸氧性之觀點，於α碳(相鄰於羧基之碳原子)具有3級氫之羧酸單元更佳，前述通式(III)表示之構成單元尤佳。 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.

前述通式(III)中，針對R如上述，但其中經取代或未經取代之烷基及經取代或未經取代之芳基更佳，經取代或未經取代之碳數 1~6之烷基及經取代或未經取代之碳數6~10之芳基更佳，經取代或未經取代之碳數1~4之烷基及經取代或未經取代之苯基尤佳。 In the above formula (III), R is as defined above, but wherein the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group are more preferably a substituted or unsubstituted carbon number. 1 to 6 alkyl groups and substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms and substituted or unsubstituted phenyl groups Especially good.

R的理想具體例，例如：甲基、乙基、正丙基、異丙基、正丁基、第三丁基、1-甲基丙基、2-甲基丙基、羥基甲基、1-羥基乙基、巰基甲基、甲基硫烷基(sulfanyl)乙基、苯基、萘基、苄基、4-羥基苄基等，但不限於該等。該等之中，甲基、乙基、異丙基、2-甲基丙基、及苄基更佳。 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.

能構成前述通式(III)表示之構成單元之化合物，可列舉：丙胺酸、2-胺基丁酸、纈胺酸、正纈胺酸、白胺酸、正白胺酸、第三白胺酸、異白胺酸、絲胺酸、蘇胺酸、半胱胺酸、甲硫胺酸、2-苯基甘胺酸、苯基丙胺酸、酪胺酸、組胺酸、色胺酸、脯胺酸等α-胺基酸，但不限於該等。 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.

又，能構成前述通式(IV)表示之構成單元之化合物，例如3-胺基丁酸等β-胺基酸，能構成前述通式(V)表示之構成單元之化合物，例如甲基丙二酸、甲基琥珀酸、蘋果酸、酒石酸等二羧酸，但不限於該等。 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.

該等可為D體、L體、消旋體中任一者，也可為異(allo-)體。又，該等可以單獨使用也可組合2種以上使用。 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.

該等之中，從原料取得性或吸氧性提高等觀點，於α碳具有3級氫之α-胺基酸尤佳。又，α-胺基酸之中，從供給容易度、價格低廉、聚合容易度、聚合物之黃色度(YI)低的觀點，丙胺酸最佳。丙胺酸由於分子量較低，聚醯胺樹脂(A)每1g之共聚合率高，所以聚醯胺樹脂(A)每1g之吸氧性能良好。 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.

又，能構成前述含3級氫之羧酸單元之化合物之純度，從聚合速度之延遲等對於聚合造成的影響或對於聚合物之黃色度等品質面之影響之觀點，為95%以上較佳，更佳為98.5%以上，又更佳為 99%以上。又，作為雜質而含有的硫酸離子或銨離子，宜為500ppm以下較佳，更佳為200ppm以下，又更佳為50ppm以下。 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 98.5% or more, and even better More than 99%. 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-胺基羧酸單元] [ω-amino carboxylic acid unit]

本發明中，聚醯胺樹脂(A)當聚醯胺樹脂(A)需要柔軟性等時，前述二胺單元，除了前述二羧酸單元及前述含3級氫之羧酸單元以外，也可更含有下列通式(X)表示之ω-胺基羧酸單元。 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).

[前述通式(X)中，p表示2~18之整數。] [In the above formula (X), p represents an integer of 2 to 18. ]

前述ω-胺基羧酸單元之含量，在聚醯胺樹脂(A)之全部構成單元中，較佳為0.1~49.9莫耳%，更佳為3~40莫耳%，又更佳為5~35莫耳%。惟前述二胺單元、二羧酸單元、含3級氫之羧酸單元、及ω-胺基羧酸單元之合計量不超過100莫耳%。 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%.

前述通式(X)中，p表示2~18之整數，較佳為3~16，更佳為4~14，又更佳為5~12。 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.

能構成前述通式(X)表示之ω-胺基羧酸單元之化合物，例如：碳數5~19之ω-胺基羧酸或碳數5~19之內醯胺。碳數5~19之ω-胺基羧酸，例如6-胺基己酸及12-胺基十二烷酸等，碳數5~19之內醯胺例如ε-己內醯胺及月桂內醯胺，但不限於此等。該等可以單獨使用也可組合2種以上使用。 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.

前述ω-胺基羧酸單元，在ω-胺基羧酸單元中宜含有6-胺基己酸單元及/或12-胺基十二烷酸單元合計50莫耳%以上較佳，該含量更佳為70莫耳%以上，更佳為80莫耳%以上，又更佳為90莫耳%以上， 又，較佳為100莫耳%以下。 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, and even more preferably 90 mol% or more. Further, it is preferably 100% by mole or less.

[聚醯胺樹脂(A)之聚合度] [Polymerization degree of polyamine resin (A)]

針對聚醯胺樹脂(A)之聚合度，使用相對黏度。聚醯胺樹脂(A)之理想相對黏度，從成型品之強度或外觀、成型加工性之觀點，較佳為1.8~4.2，更佳為1.9~4.0，又更佳為2.0~3.8。 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.

又，在此所指的相對黏度，係將聚醯胺樹脂(A)1g溶於96%硫酸100mL，並以Cannon-Fenske型黏度計於25℃測定之落下時間(t)、與同樣測定之96%硫酸本身的落下時間(t₀)之比，以次式表示。 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.

相對黏度=t/t₀ Relative viscosity = t / t ₀

[末端胺基濃度] [terminal amino group concentration]

聚醯胺樹脂(A)之吸氧速度、及由於吸氧造成之聚醯胺樹脂(A)之氧化劣化，可利用改變聚醯胺樹脂(A)之末端胺基濃度而控制。本發明中，從吸氧速度與氧化劣化之均衡性之觀點，聚醯胺樹脂(A)之末端胺基濃度為5~150μeq/g之範圍較佳，更佳為10~100μeq/g，又更佳為15~80μeq/g。 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.

<聚醯胺樹脂(A)之製造方法> <Method for Producing Polyamide Resin (A)>

聚醯胺樹脂(A)，可藉由將能構成前述二胺單元之二胺成分、能構成前述二羧酸單元之二羧酸成分、能構成前述含3級氫之羧酸單元之含3級氫之羧酸成分，以及視需要之能構成前述ω-胺基羧酸單元之ω-胺基羧酸成分予以縮聚而製造，可藉由調整縮聚條件等以控制聚合度。縮聚時也可添加少量單元胺或單元羧酸當作分子量調整劑。又，為了抑制縮聚反應以成為理想聚合度，構成聚醯胺樹脂(A)之二胺成分與羧酸成分之比率(莫耳比)也可調整為偏離1。 The polyamine resin (A) can be composed of a diamine component which can constitute the diamine unit, a dicarboxylic acid component which can constitute the dicarboxylic acid unit, and a carboxylic acid unit which can constitute the tertiary hydrogen-containing unit. The carboxylic acid component of the hydrogen group and, if necessary, the ω-amino carboxylic acid component constituting the ω-amino carboxylic acid unit are produced by polycondensation, and the polymerization degree can be controlled by adjusting the polycondensation conditions and the like. A small amount of a unit amine or a unit carboxylic acid may also be added as a molecular weight regulator during the polycondensation. Further, in order to suppress the polycondensation reaction to have a desired degree of polymerization, the ratio (mol ratio) of the diamine component and the carboxylic acid component constituting the polyamide resin (A) may be adjusted to be shifted by 1.

聚醯胺樹脂(A)之縮聚方法例如反應擠製法、加壓鹽法、常壓滴加法、加壓滴加法等，但不限於該等。又，反應溫度儘可能低時， 能抑制聚醯胺樹脂(A)之黃色化或凝膠化，可獲得安定性狀之聚醯胺樹脂(A)。 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. Also, 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.

[反應擠製法] [Reaction extrusion method]

反應擠製法，係將由二胺成分及二羧酸成分構成之聚醯胺(相當於聚醯胺樹脂(A)之前驅體的聚醯胺)或二胺成分、與由二羧酸成分及ω-胺基羧酸成分構成之聚醯胺(相當於聚醯胺樹脂(A)之前驅體之聚醯胺)、與含3級氫之羧酸成分，以擠製機進行熔融混練並反應之方法。係藉由將含3級氫之羧酸成分進行醯胺交換反應而導入聚醯胺之骨架中的方法，為了充分反應，宜使用適於反應擠製的螺桿，且L/D大的雙軸擠製機較佳。當製造含少量之含3級氫之羧酸單元的聚醯胺樹脂(A)的情形，為簡便的方法為理想。 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.

[加壓鹽法] [pressurized salt method]

加壓鹽法，係以尼龍鹽作為原料於加壓下進行熔融縮聚之方法。具體而言，係製備由二胺成分、二羧酸成分、含3級氫之羧酸成分、及視需要之ω-胺基羧酸成分構成的尼龍鹽水溶液後，將該水溶液濃縮，其次在加壓下升溫，邊除去縮合水邊進行縮聚。緩慢將罐內回復到常壓，且同時升溫到聚醯胺樹脂(A)之熔點+10℃左右並保持，之後再緩慢減壓到-0.02MPaG，維持此溫度繼續縮聚。於到達一定的攪拌轉矩即將罐內以氮氣加壓到約0.3MPaG，回收聚醯胺樹脂(A)。 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. 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.

加壓鹽法，於使用揮發性成分作為單體之情形有用，為含3級氫之羧酸成分之共聚合率高時的理想縮聚方法。尤其，當製造含3級氫之羧酸單元在聚醯胺樹脂(A)之全部構成單元中含量為15莫耳%以上之聚醯胺樹脂(A)時，為理想。藉由使用加壓鹽法，可防止含3級氫之羧酸成分蒸散，而且可抑制含3級氫之羧酸成分彼此縮聚，能順暢地進行縮聚反應，故能獲得性狀優異之聚醯胺樹脂(A)。 The pressurized salt method is useful when a volatile component is used as a monomer, and is an ideal polycondensation method when the copolymerization ratio of the carboxylic acid component containing a tertiary hydrogen is high. In particular, it is preferred to produce a 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).

[常壓滴加法] [Atmospheric pressure drop method]

常壓滴加法，係於常壓下於將二羧酸成分、含3級氫之羧酸成分、及視需要之ω-胺基羧酸成分予以加熱熔融而得之混合物中，連續滴加二胺成分，並邊去除縮合水邊進行縮聚。又，以使反應溫度不致低於生成之聚醯胺樹脂(A)之熔點之方式邊將反應系升溫邊進行縮聚反應。 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).

常壓滴加法，若與前述加壓鹽法相比較，由於不使用用於溶解鹽的水，所以每單位批次的產量大，且不需要將原料成分之氣化、冷凝，反應速度下降少，可縮短製程時間。 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.

[加壓滴加法] [Pressure drop method]

加壓滴加法中，首先於縮聚罐中加入二羧酸成分、含3級氫之羧酸成分、及視需要之ω-胺基羧酸成分，將各成分攪拌並熔融混合，製成混合物。其次，邊將罐內較佳加壓至約0.3~0.4MPaG邊對混合物連續滴加二胺成分，並邊去除縮合水邊進行縮聚。於此時，以使反應溫度不致低於生成之聚醯胺樹脂(A)之熔點之方式，邊將反應系升溫邊進行縮聚反應。於到達設定莫耳比即結束二胺成分之滴加，緩慢使罐內回復到常壓，同時升溫到聚醯胺樹脂(A)之熔點+10℃左右並保持後，再緩慢減壓到-0.02MPaG，同時保持該溫度繼續縮聚反應。於到達一定的攪拌轉矩即將罐內以氮氣加壓到約0.3MPaG，回收聚醯胺樹脂(A)。 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.

加壓滴加法，與加壓鹽法同樣，當使用揮發性成分作為單體之情形有用，且當含3級氫之羧酸成分之共聚合率高時，為理想的縮聚方法。尤其，當製造含3級氫之羧酸單元在聚醯胺樹脂(A)之全部構成單元中的含量為15莫耳%以上之聚醯胺樹脂(A)時為理想。藉由使用加壓滴加法，能防止含3級氫之羧酸成分蒸散，再者，能抑制含3級氫之羧酸成分彼此縮聚，能使縮聚反應順暢地進行，可獲得性狀優異之聚醯胺樹脂(A)。再者，加壓滴加法，相較於加壓鹽法，由於不使用用於溶解鹽的水，所以單位批次的產量大，與常壓 滴加法同樣可縮短反應時間，所以可抑制凝膠化等，獲得黃色度低之聚醯胺樹脂(A)。 The pressurized dropping method is useful in the case of using a volatile component as a monomer as in the case of the pressurized salt method, and is an ideal polycondensation method when the copolymerization ratio of the carboxylic acid component containing the tertiary hydrogen is high. In particular, it is preferred to produce a 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). Furthermore, the pressurized dropping method has a large yield per unit lot, compared with the pressurized salt method, since water for dissolving the salt is not used. In the same manner as the dropping method, the reaction time can be shortened, so that gelation or the like can be suppressed, and a polyamide resin (A) having a low yellowness can be obtained.

[提高聚合度之步驟] [Steps to increase the degree of polymerization]

上述縮聚方法製造之聚醯胺樹脂(A)可以直接使用，也可經過用於使聚合度更提高的步驟。使聚合度更提高的步驟，可舉例在擠製機內進行之反應擠製或固相聚合等。於固相聚合使用之加熱裝置，宜使用連續式加熱乾燥裝置或稱為轉筒式乾燥機、錐型乾燥機、旋轉乾燥機等的旋轉滾筒式加熱裝置及稱為圓錐型(Nauta)混合機的內部具有旋轉葉片的圓錐型加熱裝置，但不限於該等，可使用公知方法、裝置。尤其，進行聚醯胺樹脂(A)之固相聚合時，上述裝置之中，旋轉滾筒式之加熱裝置從能將系內密閉化且容易於去除成為著色原因之氧之狀態進行縮聚之觀點，為較佳。 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.

[含磷原子之化合物、鹼金屬化合物] [Compound containing phosphorus atom, alkali metal compound]

於聚醯胺樹脂(A)之縮聚，從促進醯胺化反應之觀點，宜添加含磷原子之化合物較佳。 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.

含磷原子之化合物，例如：二甲基次膦酸、苯基甲基次膦酸等次膦酸化合物；次亞磷酸、次亞磷酸鈉、次亞磷酸鉀、次亞磷酸鋰、次亞磷酸鎂、次亞磷酸鈣、次亞磷酸乙酯等二亞磷酸化合物；膦酸、膦酸鈉、膦酸鉀、膦酸鋰、膦酸鎂、膦酸鈣、苯基膦酸、乙基膦酸、苯基膦酸鈉、苯基膦酸鉀、苯基膦酸鋰、苯基膦酸二乙酯、乙基膦酸鈉、乙基膦酸鉀等膦酸化合物；亞膦酸、亞膦酸鈉、亞膦酸鋰、亞膦酸鉀、亞膦酸鎂、亞膦酸鈣、苯基亞膦酸、苯基亞膦酸鈉、苯基亞膦酸鉀、苯基亞膦酸鋰、苯基亞膦酸乙酯等亞膦酸化合物；亞磷酸、亞磷酸氫鈉、亞磷酸鈉、亞磷酸鋰、亞磷酸鉀、亞磷酸鎂、亞磷酸鈣、亞磷酸三乙酯、亞磷酸三苯酯、焦亞磷酸等亞磷酸化合物等。 a compound containing a phosphorus atom, for example, a phosphinic acid compound such as dimethylphosphinic acid or phenylmethylphosphinic acid; hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, hypophosphorous acid a diphosphorous acid compound such as magnesium, calcium hypophosphite or ethyl hypophosphite; phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid a phosphonic acid compound such as sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphinate, diethyl phenylphosphonate, sodium ethylphosphonate or potassium ethylphosphonate; phosphinic acid, phosphinic acid Sodium, lithium phosphinate, potassium phosphinate, magnesium phosphinate, calcium phosphinate, phenylphosphinic acid, sodium phenylphosphinate, potassium phenylphosphinate, lithium phenylphosphinate, benzene A phosphinic acid compound such as ethyl phosphinate; phosphorous acid, sodium hydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite a phosphorous acid compound such as an ester or pyrophosphoric acid.

該等之中，尤其次亞磷酸鈉、次亞磷酸鉀、次亞磷酸鋰等次亞 磷酸金屬鹽，促進醯胺化反應之效果高且著色防止效果亦優異故為較佳，尤其次亞磷酸鈉較佳。又，本發明可使用之含磷原子之化合物，不限於該等化合物。 Among these, especially sub-sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, etc. The metal phosphate salt is preferred because it has a high effect of promoting the amide amination reaction and is excellent in coloring prevention effect, and particularly sodium hypophosphite is preferred. Further, the compound containing a phosphorus atom which can be used in the present invention is not limited to these compounds.

含磷原子之化合物之添加量，以聚醯胺樹脂(A)中之磷原子濃度換算，為0.1~1000ppm較佳，更佳為1~600ppm，又更佳為5~400ppm。若為0.1ppm以上，聚醯胺樹脂(A)不易於聚合中著色，透明性會提高。若為1000ppm以下，聚醯胺樹脂(A)不易凝膠化，又，也可減少據認為是由於含磷原子之化合物引起的銀點(fisheye)混入成型品中，成型品之外觀良好。 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 the fisheye which is considered to be due to the phosphorus atom-containing compound is mixed into the molded article, and the appearance of the molded article is good.

又，聚醯胺樹脂(A)之縮聚系內，宜與含磷原子之化合物併用而添加鹼金屬化合物較佳。為了防止聚醯胺樹脂(A)在縮聚中著色，需存在足量的含磷原子之化合物，但視情形，有時會有導致聚醯胺樹脂(A)凝膠化之虞，所以為了調整醯胺化反應速度亦以共存鹼金屬化合物較佳。 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.

鹼金屬化合物宜為鹼金屬氫氧化物或鹼金屬乙酸鹽、鹼金屬碳酸鹽、鹼金屬醇鹽等為較佳。本發明可使用之鹼金屬化合物，具體例例如：氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫、乙酸鋰、乙酸鈉、乙酸鉀、乙酸銣、乙酸銫、甲醇鈉、乙醇鈉、丙醇鈉、丁醇鈉、甲醇鉀、甲醇鋰、碳酸鈉等，但不限使用該等化合物。又，含磷原子之化合物與鹼金屬化合物之比率(莫耳比)，從控制聚合速度之觀點、或減低黃色度之觀點，宜為含磷原子之化合物/鹼金屬化合物=1.0/0.05~1.0/1.5之範圍較佳，更佳為1.0/0.1~1.0/1.2，又更佳為1.0/0.2~1.0/1.1。 The alkali metal compound is preferably an alkali metal hydroxide or an alkali metal acetate, an alkali metal carbonate, an alkali metal alkoxide or the like. The alkali metal compound which can be used in the present invention, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, barium hydroxide, lithium acetate, sodium acetate, potassium acetate, barium acetate, barium acetate, sodium methoxide , sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium carbonate, etc., but are not limited to the use of such compounds. Further, the ratio of the phosphorus atom-containing compound to the alkali metal compound (mol ratio) is preferably a compound containing a phosphorus atom/alkali metal compound = 1.0/0.05 to 1.0 from the viewpoint of controlling the polymerization rate or reducing the yellowness. The range of /1.5 is better, more preferably 1.0/0.1 to 1.0/1.2, and even more preferably 1.0/0.2 to 1.0/1.1.

1-2.添加劑(B) 1-2. Additives (B)

本發明之吸氧阻隔層，除了含有前述聚醯胺樹脂(A)以外，視需要也可更含有添加劑(B)。添加劑(B)可為1種，也可組合2種以上。吸氧阻隔層中之添加劑(B)之含量，取決於添加劑之種類，但以10 質量%以下較佳、5質量%以下更佳。 The oxygen-absorbing barrier layer of the present invention may further contain an additive (B) as needed in addition to the polyamine resin (A). The additive (B) may be used alone or in combination of two or more. The content of the additive (B) in the oxygen barrier layer depends on the type of the additive, but is 10 The mass% or less is preferably 5% by mass or less.

[白化防止劑] [Alkylation inhibitor]

本發明中，宜於聚醯胺樹脂(A)添加二醯胺化合物及/或二酯化合物，以抑制熱水處理後或經過長時間後之白化。二醯胺化合物及二酯化合物，於抑制由於寡聚物析出導致的白化有效。二醯胺化合物與二酯化合物可單獨使用，也可併用。 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.

本發明可用之二醯胺化合物，宜為由碳數8~30之脂肪族二羧酸與碳數2~10之二胺獲得之二醯胺化合物較佳。脂肪族二羧酸之碳數為8以上、二胺之碳數為2以上時，可期待白化防止效果。又，脂肪族二羧酸之碳數為30以下、二胺之碳數為10以下時，於吸氧阻隔層中的均勻分散會變得良好。脂肪族二羧酸可有側鏈或雙鍵，但以直鏈飽和脂肪族二羧酸為較佳。二醯胺化合物可使用1種，也可併用2種以上。 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.

前述脂肪族二羧酸，例如：硬脂酸(C18)、二十烷酸(C20)、二十二烷酸(C22)、二十八烷酸(C28)、三十烷酸(C30)等。前述二胺例如：乙二胺、丁二胺、己二胺、亞二甲苯二胺、雙(胺基甲基)環己烷等。宜為將該等予以組合得到的二醯胺化合物較佳。 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.

從碳數8~30之脂肪族二羧酸與主要為乙二胺構成的二胺得到的二醯胺化合物、或從主要為二十八烷酸構成之脂肪族二羧酸與碳數2~10之二胺獲得之二醯胺化合物較佳，尤佳為從主要為硬脂酸構成之脂肪族二羧酸及主要為乙二胺構成之二胺獲得的二醯胺化合物。 a diammonium compound obtained from a diamine having 8 to 30 carbon atoms and a diamine mainly composed of ethylenediamine, or an aliphatic dicarboxylic acid composed mainly of octadecanoic acid and a carbon number 2~ The diamine compound obtained from the diamine of 10 is preferably a diamine compound obtained from an aliphatic dicarboxylic acid mainly composed of stearic acid and a diamine mainly composed of ethylenediamine.

本發明可使用之二酯化合物，較佳為從碳數8~30之脂肪族二羧酸與碳數2~10之二醇獲得之二酯化合物。脂肪族二羧酸之碳數為8以上、二醇之碳數為2以上時，可期待白化防止效果。又，脂肪族 二羧酸之碳數為30以下、二醇之碳數為10以下時，於吸氧阻隔層中的均勻分散良好。脂肪族二羧酸也可有側鏈或雙鍵，但直鏈飽和脂肪族二羧酸為較佳。二酯化合物可使用1種也可併用2種以上。 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. Also, aliphatic When the carbon number of the 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.

前述脂肪族二羧酸，例如硬脂酸(C18)、二十烷酸(C20)、二十二烷酸(C22)、二十八烷酸(C28)、三十烷酸(C30)等。前述二醇例如乙二醇、丙二醇、丁二醇、己二醇、亞二甲苯二醇、環己烷二甲醇等。將該等予以組合得到之二酯化合物較佳。 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.

尤佳為由主要為二十八烷酸構成之脂肪族二羧酸與主要為乙二醇及/或1,3-丁二醇構成之二醇獲得之二酯化合物。 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.

本發明中，二醯胺化合物及/或二酯化合物之添加量，在吸氧阻隔層中較佳為0.005~0.5質量%，更佳為0.05~0.5質量%，又更佳為0.12~0.5質量%。藉由在吸氧阻隔層中添加0.005質量%以上且併用結晶化核劑，能期待防止白化之協同效果。又，添加量若在吸氧阻隔層中為0.5質量%以下，能保持將本發明之聚醯胺樹脂(A)成型而得之成型體之霧度值為低值。 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 polyamine resin (A) of the present invention can be kept low.

[層狀矽酸鹽] [layered citrate]

本發明中，吸氧阻隔層也可含有層狀矽酸鹽。藉由添加層狀矽酸鹽，不僅可對於多層薄膜賦予氧氣阻隔性，也可賦予對於二氧化碳等氣體之阻隔性。 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.

層狀矽酸鹽為電荷密度0.25~0.6之2-八面體型或3-八面體型之層狀矽酸鹽，2-八面體型例如：蒙特石(montmorillonite)、鋁蒙脫石等、3-八面體型例如：鋰膨潤石、鎂膨潤石(saponite)等。該等之中，蒙特石較佳。 The layered niobate is a 2-octahedral or 3-octahedral layered niobate having a charge density of 0.25 to 0.6, and a 2-octahedral type such as montmorillonite or aluminum montmorillonite, 3 - Octahedral type, for example, lithium bentonite, magnesium saponite, and the like. Among these, Monte Rock is preferred.

層狀矽酸鹽，宜使高分子化合物或有機系化合物等有機膨潤化劑預先與層狀矽酸鹽接觸使層狀矽酸鹽之層間擴大較佳。有機膨潤 化劑，可使用四級銨鹽較佳，但更佳為使用具有碳數12以上之烷基或烯基至少其中之一以上之四級銨鹽。 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. Organic swelling As the chemical 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 a carbon number of 12 or more.

有機膨潤化劑之具體例，例如：三甲基十二基銨鹽、三甲基十四基銨鹽、三甲基十六基銨鹽、三甲基十八基銨鹽、三甲基二十基銨鹽等三甲基烷基銨鹽；三甲基十八烯基銨鹽、三甲基十八-二烯基銨鹽等三甲基烯基銨鹽；三乙基十二基銨鹽、三乙基十四基銨鹽、三乙基十六基銨鹽、三乙基十八基銨等三乙基烷基銨鹽；三丁基十二基銨鹽、三丁基十四基銨鹽、三丁基十六基銨鹽、三丁基十八基銨鹽等三丁基烷基銨鹽；二甲基二-十二基銨鹽、二甲基二-十四基銨鹽、二甲基二-十六基銨鹽、二甲基二-十八基銨鹽、二甲基二牛脂(tallow)銨鹽等二甲基二烷基銨鹽；二甲基二-十八烯基銨鹽、二甲基二-十八-二烯基銨鹽等二甲基二烯基銨鹽；二乙基二-十二基銨鹽、二乙基二-十四基銨鹽、二乙基二-十六基銨鹽、二乙基二-十八基銨等二乙基二烷基銨鹽；二丁基二-十二基銨鹽、二丁基二-十四基銨鹽、二丁基二-十六基銨鹽、二丁基二-十八基銨鹽等二丁基二烷基銨鹽；甲基苄基二-十六基銨鹽等甲基苄基二烷基銨鹽；二苄基二-十六基銨鹽等二苄基二烷基銨鹽；三-十二基甲基銨鹽、三-十四基甲基銨鹽、三-十八基甲基銨鹽等三烷基甲基銨鹽；三-十二基乙基銨鹽等三烷基乙基銨鹽；三-十二基丁基銨鹽等三烷基丁基銨鹽；4-胺基-正丁酸、6-胺基-正己酸、8-胺基辛酸、10-胺基癸酸、12-胺基十二烷酸、14-胺基十四烷酸、16-胺基十六烷酸、18-胺基十八烷酸等ω-胺基酸等。又，含羥基及/或醚基之銨鹽，其中，甲基二烷基(PAG)銨鹽、乙基二烷基(PAG)銨鹽、丁基二烷基(PAG)銨鹽、二甲基雙(PAG)銨鹽、二乙基雙(PAG)銨鹽、二丁基雙(PAG)銨鹽、甲基烷基雙(PAG)銨鹽、乙基烷基雙(PAG)銨鹽、丁基烷基雙(PAG)銨鹽、甲基三(PAG)銨鹽、乙基三(PAG)銨鹽、丁基三(PAG)銨鹽、四(PAG)銨鹽(惟烷基表示十二基、十四基、十六基、十八基、二十基等碳數12以上之烷基，且PAG表示聚伸烷基二醇殘 基，較佳為碳數20以下之聚乙二醇殘基或聚丙二醇殘基)等至少含有1個伸烷基二醇殘基之4級銨鹽，也可作為有機膨潤化劑使用。其中，三甲基十二基銨鹽、三甲基十四基銨鹽、三甲基十六基銨鹽、三甲基十八基銨鹽、二甲基二-十二基銨鹽、二甲基二-十四基銨鹽、二甲基二-十六基銨鹽、二甲基二-十八基銨鹽、二甲基二牛脂銨鹽為較佳。又，該等有機膨潤化劑，可單獨使用，也可製成多種的混合物使用。 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. Bis (PAG) ammonium salt, diethyl bis (PAG) ammonium salt, dibutyl bis (PAG) ammonium salt, methyl alkyl bis (PAG) ammonium salt, ethyl alkyl bis (PAG) ammonium salt, Butylalkyl bis(PAG) ammonium salt, methyl tris(PAG) ammonium salt, ethyl tris(PAG) ammonium salt, butyl tris(PAG) ammonium salt, tetra (PAG) ammonium salt (only alkyl group represents ten Alkyl group having 12 or more carbon atoms such as diyl, tetradecyl, hexadecyl, octadecyl and decyl, and PAG means polyalkylene glycol residue The base, preferably a polyethylene glycol residue having a carbon number of 20 or less or a polypropylene glycol residue, or the like, may contain at least one alkyl ammonium salt of an alkylene glycol residue, and may 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.

本發明中，經有機膨潤化劑處理的層狀矽酸鹽，在吸氧阻隔層中宜添加0.5~8質量%，更佳為1~6質量%，又更佳為2~5質量%。層狀矽酸鹽之添加量若為0.5質量%以上，可得到足夠的氣體阻隔性的改善效果，若為8質量%以下，不易發生由於吸氧阻隔層的柔軟性惡化造成產生針孔等問題。 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. .

吸氧阻隔層中，層狀矽酸鹽宜不是局部凝集而是均勻分散較佳。在此所指之均勻分散，係指層狀矽酸鹽在吸氧阻隔層中以平板狀分離，且此等的50%以上有5nm以上的層間距離。在此，層間距離，係指平板狀物之重心間距離。該距離愈大，分散狀態愈良好，透明性等外觀良好，且可提高氧氣、二氧化碳等氣體的阻隔性。 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.

[氧化反應促進劑] [oxidation reaction accelerator]

為了更提高吸氧阻隔層的吸氧性能，在無損本發明效果之範圍可添加以往公知的氧化反應促進劑。氧化反應促進劑，能藉由促進聚醯胺樹脂(A)具有的吸氧性能，提高吸氧阻隔層的吸氧性能。氧化反應促進劑，例如鐵、鈷、鎳等周期表第VIII族金屬、銅或銀等第I族金屬、錫、鈦、鋯等第IV族金屬、釩之第V族、鉻等第VI族、錳等第VII族之金屬之低價數的無機酸鹽或有機酸鹽、或上述過渡金屬之錯鹽。該等之中，氧反應促進效果優異之鈷鹽、或鈷鹽與錳鹽之組合為較佳。 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 promoters, such as metals such as iron, cobalt, nickel, etc., Group VIII metals, Group I metals such as copper or silver, Group IV metals such as tin, titanium, zirconium, Group V of vanadium, Group VI of chromium, etc. A low-grade inorganic or organic acid salt of a metal of Group VII such as manganese or a wrong salt of the above transition metal. Among these, a cobalt salt having an excellent oxygen reaction promoting effect or a combination of a cobalt salt and a manganese salt is preferred.

本發明中，氧反應促進劑之添加量，在吸氧阻隔層中較佳為，以金屬原子濃度計，為10~800ppm，更佳為50~600ppm，更佳為100~400ppm。 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.

[吸氧劑] [Oxygen absorber]

為了使吸氧阻隔層的吸氧性能更高，在無損本發明效果之範圍，也可添加以往公知的吸氧劑。吸氧劑，藉由在聚醯胺樹脂(A)具有之吸氧性能以外，另外對於吸氧阻隔層賦予吸氧性能，可提高吸氧阻隔層的吸氧性能。吸氧劑，例如維生素C或維生素E、丁二烯或異戊二烯之類的在分子內具有碳-碳雙鍵之化合物為代表之氧化性有機化合物。 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.

本發明中，吸氧劑之添加量，在吸氧阻隔層中較佳為0.01~5質量%，更佳為0.1~4質量%，又更佳為0.5~3質量%。 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.

[防凝膠化‧減少銀點之藥劑] [Anti-gelation ‧ reduction of silver spots]

本發明中，宜添加從乙酸鈉、乙酸鈣、乙酸鎂、硬脂酸鈣、硬脂酸鎂、硬脂酸鈉及此等的衍生物選出之1種以上之羧酸鹽類較佳。在此，該衍生物例如12-羥基硬脂酸鈣、12-羥基硬脂酸鎂、12-羥基硬脂酸鈉等12-羥基硬脂酸金屬鹽等。藉由添加前述羧酸鹽類，能防止在成型加工中發生之聚醯胺樹脂(A)之凝膠化或減少成型體中之銀點，成型加工適性提高。 In the present invention, it is preferred to add one or more kinds of carboxylate salts selected from the group consisting of sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate, and the like. 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.

前述羧酸鹽類之添加量，就吸氧阻隔層中之濃度而言，較佳為400~10000ppm，更佳為800~5000ppm，又更佳為1000~3000ppm。若為400ppm以上，可抑制聚醯胺樹脂(A)之熱劣化，防止凝膠化。又，若為10000ppm以下，聚醯胺樹脂(A)不會發生成型不良，也不會有著色或白化。若熔融的聚醯胺樹脂(A)中有為鹼性物質之羧酸鹽類存在，據推測會減慢聚醯胺樹脂(A)由於熱所致之改性，且可抑制據認為是最終改性物的凝膠生成。 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, when it is 10000 ppm or less, the polyamide resin (A) does not cause molding failure, and there is 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.

又，前述羧酸鹽類的操作性優異，其中硬脂酸金屬鹽價格低廉，且有作為潤滑劑的效果，能使成型加工更安定故為較佳。再者，羧酸鹽類的形狀不特別限制，為粉體且粒徑小者在進行乾式混合的情形，容易均勻分散在吸氧阻隔層中，故其粒徑為0.2mm以下為較佳。 Further, the carboxylate is excellent in handleability, and the stearic acid metal salt is inexpensive, and has an effect as a lubricant, and it is preferable to 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.

[抗氧化劑] [Antioxidants]

本發明中，從控制吸氧性能之觀點或抑制機械物性下降之觀點，添加抗氧化劑較佳。抗氧化劑例如銅系抗氧化劑、受阻苯酚系抗氧化劑、受阻胺系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等，其中受阻苯酚系抗氧化劑、磷系抗氧化劑為較佳。 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.

受阻苯酚系抗氧化劑之具體例，例如：三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯、4,4’-亞丁基雙(3-甲基-6-第三丁基苯酚)、1,6-己二醇-雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、2,4-雙-(正辛硫基)-6-(4-羥基-3,5-二第三丁基苯胺基)-1,3,5-三、季戊四醇-肆[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2,2-硫-二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、十八基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、2,2-硫雙(4-甲基-6-1-丁基苯酚)、N,N’-六亞甲基雙(3,5-二第三丁基-4-羥基-羥基肉桂醯胺)、3,5-二第三丁基-4-羥基-苄基膦酸酯-二乙酯、1,3,5-三甲基-2,4,6-參(3,5-二-丁基-4-羥基苄基)苯、雙(3,5-二第三丁基-4-羥基苄基磺酸乙酯鈣、參-(3,5-二第三丁基-4-羥基苄基)-異氰尿酸酯、2,6-二第三丁基-對甲酚、丁基化羥基苯甲醚、2,6-二第三丁基-4-乙基苯酚、硬脂基-β-(3,5-二第三丁基-4-羥基苯基)丙酸酯、2,2’-亞甲基雙-(4-甲基-6-第三丁基苯酚)、2,2’-亞甲基-雙-(4-乙基-6-第三丁基苯酚)、4,4’-硫雙-(3-甲基-6-第三丁基苯酚)、辛基化二苯胺、2,4-雙[(辛硫基)甲基]-O-甲酚、異辛基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、4,4’-亞丁基雙(3-甲基-6-第三丁基苯酚、3,9-雙[1,1-二甲基-2-[β-(3-第三丁基-4-羥基-5-甲基苯基)丙醯 氧基]乙基]-2,4,8,10-四氧雜螺環[5,5]十一烷、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二第三丁基-4-羥基苄基)苯、雙[3,3’-雙-(4’-羥基-3’-第三丁基苯基)丁酸]二醇酯、1,3,5-參(3’,5’-二第三丁基-4’-羥基苄基)-第二-三-2,4,6-(1H,3H,5H)三酮、d-α-生育酚等。該等可以單獨使用也可使用該等的混合物。受阻苯酚化合物之市售品，具體例比如BASF公司製之Irganox1010或Irganox1098(均為商品名)。 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.

磷系抗氧化劑之具體例，例如亞磷酸三苯酯、三-十八基亞磷酸酯、亞磷酸十三基酯、亞磷酸三壬基苯酯、亞磷酸二苯基異癸酯、雙(2,6-二-第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4-二-第三丁基苯基)季戊四醇二亞磷酸酯、參(2,4-二-第三丁基苯基)亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、四(十三基-4,4’-異亞丙基二苯基二亞磷酸酯、2,2-亞甲基雙(4,6-二-第三丁基苯基)辛基亞磷酸酯等有機磷化合物。該等可以單獨使用也可使用該等的混合物。 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 organophosphorus compound such as methylenebis(4,6-di-t-butylphenyl)octylphosphite. These may be used singly or as a mixture.

抗氧化劑之含量，只要是不損及組成物之各種性能之範圍即可，無特別限制，但從控制吸氧性能之觀點或抑制機械物性下降之觀點，在吸氧阻隔層中較佳為0.001~3質量%，更佳為0.01~1質量%。 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%.

[其他之添加劑] [Other additives]

吸氧阻隔層中，因應要求之用途或性能，也可添加潤滑劑、消光劑、耐熱安定劑、耐候安定劑、紫外線吸收劑、塑化劑、難燃劑、抗靜電劑、著色防止劑、結晶化核劑等添加劑。該等添加劑，可在不妨礙本發明之效果之範圍內視需要添加。 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.任意層 2. Any layer

2-1.熔接層 2-1. Welding layer

本發明之管狀容器，除了吸氧阻隔層以外，宜更包含熔接層作 為管狀容器之最內層及/或最外層更佳。藉由設置熔接層。當從多層疊層體將端部彼此熔接而製造套筒(sleeve)體時，或將套筒體及以多層擠壓製造之筒狀多層體(吹塑成型坏料(parison))與具有注出口之容器頭部熔接時，及進一步於填充內容物之後熔接管狀容器之開口部時等，可提高加工性。又，取決於內容物的種類，可提高容器之耐內容物性。 The tubular container of the present invention, in addition to the oxygen-absorbing barrier layer, preferably further comprises a welded layer It is preferably the innermost layer and/or the outermost layer of the tubular container. By providing a fusion layer. When a sleeve body is manufactured by fusing the ends from the multilayer laminate, or the sleeve body and the cylindrical multilayer body (blow molding parison) which is extruded in a plurality of layers and have a note The workability can be improved when the head of the outlet container is welded, and when the opening of the tubular container is further welded after filling the contents. Moreover, depending on the type of the contents, the physical properties of the container can be improved.

熔接層為含有具熔接性之熱塑性樹脂之層。前述具熔接性之熱塑性樹脂，可使用能因為熱而熔融並彼此熔接的各種聚烯烴系樹脂，或其他熱塑性樹脂等，例如：低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、直鏈狀(線狀)低密度聚乙烯、使用二茂金屬觸媒而聚合之乙烯-α‧烯烴共聚物、聚丙烯、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-丙烯共聚物、甲基戊烯聚合物、聚丁烯聚合物、聚乙酸乙烯酯系樹脂、聚(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、將聚乙烯或聚丙烯等聚烯烴系樹脂利用丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、富馬酸、伊康酸等不飽和羧酸改性而得之酸改性聚烯烴樹脂等，該等可以單獨使用，也可混用2種以上的材料。該等之中，從成型加工性或衛生性、氣味等觀點，宜使用低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、直鏈狀(線狀)低密度聚乙烯、使用二茂金屬觸媒而聚合得到的乙烯-α‧烯烴共聚物。 The fusion layer is a layer containing a thermoplastic resin having a weldability. As the thermoplastic resin having the weldability, various polyolefin resins which can be melted by heat and welded to each other, or other thermoplastic resins, for example, low density polyethylene, medium density polyethylene, high density polyethylene, and linear chain can be used. Shape (linear) low density polyethylene, ethylene-α‧ olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-acrylic acid copolymer, ethylene - an ethyl acrylate copolymer, an ethylene-methacrylic acid copolymer, an ethylene-propylene copolymer, a methylpentene polymer, a polybutene polymer, a polyvinyl acetate resin, a poly(meth)acrylic resin, Polyvinyl chloride resin, acid obtained by modifying a polyolefin resin such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid The modified polyolefin resin or the like may be used singly or in combination of two or more kinds. Among these, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, and metallocene are preferably used from the viewpoints of moldability, hygiene, and odor. The ethylene-α‧ olefin copolymer obtained by polymerization of a catalyst.

又，熔接層在不損及其效果的範圍，也可含有潤滑劑、結晶化核劑、白化防止劑、消光劑、耐熱安定劑、耐候安定劑、紫外線吸收劑、塑化劑、難燃劑、抗靜電劑、著色防止劑、抗氧化劑、耐衝撃性改良材等添加劑。 Further, the weld layer may contain a lubricant, a crystallization nucleating agent, a whitening preventive agent, a matting agent, a heat stabilizer, a weathering stabilizer, a UV absorber, a plasticizer, and a flame retardant in a range that does not impair the effect thereof. Additives such as antistatic agents, coloring inhibitors, antioxidants, and impact-resistant materials.

又，管狀容器之最內層及最外層兩者設置熔接層之情形，兩熔接層的構成可為彼此相同或不同，但宜選擇能穩定發揮熔接性的材料較佳。 Further, in the case where both the innermost layer and the outermost layer of the tubular container are provided with the welded layer, the two welded layers may be the same or different from each other, but it is preferable to select a material which can stably exhibit the weldability.

本發明中，熔接層之厚度，從發揮實用的熔接強度並同時確保 加工性的觀點，定為5~200μm較佳，更佳為10~150μm，又更佳為15~100μm。 In the present invention, the thickness of the welded layer is exerted from the practical welding strength while ensuring The viewpoint of workability is preferably 5 to 200 μm, more preferably 10 to 150 μm, still more preferably 15 to 100 μm.

2-2.黏著層 2-2. Adhesive layer

本發明之管狀容器，除了吸氧阻隔層以外，也可更含有黏著層。管狀容器中，當相鄰的2層(例如：吸氧阻隔層與熔接層)之間未能獲得實用的層間黏著強度的情形，宜在該2層之間設置黏著劑層較佳。 The tubular container of the present invention may further contain an adhesive layer in addition to the oxygen-absorbing barrier layer. In the tubular container, when a practical interlayer adhesive strength is not obtained between two adjacent layers (for example, an oxygen barrier layer and a welded layer), it is preferred to provide an adhesive layer between the two layers.

黏著層宜含有具黏著性之熱塑性樹脂較佳。有黏著性之熱塑性樹脂，例如：將聚乙烯或聚丙烯等聚烯烴系樹脂以丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、富馬酸、伊康酸等不飽和羧酸改性而得之酸改性聚烯烴樹脂。宜選擇將與有熔接性之熱塑性樹脂為同種之樹脂改性者作為有黏著性的熱塑性樹脂較佳。 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. Acid modified polyolefin resin. It is preferable to use a resin modified with the same kind as the thermoplastic resin having a weldability as the adhesive thermoplastic resin.

黏著層的厚度，從發揮實用的黏著強度且同時確保加工性的觀點而言，較佳為2~100μm，更佳為5~90μm，又更佳為10~80μm。 The thickness of the adhesive layer is preferably from 2 to 100 μm, more preferably from 5 to 90 μm, still more preferably from 10 to 80 μm, from the viewpoint of exerting practical adhesive strength and ensuring workability.

2-3.其他任意層 2-3. Any other layer

本發明之管狀容器，因應所望性能等，也可更含有上述以外的任意層。構成如此之層之材料，可列舉上述各種聚烯烴類、尼龍6或尼龍MXD6等各種聚醯胺類、聚對苯二甲酸乙二醇酯、聚甘醇酸等各種聚酯類、乙烯乙烯醇共聚物等熱塑性樹脂單獨或混合者。又，也可使用蒸鍍有各種金屬箔、金屬氧化物膜的樹脂膜等。 The tubular container of the present invention may further contain any layer other than the above depending on the desired performance and the like. Examples of the material constituting such a layer include various polyesters such as various polyolefins, nylon 6 or nylon MXD6, various polyesters such as polyethylene terephthalate and polyglycolic acid, and ethylene vinyl alcohol. Thermoplastic resins such as copolymers are used alone or in combination. Further, a resin film obtained by vapor-depositing various metal foils or metal oxide films may be used.

3.管狀容器之製造方法 3. Method for manufacturing tubular container

本發明之管狀容器，可藉由利用T模製作薄膜後，或以擠壓層合或共擠壓層合、乾式層合等方法製造多層疊層薄膜後，將薄膜端部彼此熔接形成套筒體後，切割為所望尺寸而成型為管道(pipe)狀，再將設有注出部的口部接合於管道端部的方法製造。又，也可 利用以共擠壓製造具多層構造之吹塑成型坏料(parison)後將口部予以接合之方法等以往公知之製造方法製造。 In the tubular container of the present invention, after the film is formed by using a T-die, or a multilayer laminated film is produced by extrusion lamination or co-extrusion lamination, dry lamination, etc., the ends of the film are welded to each other to form a sleeve. After the body is cut into a desired shape, the shape is formed into a pipe shape, and the mouth portion provided with the injection portion is joined to the end portion of the pipe. Also, A conventionally known manufacturing method such as a method of co-extruding a blow molded blank having a multilayer structure and then joining the mouth portions is used.

本發明中，吸氧阻隔層使用在管狀容器的至少一部分即可，其使用處也取決於管狀容器之製造方法。例如：當將上述薄膜並成型為管道，在該管道的端部將口部予以接合而製造管狀容器之情形，藉由在該薄膜中設置吸氧阻隔層，能於管狀容器之體(body)部設置吸氧阻隔層。 In the present invention, the oxygen-absorbing barrier layer may be used in at least a part of the tubular container, and its use depends on the method of manufacturing the tubular container. For example, when the film is formed into a pipe and the mouth is joined at the end of the pipe to manufacture a tubular container, the body of the tubular container can be formed by providing an oxygen-absorbing barrier layer in the film. The part is provided with an oxygen barrier layer.

4.管狀容器之用途 4. Use of tubular containers

本發明之管狀容器可以容納、保存例如：美乃滋、味噌、芥末、山葵、薑、蒜等磨粉灑布香辛料等調味料、果醬、奶油、黃油、乳瑪林、巧克力醬等糊狀食品、醫藥品、化粧品、牙膏、染髮劑、染色劑、肥皂、化學品等各種黏體狀物等各式各樣的物品。 The tubular container of the present invention can accommodate and store, for example, melon, miso, mustard, wasabi, ginger, garlic, and other spices such as spices, jams, butter, butter, milk marlin, chocolate sauce, and the like. Various kinds of articles such as pharmaceuticals, cosmetics, toothpaste, hair dyes, dyes, soaps, chemicals, and the like.

實施例 Example

以下利用實施例更詳細說明本發明，但本發明不限於該等實施例。 The invention will be described in more detail below by way of examples, but the invention is not limited to the examples.

又，以下實施例中，關於構成共聚物之單元，將來自間亞二甲苯二胺之單元稱為「MXDA」、來自1,3-雙(胺基甲基)環己烷之單元稱為「1,3BAC」、來自六亞甲基二胺之單元稱為「HMDA」、來自己二酸之單元稱為「AA」、來自間苯二甲酸之單元稱為「IPA」、來自DL-丙胺酸之單元稱為「DL-Ala」、來自DL-白胺酸之單元稱為「DL-Leu」、來自DL-纈胺酸之單元稱為「DL-Val」、來自ε-己內醯胺之單元稱為「ε-CL」。 Further, in the following examples, the unit constituting the copolymer is referred to as "MXDA" and the unit derived from 1,3-bis(aminomethyl)cyclohexane is referred to as "unit". 1,3BAC", the unit derived from hexamethylenediamine is called "HMDA", the unit derived from hexamethylenedicarboxylic acid is called "AA", the unit derived from isophthalic acid is called "IPA", and the unit derived from DL-alanine The unit is called "DL-Ala", the unit from DL-leucine is called "DL-Leu", the unit from DL-proline is called "DL-Val", and the unit from ε-caprolactam is called The unit is called "ε-CL".

又，聚間亞二甲苯己二醯胺稱為「N-MXD6」。 Further, polymethylene xylene hexamethylenediamine is referred to as "N-MXD6".

製造例獲得之聚醯胺樹脂之α-胺基酸含有率、相對黏度、末端胺基濃度、玻璃轉移溫度及熔點，依以下方法測定。又，由製造例獲得之聚醯胺樹脂製作薄膜，並以下列方法測定其吸氧量。 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-胺基酸含有率 (1) α-amino acid content rate

使用¹H-NMR(400MHz，日本電子(股)製、商品名：JNM-AL 400、測定模式：NON(¹H))，實施聚醯胺樹脂之α-胺基酸含有率之定量。具體而言，使用甲酸-d作為溶劑，製備聚醯胺樹脂之5質量%之溶液，並實施¹H-NMR測定。 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-AL 400, 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)相對黏度 (2) Relative viscosity

精稱丸粒狀樣本1g，於20~30℃攪拌溶解於96%硫酸100ml。完全溶解後，迅速取溶液5ml到Cannon-Fenske型黏度計，於25℃之恆溫漕中放置10分鐘後，測定落下時間(t)。又，也同樣測定96%硫酸本身的落下時間(t₀)。從t及t₀，以次式計算相對黏度。 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.

相對黏度=t/t₀ Relative viscosity = t / t ₀

(3)末端胺基濃度[NH₂] (3) terminal amine group concentration [NH ₂ ]

精稱聚醯胺樹脂，於20~30℃攪拌溶解於苯酚/乙醇=4/1容量溶液，完全溶解後，邊攪拌邊以甲醇5ml流洗容器內壁，以0.01mol/L鹽酸水溶液進行中和滴定，求取末端胺基濃度[NH₂]。 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)玻璃轉移溫度及熔點 (4) Glass transition temperature and melting point

使用差示掃描熱量計(島津製作所(股)製、商品名：DSC-60)，以升溫速度10℃/分在氮氣流下進行DSC測定(差示掃描熱量測定)，求取玻璃轉移溫度(Tg)及熔點(Tm)。 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)吸氧量 (5) oxygen uptake

使用設有T模之30mmφ雙軸擠製機(塑膠工學研究所(股)製)，以 (聚醯胺樹脂之熔點+20℃)之缸筒‧T模溫度，從聚醯胺樹脂成型出厚度約100μm之無延伸單層薄膜成型。 Using a 30mmφ twin-shaft extruder with a T-die (manufactured by the Institute of Plastics Engineering) (Crystalline resin melting point + 20 ° C) cylinder ‧ T mold temperature, molded from polyamine resin to a thickness of about 100 μm without stretching single layer film molding.

將2片從製造的無延伸單層薄膜切出的10cm×10cm的試驗片，與含水10ml的棉片一起加入到由鋁箔疊層薄膜構成的25cm×18cm的3向密封袋，以使袋內空氣量為400ml的方式進行密封。定袋內濕度為100%RH(相對濕度)。於40℃下保存7日後、保存14日後、保存28日後，各以氧濃度計(東麗工程(股)製、商品名：LC-700F)測定袋內的氧濃度，並從該氧濃度計算吸氧量。 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.

製造例1(聚醯胺樹脂1之製造) Production Example 1 (Manufacture of Polyamide Resin 1)

於配備攪拌機、分凝器、全凝器、壓力調整器、溫度計、滴加槽及泵浦、抽氣機、氮氣導入管、底排閥、拉絲模之內容積50L之耐壓反應容器，裝入經過精稱的己二酸(旭化成化學(股)製)13000g(88.96mol)、DL-丙胺酸(武藏野化學研究所(股)製)880.56g(9.88mol)、次亞磷酸鈉11.7g(0.11mol)、乙酸鈉6.06g(0.074mol)，充分進行氮氣取代後，將反應容器內密閉，保持容器內在0.4MPa的狀態，於攪拌下升溫到170℃。到達170℃之後，開始將滴加槽貯存的間亞二甲苯二胺(三菱瓦斯化學(股)製)12082.2g(88.71mol)滴加到反應容器內的已熔融的原料，於保持容器內為0.4MPa的狀態，邊排除生成之縮合水到系外邊將反應槽內連續升溫到240℃。間亞二甲苯二胺滴加結束後，使反應容器內緩慢回復到常壓，其次，使用抽氣機將反應槽內減壓為80kPa，去除縮合水。於減壓中觀察攪拌機的攪拌轉矩，於到達既定轉矩之時點，停止攪拌，將反應槽內以氮氣加壓，打開底排閥，從拉絲模拉出聚合物使成股線(strand)狀後，冷卻並以造粒機予以丸粒化，獲得MXDA/AA/DL-Ala共聚物(聚醯胺樹脂1)。又，各單體之添加組成比，為間亞二甲苯二胺：己二酸：DL-丙胺酸=47.3：47.4：5.3(mol%)。 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 (manufactured by Asahi Kasei Chemicals Co., Ltd.), 880-56 g (9.88 mol) of DL-alanine (made by Musashino Chemical Research 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 (Mitsubishi Gas Chemical Co., Ltd.) stored in the dropping tank was added dropwise to the molten raw material in the reaction vessel, and the inside of the holding vessel was kept in the holding vessel. In the state of 0.4 MPa, the generated condensation water was removed from the outside of the system and the temperature was continuously raised to 240 ° C in the reaction vessel. After the dropwise addition of m-xylylenediamine was completed, the inside of the reaction vessel was gradually returned to normal pressure, and then, the inside of the reaction vessel was depressurized to 80 kPa using an aspirator to remove the condensed water. Observe the stirring torque of the mixer under reduced pressure. When the predetermined torque is reached, the stirring is stopped, the reaction tank is pressurized with nitrogen, the bottom valve is opened, and the polymer is pulled out from the drawing die to form a strand. After the form, it was cooled and pelletized by a granulator 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%).

製造例2 Manufacturing Example 2

(聚醯胺樹脂2之製造) (Manufacture of Polyamide Resin 2)

將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：DL-丙胺酸=44.4：44.5：11.1(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Ala共聚物(聚醯胺樹脂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).

製造例3 Manufacturing Example 3

(聚醯胺樹脂3之製造) (Manufacture of Polyamide Resin 3)

將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：DL-丙 胺酸=41.1：41.3：17.6(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Ala共聚物(聚醯胺樹脂3)。 The addition ratio of each monomer is set to m-xylylenediamine: adipic acid: DL-propyl The MXDA/AA/DL-Ala copolymer (polyamide resin 3) was obtained in the same manner as in Production Example 1 except that the amine acid was 41.1:41.3:17.6 (mol%).

製造例4 Manufacturing Example 4

(聚醯胺樹脂4之製造) (Manufacture of Polyamide Resin 4)

將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：DL-丙胺酸=37.5：37.5：25.0(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Ala共聚物(聚醯胺樹脂4)。 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 = 37.5:37.5:25.0 (mol%). /DL-Ala copolymer (polyamide resin 4).

製造例5 Manufacturing Example 5

(聚醯胺樹脂5之製造) (Manufacture of Polyamide Resin 5)

將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：DL-丙 胺酸=33.3：33.4：33.3(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Ala共聚物(聚醯胺樹脂5)。 The addition ratio of each monomer is set to m-xylylenediamine: adipic acid: DL-propyl The MXDA/AA/DL-Ala copolymer (polyamide resin 5) was obtained in the same manner as in Production Example 1 except that the amine acid was changed to 33.3:33.4:33.3 (mol%).

製造例6(聚醯胺樹脂6之製造) Production Example 6 (Manufacture of Polyamide Resin 6)

將α-胺基酸替換為DL-白胺酸(Ningbo Haishuo Bio-technology製)，並將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：DL-白胺酸=44.3：44.6：11.1(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Leu共聚物(聚醯胺樹脂6)。 The α-amino acid was replaced with DL-leucine (manufactured by Ningbo Haishuo Bio-technology), and the addition ratio of each monomer was set to m-xylylenediamine: adipic acid: DL-leucine = In the same manner as in Production Example 1, except that 44.3: 44.6: 11.1 (mol%), MXDA/AA/DL-Leu copolymer (polyamide resin 6) was obtained.

製造例7 Manufacturing Example 7

(聚醯胺樹脂7之製造) (Manufacture of Polyamide Resin 7)

將α-胺基酸改為DL-纈胺酸(SinogelAminoAcidCo.,Ltd製)，並設定各單體之添加組成比為間亞二甲苯二胺：己二酸：DL-纈胺酸=44.3：44.6：11.1(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Val共聚物(聚醯胺樹脂7)。 The α-amino acid was changed to DL-proline (Sinogel AminoAcid Co., Ltd.), and the addition ratio of each monomer was set to m-xylylenediamine: adipic acid: DL-proline = 44.3: The MXDA/AA/DL-Val copolymer (polyamide resin 7) was obtained in the same manner as in Production Example 1 except that the amount of the MXDA/AA/DL-Val copolymer was 44.1 (mol%).

製造例8(聚醯胺樹脂8之製造) Production Example 8 (Manufacture of Polyamide Resin 8)

將二羧酸成分替換為間苯二甲酸(AGInternationalChemical(股)製)與己二酸之混合物，並將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：間苯二甲酸：DL-丙胺酸=44.3：39.0：5.6：11.1(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/IPA/DL-Ala共聚物(聚醯胺樹脂8)。 The dicarboxylic acid component is replaced by a mixture of isophthalic acid (manufactured by AG International Chemical Co., Ltd.) and adipic acid, and the addition ratio of each monomer is set to m-xylylenediamine: adipic acid: m-benzoic acid The MXDA/AA/IPA/DL-Ala copolymer (polyamide resin 8) was obtained in the same manner as in Production Example 1 except that the carboxylic acid: DL-alanine = 44.3:39.0:5.6:11.1 (mol%).

製造例9(聚醯胺樹脂9之製造) Production Example 9 (Manufacture of Polyamide Resin 9)

使用ε-己內醯胺(宇部興產(股)製)作為共聚單體，並將α-胺基酸替換為DL-白胺酸，將各單體之添加組成比設定為間亞二甲苯二胺：己二酸：DL-白胺酸：ε-己內醯胺=41.0：41.3：11.8：5.9(mol%)，除此以外與製造例1同樣進行，獲得MXDA/AA/DL-Leu/ε-CL共聚物(聚醯胺樹脂9)。 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 9).

製造例10(聚醯胺樹脂10之製造) Production Example 10 (Manufacture of Polyamide Resin 10)

將二胺成分替換為1,3-雙(胺基甲基)環己烷(三菱瓦斯化學(股)製)與間亞二甲苯二胺之混合物，並將各單體之添加組成比設定為間亞二甲苯二胺：1,3-雙(胺基甲基)環己烷：己二酸：DL-丙胺酸=33.2：11.1：44.6：11.1(mol%)，除此以外與製造例1同樣進行，獲得MXDA/1,3BAC/AA/DL-Ala共聚物(聚醯胺樹脂10)。 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 M-xylylenediamine: 1,3-bis(aminomethyl)cyclohexane: adipic acid: DL-alanine = 33.2: 11.1: 44.6: 11.1 (mol%), except for Production Example 1 Also proceeding, MXDA/1,3BAC/AA/DL-Ala copolymer (polyamide resin 10) was obtained.

製造例11(聚醯胺樹脂11之製造) Production Example 11 (Manufacture of Polyamide Resin 11)

將二胺成分替換為六亞甲基二胺(昭和化學(股)製)與間亞二甲苯二胺之混合物，並將各單體之添加組成比設定為間亞二甲苯二胺：六亞甲基二胺：己二酸：DL-丙胺酸=33.3：11.1：44.5：11.1(mol%)，除此以外與製造例1同樣進行，獲得MXDA/HMDA/AA/DL-Ala共聚物(聚醯胺樹脂11)。 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 resin 11).

製造例12(聚醯胺樹脂12之製造) Production Example 12 (Manufacture of Polyamide Resin 12)

不添加DL-丙胺酸，且將各單體之添加組成比設定為間亞二甲苯二胺：己二酸=49.8：50.2(mol%)，除此以外與製造例1同樣進行，獲得N-MXD6(聚醯胺樹脂12)。 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 12).

製造例13 Manufacturing Example 13

(聚醯胺樹脂13之製造) (Manufacture of polyamide resin 13)

不添加DL-丙胺酸，並設定各單體之添加組成比為間亞二甲苯二胺：己二酸=50.2：49.8(mol%)，除此以外與製造例1同樣進行，獲得N-MXD6(聚醯胺樹脂13)。 N-MXD6 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 = 50.2: 49.8 (mol%). (Polyuramine resin 13).

表1顯示聚醯胺樹脂1~13之添加單體組成、及獲得之聚醯胺樹脂之α-胺基酸含有率、相對黏度、末端胺基濃度、玻璃轉移溫度、熔點及吸氧量之測定結果。 Table 1 shows the monomer composition of the polyamidamide resins 1 to 13, 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.

其次，於實施例1~11及比較例1~4，使用上述聚醯胺樹脂1~13製作管狀容器。 Next, in Examples 1 to 11 and Comparative Examples 1 to 4, a tubular container was produced using the above polyamine resins 1 to 13.

實施例1 Example 1

使用由第1~第4擠製機、進料器具、模及冷卻裝置構成之4種5層之多層管道擠製裝置，從第1擠製機擠製高密度聚乙烯(日本聚乙烯(股)製，NovatecHD-HB431，以下簡稱為HDPE)，從第2擠製機擠製黏著性聚乙烯(三菱化學(股)製、商品名：Modic L553，以下簡稱為黏著性PE)，從第3擠製機擠製製造例1製造之聚醯胺樹脂1，從第4擠製機擠製低密度聚乙烯(日本聚乙烯(股)製，NovatecLD-YF30，以下簡稱為LDPE)，製造從內層側往外層側依序有HDPE層(120μm)/黏著性PE層(30μm)/聚醯胺樹脂層(50μm)/黏著性PE層(30μm)/LDPE層(120μm)之構成之內徑35mm之4種5層多層管道。將該多層管道裁切成長度160mm後，將有氣體阻隔性且係以高密度聚乙烯(日本聚乙烯(股)製，Novatec HD-HJ360)作為主材的口部接合於管道的其中一端部，獲得管狀容器。又，該管狀容器由於在後述評價試驗填充內容物，故管道的另一端部未封閉而為開口的狀態。 Extrusion of high-density polyethylene (Japan Polyethylene) from the first extruder using four 5-layer multi-layer pipe extrusion devices consisting of the first to fourth extruders, feeding devices, molds, and cooling devices ), Novatec HD-HB431, hereinafter referred to as HDPE), extruded adhesive polyethylene from the second extruder (Mitsubishi Chemical Co., Ltd., trade name: Modic L553, hereinafter referred to as adhesive PE), from the third The extrusion process was used to extrude the polyamide resin 1 produced in the production example 1, and the low-density polyethylene (Nippon Polyethylene Co., Ltd., Novatec LD-YF30, hereinafter referred to as LDPE) was extruded from the fourth extruder. The inner side of the layer side has an HDPE layer (120 μm)/adhesive PE layer (30 μm)/polyamide resin layer (50 μm)/adhesive PE layer (30 μm)/LDPE layer (120 μm). 4 kinds of 5 layers of multi-layer pipes. After the multilayered pipe was cut into a length of 160 mm, a gas barrier property was bonded to the one end of the pipe by a mouth portion made of high-density polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD-HJ360). , obtain a tubular container. Moreover, since the tubular container was filled with the contents in the evaluation test described later, the other end portion of the pipe was not closed and was in an open state.

實施例2~11 Example 2~11

於聚醯胺樹脂層將聚醯胺樹脂1替換為聚醯胺樹脂2~11，除此以外與實施例1同樣進行，製作管狀容器。 A tubular container was produced in the same manner as in Example 1 except that the polyamide resin 1 was replaced with the polyamide resin 2 to 11 in the polyamide resin layer.

比較例1 Comparative example 1

於聚醯胺樹脂層將聚醯胺樹脂1替換為使用聚醯胺樹脂12，除此以外與實施例1同樣進行，製作管狀容器。 A tubular container was produced in the same manner as in Example 1 except that the polyamide resin 1 was replaced with the polyamide resin 12 in the polyimide resin layer.

比較例2 Comparative example 2

於聚醯胺樹脂層，將聚醯胺樹脂1替換為使用將100質量份之 聚醯胺樹脂12與0.21質量份之硬脂酸鈷(II)予以乾式摻混而得者，除此以外，與實施例1同樣進行，製作管狀容器。 In the polyamide resin layer, the polyamide resin 1 is replaced with 100 parts by mass. A tubular container was produced in the same manner as in Example 1 except that the polyamide resin 12 was dry-blended with 0.21 part by mass of cobalt stearate (II).

比較例3 Comparative example 3

於聚醯胺樹脂層將聚醯胺樹脂1替換為使用將100質量份之聚醯胺樹脂13與0.15質量份之硬脂酸鈷(II)與3質量份之馬來酸改性聚丁二烯(日本石油化學(股)製、商品名：M-2000-20)予以乾式摻混而得者，除此以外與實施例1同樣進行，製作管狀容器。 The polyamide resin 1 is replaced with a polyamine resin layer of 100 parts by mass with 0.15 parts by mass of cobalt stearate (II) and 3 parts by mass of maleic acid modified polybutylene. A tubular container was produced in the same manner as in Example 1 except that the olefin (manufactured by Nippon Petrochemical Co., Ltd., trade name: M-2000-20) was dry-blended.

比較例4 Comparative example 4

將對於平均粒徑30μm之還原鐵粉100質量份塗覆有氯化鈣3質量份而得的粒狀吸氧劑40質量份與HDPE60質量份予以乾式摻混，以35mm雙軸擠製機擠製，並以附有吹風機的網帶冷卻後經過造粒機，獲得含吸氧劑之HDPE。 40 parts by mass of the reduced iron powder having an average particle diameter of 30 μm coated with 3 parts by mass of calcium chloride and 40 parts by mass of the particulate oxygen absorber were dry blended with 60 parts by mass of HDPE, and extruded by a 35 mm biaxial extruder. The system is cooled by a mesh belt with a hair dryer and passed through a granulator to obtain an HDPE containing an oxygen absorber.

使用由第1~第5擠製機、進料器具、模及冷卻裝置構成之5種6層之多層管道擠製裝置，從第1擠製機擠製HDPE，從第2擠製機擠製前述含吸氧劑之HDPE，從第3擠製機擠製黏著性PE，從第4擠製機擠製製造例12獲得之聚醯胺樹脂12，從第5擠製機擠製LDPE，製造從內層側往外層側依序為HDPE層(60μm)/含吸氧劑之HDPE層(60μm)/黏著性PE層(30μm)/聚醯胺樹脂層(50μm)/黏著性PE層(30μm)/LDPE層(120μm)之構成的內徑35mm的5種6層多層管道。將該多層管道裁切成長度160mm之後，將有氣體阻隔性且係以高密度聚乙烯(日本聚乙烯(股)製，NovatecHD-HJ360)為主材之口部接合在管道的其中一端部，獲得管狀容器。又，該管狀容器由於在後述評價試驗填充內容物，故管道的另一端部不封閉而為開口的狀態。 Five kinds of six-layer multi-layer pipe extrusion devices consisting of first to fifth extruders, feeding devices, molds and cooling devices, and HDPE from the first extruder, and extruded from the second extruder The above-mentioned HDPE containing an oxygen absorbing agent, extruded from the third extruder to the adhesive PE, extruded from the fourth extruder to the polyamide resin 12 obtained in the production example 12, and extruded from the fifth extruder to the LDPE. From the inner layer side to the outer layer side, the HDPE layer (60 μm) / the oxygen-absorbing agent HDPE layer (60 μm) / the adhesive PE layer (30 μm) / the polyamide resin layer (50 μm) / the adhesive PE layer (30 μm) / LDPE layer (120 μm) consisting of five 6-layer multi-layer pipes with an inner diameter of 35 mm. After the multi-layered pipe is cut into a length of 160 mm, a gas barrier is used, and a mouth portion of a high-density polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD-HJ360) is joined to one end portion of the pipe. A tubular container is obtained. Moreover, since the tubular container was filled with the contents in the evaluation test described later, the other end portion of the pipe was not closed and was in an open state.

使用上述實施例1~11及比較例1~4製作的管狀容器，依以下方式評價氧化劣化抑制效果、風味保持性、及強度維持性。 Using the tubular containers produced in the above Examples 1 to 11 and Comparative Examples 1 to 4, the oxidative degradation inhibiting effect, the flavor retaining property, and the strength maintaining property were evaluated as follows.

(1)氧化劣化抑制效果(L-抗壞血酸殘存率) (1) Oxidation deterioration inhibition effect (L-ascorbic acid residual ratio)

將設置於管狀容器之口部之前端孔洞以鋁箔疊層膜密封，將蓋子封閉。其次，從管狀容器的開口部填充L-抗壞血酸10%水溶液100ml，熱封以密封開口部。將該容器於25℃、50%RH的環境下保存3個月後，取出內容液，在容量100ml的高燒杯內裝入內容液10ml，其次加入偏磷酸與乙酸的混合水溶液5ml與蒸餾水40ml。其次，以0.05mol/l的碘溶液作為滴定液，使用電位差滴定裝置以反曲點檢測法實施滴定，從其結果求取L-抗壞血酸殘存率。又，L-抗壞血酸之殘存率愈高，則意指抑制內容物之氧化劣化的效果愈優異。 The hole at the end of the mouth of the tubular container is sealed with an aluminum foil laminate film to close the lid. Next, 100 ml of a 10% aqueous solution of L-ascorbic acid was filled from the opening of the tubular container, and heat-sealed to seal the opening. After storing the container in an environment of 25° C. and 50% RH for 3 months, the content liquid was taken out, and 10 ml of a content liquid was placed in a high-capacity beaker having a capacity of 100 ml, and then 5 ml of a mixed aqueous solution of metaphosphoric acid and acetic acid and 40 ml of distilled water were added. Next, using a 0.05 mol/l iodine solution as a titration solution, titration was carried out by a potential difference titration apparatus using an inflection point detecting method, and the residual ratio of L-ascorbic acid was determined from the results. Further, the higher the residual ratio of L-ascorbic acid, the more excellent the effect of suppressing oxidative degradation of the content.

(2)風味保持性 (2) flavor retention

將管狀容器的開口部熱封以密封後，從設置於管狀容器的口部的前端孔洞填充蒸餾水100ml，以鋁箔疊層膜將口部的前端孔洞密封以封閉蓋子。將該容器於25℃、50%RH的環境下保存1個月後，剝開鋁箔疊層膜，以檢查容器內頂部空間的氣味。 After the opening of the tubular container was heat-sealed and sealed, 100 ml of distilled water was filled from the front end hole provided in the mouth of the tubular container, and the front end hole of the mouth was sealed with an aluminum foil laminated film to close the lid. After the container was stored in an environment of 25 ° C and 50% RH for one month, the aluminum foil laminated film was peeled off to examine the odor of the head space inside the container.

未認為有氣味者評為○，認為有氣味者評為×。 Those who are not considered to have odor are rated as ○, and those who are considered to have odor are rated as ×.

(3)強度維持性 (3) Strength maintenance

從在上述風味保持性之試驗中保存蒸餾水1個月後的容器抽出蒸餾水，將容器以手搓揉50次後，觀察容器並檢查是否有層間剝離。 Distilled water was taken out from the container in which the distilled water was stored for one month in the above-described flavor retention test, and the container was hand-twisted 50 times, and the container was observed to examine whether or not there was interlayer peeling.

未認為有層間剝離者評為○，認為有層間剝離者評為×。 It was not considered that the interlayer peeling was rated as ○, and it was considered that the interlayer peeling was rated as ×.

表2顯示評價結果。 Table 2 shows the results of the evaluation.

[表2-1] [table 2-1]

實施例1~11之管狀容器均為氧化劣化抑制效果、風味保持性、及強度維持性皆優異。 The tubular containers of Examples 1 to 11 were excellent in oxidative degradation suppressing effect, flavor retaining property, and strength maintaining property.

比較例1之管狀容器，雖然風味保持性及強度維持性優異，但是L-抗壞血酸的殘存率低，於氧化劣化抑制效果之點不佳。據認為原因在於：比較例1之管狀容器使用之聚醯胺樹脂12雖有氧阻隔性能，但無吸氧性能，L-抗壞血酸氧化的原故。 The tubular container of Comparative Example 1 is excellent in flavor retention and strength maintenance, but has a low residual ratio of L-ascorbic acid and is inferior in the effect of suppressing oxidative degradation. The reason is considered to be that the polyamine resin 12 used in the tubular container of Comparative Example 1 has oxygen barrier properties, but has no oxygen absorbing property and is oxidized by L-ascorbic acid.

比較例2的管狀容器，雖然氧化劣化抑制效果及風味保持性優異，但是於容器之手搓揉試驗中，聚醯胺層破壞且發生層間剝離，容器的外觀惡化。據認為原因在於：藉由使聚醯胺樹脂12與過渡金屬化合物(硬脂酸鈷(II))共存雖能展現吸氧性能，但同時聚醯胺樹脂12會氧化分解，且聚醯胺樹脂層強度劣化。 In the tubular container of Comparative Example 2, although the oxidative degradation inhibiting effect and the flavor retaining property were excellent, in the handcuff test of the container, the polyamide layer was broken and delamination occurred, and the appearance of the container was deteriorated. It is considered that the reason is that the polyamine resin 12 and the transition metal compound (cobalt (II) stearate) can exhibit oxygen absorption properties, but at the same time, the polyamide resin 12 oxidatively decomposes, and the polyamide resin The layer strength is deteriorated.

比較例3之管狀容器3，雖然氧化劣化抑制效果及強度維持性優異，但開封時會認為有異味，於風味保持性之點不佳。據認為原因在於：聚醯胺樹脂13的末端胺基濃度高，實質上不易氧化，所以聚醯胺樹脂層不會大幅地強度劣化，且藉由使馬來酸改性聚丁二烯與硬脂酸鈷共存，會展現吸氧性能，但是由於伴隨聚丁二烯之氧化劣化產生低分子量化合物，會發生異味。 In the tubular container 3 of the comparative example 3, although the oxidative degradation inhibiting effect and the strength maintaining property are excellent, an odor is considered at the time of opening, and the flavor retaining property is not preferable. It is considered that the reason is that the polyamide amine group 13 has a high terminal amine group concentration and is substantially not easily oxidized, so that the polyamide resin layer does not greatly deteriorate in strength, and the maleic acid-modified polybutadiene is hardened. Coexistence of cobalt citrate exhibits oxygen absorbing properties, but odor is generated due to oxidative degradation of polybutadiene to produce low molecular weight compounds.

比較例4之管狀容器4，氧化劣化抑制效果及強度維持性雖優異，但是開封時會察覺有鐵味。據認為原因在於：聚醯胺樹脂層會展現氧阻隔性能且含吸氧劑之LDPE會展現吸氧性能，但由於使用鐵粉作為吸氧劑，因為該鐵粉產生鐵味。 The tubular container 4 of Comparative Example 4 is excellent in oxidative degradation suppressing effect and strength maintaining property, but is noticeable in iron flavor at the time of opening. It is considered that the reason is that the polyimide resin layer exhibits oxygen barrier properties and the LDPE containing the oxygen absorbing agent exhibits oxygen absorbing performance, but iron powder is used as the oxygen absorbing agent because the iron powder generates iron odor.

[產業利用性] [Industry Utilization]

本發明之管狀容器可理想地當作包裝材料。 The tubular container of the present invention is desirably used as a packaging material.

Claims (8)

一種管狀容器，其係包含含有聚醯胺樹脂之層；該聚醯胺樹脂包含：二胺單元25~50莫耳%，其中，含有選自於由以下列通式(I-1)表示之芳香族二胺單元、以下列通式(I-2)表示之脂環族二胺單元、及以下列通式(I-3)表示之直鏈脂肪族二胺單元構成之群組中之至少1種二胺單元總計含量為50莫耳%以上；二羧酸單元25~50莫耳%，其中，含有以下列通式(II-1)表示之直鏈脂肪族二羧酸單元及/或以下列通式(II-2)表示之芳香族二羧酸單元總計含量為50莫耳%以上；及以下列通式(III)表示之構成單元0.1~50莫耳%； [該通式(I-3)中，m表示2~18之整數；該通式(II-1)中，n表示2~18之整數；該通式(II-2)中，Ar表示伸芳基；該通式(III)中，R表示取代或無取代之烷基或取代或無取代之芳基]。 A tubular container comprising a layer containing a polyamide resin; the polyamide resin comprising: 25 to 50 mol% of a diamine unit, wherein the content of the polyamine resin is selected from the group consisting of the following formula (I-1) At least one of the group consisting of an aromatic diamine unit, an alicyclic diamine unit represented by the following formula (I-2), and a linear aliphatic diamine unit represented by the following formula (I-3) a diamine unit having a total content of 50 mol% or more; a dicarboxylic acid unit of 25 to 50 mol%, wherein the linear dicarboxylic acid unit represented by the following formula (II-1) and/or The total content of the aromatic dicarboxylic acid unit represented by the following formula (II-2) is 50 mol% or more; and the constituent unit represented by the following general formula (III) is 0.1 to 50 mol%; [In the general formula (I-3), m represents an integer of 2 to 18; in the general formula (II-1), n represents an integer of 2 to 18; in the general formula (II-2), Ar represents an extension An aryl group; in the formula (III), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group]. 如申請專利範圍第1項之管狀容器，其中，該通式(III)之R為取代或無取代之碳數1~6之烷基或取代或無取代之碳數6~10之芳基。 The tubular container 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 aryl group having 6 to 10 carbon atoms. 如申請專利範圍第1或2項之管狀容器，其中，該二胺單元含有間亞二甲苯二胺單元50莫耳%以上。 A tubular container according to claim 1 or 2, wherein the diamine unit contains 50 mol% or more of m-xylylenediamine unit. 如申請專利範圍第1至3項中任一項之管狀容器，其中，該直鏈脂肪族二羧酸單元含有選自於由己二酸單元、癸二酸單元、 及1,12-十二烷二羧酸單元構成的群組中之至少1種總計含量為50莫耳%以上。 The tubular container 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 and sebacic acid units. At least one of the group consisting of 1,12-dodecanedicarboxylic acid units has a total content of 50 mol% or more. 如申請專利範圍第1至4項中任一項之管狀容器，其中，該芳香族二羧酸單元含有選自於由間苯二甲酸單元、對苯二甲酸單元、及2,6-萘二羧酸單元構成之群組中之至少1種總計含量為50莫耳%以上。 The tubular container 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-naphthalene At least one of the group consisting of carboxylic acid units has a total content of 50 mol% or more. 如申請專利範圍第1至5項中任一項之管狀容器，其中，該聚醯胺樹脂更含有含量為聚醯胺樹脂之全部構成單元中之0.1~49.9莫耳%的以下列通式(X)表示之ω-胺基羧酸單元； [該通式(X)中，p表示2~18之整數]。 The tubular container according to any one of claims 1 to 5, wherein the polyamide resin further contains 0.1 to 49.9 mol% of all constituent units of the polyamide resin in the following formula ( X) represents an ω-amino carboxylic acid unit; [In the general formula (X), p represents an integer of 2 to 18]. 如申請專利範圍第6項之管狀容器，其中，該ω-胺基羧酸單元含有6-胺基己酸單元及/或12-胺基十二烷酸單元總計含量為50莫耳%以上。 The tubular container according to claim 6, wherein the ω-amino carboxylic acid unit contains a 6-aminocaproic acid unit and/or a 12-aminododecanoic acid unit in a total amount of 50 mol% or more. 如申請專利範圍第1至7項中任一項之管狀容器，其中，該聚醯胺樹脂之相對黏度為1.8以上4.2以下。 The tubular container according to any one of claims 1 to 7, wherein the polyamidamide resin has a relative viscosity of 1.8 or more and 4.2 or less.