JP2016174731A - Multilayer blood collection tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer blood collection tube having extremely low oxygen permeability and is also excellent in other gas barrier properties.SOLUTION: A multilayer blood collection tube has: a multilayer bottomed tube comprising at least three layers of a resin layer comprising polyester (b), an oxygen absorbent layer comprising an oxygen absorbent resin composition, and a resin layer comprising polyester (b) in the stated order, and having an opening; and a plug body having a needle puncture part which can be punctured with a blood sampling needle.SELECTED DRAWING: None

Description

  The present invention relates to a multilayer blood collection tube used for storing blood.

  Polyethylene terephthalate (PET) is used for plastic medical containers. However, PET is somewhat permeable to oxygen and other gases. Therefore, a PET container essentially allows gas to pass therethrough. As the use of plastic medical products becomes more important in the medical field, these permeability issues are becoming more serious.

  In particular, the vacuum blood collection tube must meet predetermined performance standards. In general, such performance standards include the ability to maintain about 90% or more of the original inhalation over a year, so the gas permeability of PET is undesirable. Further, the vacuum blood collection tube may be pre-filled with a reagent, and when the reagent is deteriorated by oxygen, the oxygen permeability becomes a greater problem.

  Glass vacuum blood collection tubes are extremely excellent in gas barrier properties, heat resistance, and transparency, but on the other hand, they are easily damaged by dropping, etc., and humans can break glass fragments and biologically harmful contents. Exposed to. In addition, undetectable microcracks may remain in the glass container, and the container bursts due to the pressure generated when microorganisms grow in the container, causing a risk of human exposure to ecological hazardous substances. Furthermore, since glass has a large specific gravity, there is a problem that the container becomes heavy (Patent Document 1).

JP 2014-55092 A

  This invention is made | formed in view of the said subject, The objective is to provide the multilayer blood-collecting tube excellent in barrier property of gas, such as oxygen and nitrogen.

  As a result of diligent studies on multilayer blood collection tubes, the present inventors have found that a resin layer (layer B) containing polyester (b), an oxygen absorption layer (layer A) comprising an oxygen-absorbing resin composition, and polyester It has been found that the above problems can be solved by a container having at least three layers in this order with a resin layer (layer B) containing (b), and the present invention has been completed.

（式中、Ｒは、それぞれ独立して一価の置換基を示し、一価の置換基は、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基及びイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよい。ｍは０〜３、ｎは０〜７の整数を表し、テトラリン環のベンジル位に少なくとも１つ以上の水素原子が結合している。Ｘは芳香族炭化水素基、飽和または不飽和の脂環式炭化水素基、直鎖状または分岐状の飽和または不飽和の脂肪族炭化水素基及び複素環基からなる群から選ばれる少なくとも１つの基を含有する２価の基を表す。）
からなる群より選択される少なくとも１つのテトラリン環を有する構成単位（ａ）と、
３価以上の多価アルコール、３価以上の多価カルボン酸およびその誘導体、並びに３価以上のヒドロキシカルボン酸およびその誘導体、からなる群より選ばれる、少なくとも１種の多官能化合物由来の構成単位（ｂ）とを有するポリエステル化合物（ａ）である、上記＜２＞に記載の多層採血管。
＜４＞
前記ポリエステル化合物（ａ）が、前記一般式（１）で表される前記構成単位（ａ）と前記構成単位（ｂ）とを、９９．９９：０．０１〜９０：１０のモル比で含有する、上記＜３＞に記載の多層採血管。
＜５＞
前記一般式（１）におけるＸがエチレン基及び／又はテトラメチレン基である構成単位（ａ）の割合が、前記ポリエステル化合物（ａ）が有する全ての構成単位（ａ）に対して９５モル％以上である、上記＜３＞又は＜４＞のいずれかに記載の多層採血管。
＜６＞
前記一般式（１）におけるＸがエチレン基である構成単位（ａ）の割合が、前記ポリエステル化合物（ａ）が有する全ての構成単位（ａ）に対して６０モル％以上である、上記＜３＞〜＜５＞のいずれかに記載の多層採血管。
＜７＞
前記ポリエステル化合物（ａ）が有する全ての構成単位（ａ）に対する、前記一般式（１）におけるＸがエチレン基である構成単位（ａ）の割合が９５モル％以上である、上記＜３＞〜＜６＞のいずれかに記載の多層採血管。
＜８＞
前記ポリエステル化合物（ａ）の剪断速度１２１６ｓｅｃ^−１における２６０℃の溶融粘度の値が、１５０Ｐａ・ｓｅｃ以上である、上記＜３＞〜＜７＞のいずれかに記載の多層採血管。
＜９＞
前記ポリエステル化合物（ａ）のガラス転移温度の値が、５０℃以上である上記＜３＞〜＜８＞のいずれかに記載の多層採血管。
＜１０＞
前記遷移金属触媒が、マンガン、鉄、コバルト、ニッケルおよび銅からなる群より選択される少なくとも１種以上の遷移金属を含むものである、上記＜２＞〜＜９＞のいずれかに記載の多層採血管。
＜１１＞
前記遷移金属触媒が、前記ポリエステル化合物（ａ）１００質量部に対し、遷移金属量として０．００１〜１０質量部含まれる、上記＜２＞〜＜１０＞のいずれかに記載の多層採血管。 That is, the present invention provides the following <1> to <11>.
<1>
It has at least three layers of a resin layer containing polyester (b), an oxygen absorbing layer containing an oxygen-absorbing resin composition, and a resin layer containing polyester (b) in this order, and has a multilayer having an opening. The bottom tube,
A stopper having a needle piercing portion through which a blood collection needle can be pierced;
A multilayer blood collection tube.
<2>
The multilayer blood collection tube according to <1>, wherein the oxygen-absorbing resin composition contains a compound having a tetralin ring and a transition metal catalyst.
<3>
The compound having the tetralin ring is represented by the following general formulas (1) to (4).

(In the formula, each R independently represents a monovalent substituent, and the monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, or a hydroxy group. At least selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group These may be further substituted, m represents an integer of 0 to 3, n represents an integer of 0 to 7, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring. X is selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. It represents a divalent group containing at least one group barrel.)
A structural unit (a) having at least one tetralin ring selected from the group consisting of:
A structural unit derived from at least one polyfunctional compound selected from the group consisting of a trihydric or higher polyhydric alcohol, a trivalent or higher polyvalent carboxylic acid and its derivative, and a trivalent or higher hydroxycarboxylic acid and its derivative. The multilayer blood collection tube according to <2>, which is a polyester compound (a) having (b).
<4>
The polyester compound (a) contains the structural unit (a) represented by the general formula (1) and the structural unit (b) in a molar ratio of 99.99: 0.01 to 90:10. The multilayer blood collection tube according to <3> above.
<5>
The proportion of the structural unit (a) in which X in the general formula (1) is an ethylene group and / or a tetramethylene group is 95 mol% or more based on all the structural units (a) of the polyester compound (a). The multilayer blood collection tube according to any one of <3> or <4> above.
<6>
The proportion of the structural unit (a) in which X in the general formula (1) is an ethylene group is 60 mol% or more with respect to all the structural units (a) of the polyester compound (a), <3 The multilayer blood collection tube according to any one of> to <5>.
<7>
<3> to <3> above, wherein the ratio of the structural unit (a) in which X in the general formula (1) is an ethylene group to all the structural units (a) of the polyester compound (a) is 95 mol% or more. The multilayer blood collection tube according to any one of <6>.
<8>
The multilayer blood collection tube according to any one of <3> to <7>, wherein the polyester compound (a) has a melt viscosity value at 260 ° C. at a shear rate of 1216 sec ⁻¹ of 150 Pa · sec or more.
<9>
The multilayer blood collection tube according to any one of <3> to <8>, wherein the polyester compound (a) has a glass transition temperature value of 50 ° C. or higher.
<10>
The multilayer blood collection tube according to any one of <2> to <9>, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper. .
<11>
The multilayer blood collection tube according to any one of <2> to <10>, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the polyester compound (a).

  According to the present invention, it is possible to realize a multilayer blood collection tube that is excellent in barrier properties against gases such as oxygen and nitrogen, excellent in heat resistance and strength, and excellent in maintaining transparency. An oxygen-absorbing resin containing a polyester compound (a) having a structural unit derived from a trifunctional or higher polyfunctional compound and a structural unit having a predetermined tetralin ring in the oxygen-absorbing layer of the multilayer blood collection tube and a transition metal catalyst When the composition is used, oxygen can be absorbed regardless of the presence or absence of moisture in the storage object. In addition, the decrease in strength of the polyester compound (a) having the tetralin ring due to oxidation after oxygen absorption is extremely small, and the strength of the oxygen absorption layer is maintained even in long-term use. Can also be realized. Furthermore, since the production of low molecular weight organic compounds after oxygen absorption is remarkably suppressed, it is possible to realize a multi-layer blood collection tube with very little mixing of the low molecular weight organic compounds into the contents.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

<Multilayer blood collection tube>
The multilayer blood collection tube of this embodiment includes a multilayer bottomed tube having an opening, and a stopper having a needle piercing portion through which a blood collection needle can be pierced. The plug body can be attached to the opening of the multilayer bottomed tube, and any known material can be used as long as the inside of the multilayer blood collection tube can be maintained in a reduced pressure state.

<Multilayer bottomed tube>
The multi-layered bottomed tube includes a resin layer (layer B) containing polyester (b), an oxygen absorption layer (layer A) containing an oxygen-absorbing resin composition, and a resin layer (layer) containing polyester (b). B) at least three layers in this order.

  The multilayer bottomed tube of the present embodiment absorbs oxygen in the multilayer blood collection tube, and permeates or penetrates when there is little oxygen that penetrates or penetrates the multilayer bottomed tube wall from the outside of the multilayer blood collection tube. Oxygen can also be absorbed to prevent alteration of the stored blood (preserved material) due to oxygen.

  As long as these layers are arranged in the order of B / A / B, the number and types of the oxygen absorption layer (layer A) and the resin layer (layer B) are particularly the layer configuration in the multilayer bottomed tube of the present embodiment. It is not limited. For example, a five-layer configuration of B1 / B2 / A / B2 / B1 including one layer A, two layers B1, and two layers B2 may be used. Moreover, the multilayer bottomed tube of the present embodiment may include an arbitrary layer such as an adhesive layer (layer AD) as necessary, for example, seven layers of B1 / AD / B2 / A / B2 / AD / B1. It may be a configuration.

<Oxygen absorption layer (layer A)>
The oxygen-absorbing layer (layer A) of the present embodiment is not particularly limited as long as it is an oxygen-absorbing resin composition, and is obtained by blending an iron-based or organic oxygen absorber with a thermoplastic resin or an easily oxidizable resin. A composition containing a transition metal catalyst, for example, a resin composition comprising a xylylene group-containing polyamide and a transition metal catalyst, an oxygen-absorbing resin composition comprising a resin having a carbon-carbon unsaturated bond and a transition metal catalyst, substituted Examples include a polymer containing a cyclohexene functional group or a resin composition comprising a low molecular weight substance to which the cyclohexene ring is bonded and a transition metal, a compound having a tetralin ring, and a resin composition containing a transition metal catalyst. A resin composition containing a compound having a tetralin ring and a transition metal catalyst is preferred from the viewpoint of moldability, transparency maintenance after high-pressure steam sterilization, and low elution, which will be described later. A polyester compound (a) having a structural unit having a tetralin ring and a structural unit derived from a trifunctional or higher polyfunctional compound (hereinafter also simply referred to as “tetralin ring-containing polyester compound (a)”) and a transition metal catalyst. The case where it consists of an oxygen-absorbing resin composition is particularly preferred.

  50 mass% or more is preferable, as for content of the said tetralin ring containing polyester compound (a) in the layer A, 70 mass% or more is more preferable, and 90 mass% or more is especially preferable. In the case of the said range, compared with the case where it is less than 50 mass%, oxygen absorption performance can be improved more.

<Tetralin ring-containing polyester compound (a)>
The tetralin ring-containing polyester compound (a) of this embodiment is a structural unit (a) having at least one tetralin ring selected from the group consisting of structural units represented by the general formulas (1) to (4). And at least one trivalent or higher polyfunctional compound selected from the group consisting of trivalent or higher polyhydric alcohols, trivalent or higher polyvalent carboxylic acids and derivatives thereof, and trivalent or higher hydroxycarboxylic acids and derivatives thereof. Contains derived structural unit (b). Here, “containing a structural unit” means that the compound has one or more of the structural unit. Such a structural unit is preferably contained as a repeating unit in the tetralin ring-containing polyester compound (a). Thus, when the tetralin ring-containing polyester compound (a) is a polymer, a homopolymer of the structural unit, a random copolymer of the structural unit and other structural units, and a block copolymer of the structural unit and other structural units Any of these may be used.

<Structural unit (a)>
The structural unit (a) contains a structural unit having at least one tetralin ring selected from the group consisting of the general formulas (1) to (4).

  As the monovalent substituent represented by R in the general formulas (1) to (4) and the following general formulas (5) to (12), a halogeno group (for example, a chloro group, a bromo group, an iodo group), An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, more preferably 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group), alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 straight chain, branched) Or alkenyl groups such as vinyl and allyl groups), alkynyl groups (preferably alkynyl groups having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms such as ethynyl groups and propargyl groups), A reel group (preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having a carbon number of 1 to 12, more preferably A monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound having 2 to 6 carbon atoms, such as a 1-pyrazolyl group, 1 -Imidazolyl group, 2-furyl group), cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). A linear, branched or cyclic alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, For example, a phenoxy group), an acyl group (including a formyl group, preferably an alkylcarbonyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, preferably 7 to 12 carbon atoms, more preferably An arylcarbonyl group having 7 to 9 carbon atoms, for example, an acetyl group, a pivaloyl group, a benzoyl group), an amino group (preferably an alkylamino group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, preferably Is an anilino group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, preferably a heterocyclic amino group having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, such as an amino group, Methylamino group, anilino group), mercapto group, alkylthio group (preferably an alkylthio group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a methylthio group, Ethylthio group), arylthio group (preferably having 6 to 12 carbon atoms, more preferably arylthio group having 6 to 8 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having 2 to 10 carbon atoms, Preferably a heterocyclic thio group having 1 to 6 carbon atoms, such as a 2-benzothiazolylthio group, an imide group (preferably an imide group having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, Examples thereof include N-succinimide group and N-phthalimide group), but are not particularly limited thereto.

  In addition, when said monovalent substituent R has a hydrogen atom, the hydrogen atom is a substituent T (Here, the substituent T is synonymous with what was demonstrated by said monovalent substituent R.). ) May be further substituted. Specific examples thereof include, for example, an alkyl group substituted with a hydroxy group (for example, hydroxyethyl group), an alkyl group substituted with an alkoxy group (for example, methoxyethyl group), and an alkyl group substituted with an aryl group (for example, Benzyl group), alkyl groups substituted with primary or secondary amino groups (eg aminoethyl group), aryl groups substituted with alkyl groups (eg p-tolyl group), substituted with alkyl groups Aryloxy groups (for example, 2-methylphenoxy group) and the like, but are not particularly limited thereto. When the monovalent substituent R has a monovalent substituent T, the carbon number described above does not include the carbon number of the substituent T. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. When the monovalent substituent R has a substituent T, there may be a plurality of the substituents T.

  In the structural units represented by the general formulas (1) to (4), X is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. And a divalent group containing at least one group selected from the group consisting of an aliphatic hydrocarbon group and a heterocyclic group. The aromatic hydrocarbon group, saturated or unsaturated alicyclic hydrocarbon group, linear or branched saturated or unsaturated aliphatic hydrocarbon group and heterocyclic group may be substituted or unsubstituted. . X may contain a hetero atom, and may contain an ether group, sulfide group, carbonyl group, hydroxy group, amino group, sulfoxide group, sulfone group, and the like. Here, as the aromatic hydrocarbon group, for example, o-phenylene group, m-phenylene group, p-phenylene group, methylphenylene group, o-xylylene group, m-xylylene group, p-xylylene group, naphthylene group, Anthracenylene group, phenanthrylene group, biphenylene group, fluoronylene group and the like can be mentioned, but not limited thereto. Examples of the alicyclic hydrocarbon group include a cycloalkylene group such as a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group, and a cyclooctylene group, and a cycloalkenylene group such as a cyclohexenylene group. Although it is mentioned, it is not specifically limited to these. Examples of the aliphatic hydrocarbon group include methylene group, ethylene group, trimethylene group, propylene group, isopropylidene group, tetramethylene group, isobutylidene group, sec-butylidene group, pentamethylene group, hexamethylene group, heptamethylene group, Linear or branched alkylene groups such as octamethylene group, nonamethylene group, decamethylene group, vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, 1,3-butadienylene group, 1-pentenylene group Alkenylene groups such as 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 3-hexenylene group and the like, but are not particularly limited thereto. These may further have a substituent, and specific examples thereof include, for example, halogen, alkoxy group, hydroxy group, carboxyl group, carboalkoxy group, amino group, acyl group, thio group (for example, alkylthio group, Phenylthio group, tolylthio group, pyridylthio group, etc.), amino group (for example, unsubstituted amino group, methylamino group, dimethylamino group, phenylamino group, etc.), cyano group, nitro group and the like, but not limited thereto .

  In the tetralin ring-containing polyester compound (a) containing the structural unit represented by the general formula (1), the proportion of the structural unit (a) in which X is an ethylene group and / or a tetramethylene group is a tetralin ring. The case where it is 95 mol% or more with respect to all the structural units (a) which the containing polyester compound (a) has is preferable. In the case of the above range, the raw material cost tends to be reduced.

  Moreover, it is preferable that the ratio of the structural unit (a) whose X is an ethylene group is 60 mol% or more with respect to all the structural units (a) which the tetralin ring-containing polyester compound (a) has, and is 80 mol% or more. Is more preferable, and 95 mol% or more is particularly preferable. When it is within the above preferred range, a multi-layered bottomed tube having better moldability, high transparency after steam sterilization and excellent visibility can be obtained.

Among the structural units (a) in which X is an ethylene group and / or a tetramethylene group, more preferred are structural units represented by the following formulas (α) and (β), with the formula (α) being particularly preferred. .

<Structural unit (b)>
The structural unit (b) is derived from at least one polyfunctional compound among trihydric or higher polyhydric alcohols, trivalent or higher polyvalent carboxylic acids and derivatives thereof, and trivalent or higher hydroxycarboxylic acids and derivatives thereof. These polyfunctional compounds can be used alone or in combination of two or more. By containing a structural unit derived from a polyfunctional compound, a branched structure can be introduced into the tetralin ring-containing polyester compound (a), the molecular weight is higher than usual, and the viscosity is improved, and the tetralin ring-containing polyester has high moldability. Compound (a) can be obtained. Although the specific example of a polyfunctional compound is shown below, it is not specifically limited.

  Specific examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2, 6-hexanetriol, sorbitol, etc. are mentioned. A trihydric or more polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of trivalent or higher polyvalent carboxylic acids and derivatives thereof include propanetricarboxylic acid, trimellitic acid, trimellitic acid anhydride, pyromellitic acid, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, Examples thereof include cyclopentatetracarboxylic acid anhydride and trimellitic acid trimethyl ester. Trivalent or higher polyvalent carboxylic acids or derivatives thereof can be used alone or in combination of two or more.

  Specific examples of the trivalent or higher-valent hydroxycarboxylic acid and derivatives thereof include malic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid, citric acid, hydroxyisophthalic acid, hydroxyterephthalic acid, and the like. Trivalent or higher valent hydroxycarboxylic acids can be used singly or in combination of two or more.

  As the polyfunctional compound, polyhydric alcohol or polycarboxylic acid and derivatives thereof are preferable from the viewpoint of availability and reactivity. Among them, glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, trimellitic acid are preferable. Anhydride, pyromellitic acid, and pyromellitic acid anhydride are particularly preferable. These can be used alone or in combination of two or more.

<The manufacturing method of a polyester compound (a)>
The polyester compound (a) can be produced by a known method described in, for example, International Publication No. 2013/0777436. For example, it can be obtained by polycondensing a monomer having a tetralin ring or a derivative thereof with a polyfunctional compound such as a diol or a derivative thereof. Furthermore, in the polyester compound (a), a structural unit having no tetralin ring may be incorporated as a copolymer component to the extent that the performance is not affected. Specifically, a known compound described in Patent Document 1 can be used as a copolymerization component.

  The polyester compound (a) preferably has a hydrogen atom at the benzyl position of the tetralin ring. By using the polyester compound (a) having a hydrogen atom at the benzyl position of the tetralin ring and the transition metal catalyst in combination, it is considered that hydrogen at the benzyl position is extracted, thereby exhibiting excellent oxygen absorption performance (however, The operation of the present embodiment is not limited to these).

  Moreover, the oxygen absorptive resin composition of this embodiment can suppress the production | generation of the low molecular weight compound after oxygen absorption in the suitable aspect. The reason is not clear, but is presumed to be due to, for example, the following oxidation reaction mechanism. That is, in the polyester compound (a), hydrogen at the benzyl position of the tetralin ring is first extracted to generate a radical, and then the carbon at the benzyl position is oxidized by the reaction between the radical and oxygen to produce a hydroxy group or a ketone group. Is considered to generate. Therefore, in the oxygen-absorbing resin composition, the molecular chain is not broken by the oxidation reaction, and the structure of the polyester compound (a) is maintained. Therefore, a low molecular weight organic compound that causes odor is generated after oxygen absorption. As a result, the increase in odor intensity after oxygen absorption is suppressed, and it is presumed that the low molecular weight compound is prevented from being mixed into the contents (however, the action of this embodiment is limited to these). Not.)

  In the polyester compound (a) of the present embodiment, structural units having other tetralin rings other than the structural units (a) and (b) represented by the above (1) to (4), and / or A structural unit having no tetralin ring may be incorporated as a copolymerization component. Specifically, the compounds shown in the diol or its derivative (II) and the dicarboxylic acid or its derivative (IV) can be used as a copolymerization component.

  The structural ratio of the structural unit (a) and the structural unit (b) is preferably a molar ratio of 99.99: 0.01 to 90:10, and is 99.9: 0.01 to 95: 5. A molar ratio is more preferable, and a molar ratio of 99.5: 0.05 to 98: 2 is particularly preferable. When the composition ratio is in the above preferred range, a polyester compound (a) having an appropriate melt viscosity can be obtained while further suppressing the generation of gel.

The melt viscosity of the polyester compound (a) is preferably 150 Pa · sec or more, more preferably 200 Pa · sec, at a shear rate of 1216 sec ⁻¹ at 260 ° C. in consideration of molding processability to a practical form. That's it. When the melt viscosity is not less than the above-mentioned preferable range, the forming process into the multilayer bottomed tube becomes easier.

The molecular weight of the above-described polyester compound (a) can be appropriately set in consideration of desired performance and handling properties, and is not particularly limited. In general, the weight average molecular weight (Mw) is preferably 1.0 × 10 ^{3 to} 8.0 × 10 ⁶ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁶ . Similarly, the number average molecular weight (Mn) is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ , and more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁵ . In addition, all the molecular weights here mean the value of polystyrene conversion. In addition, a polyester compound (a) can be used individually by 1 type or in combination of 2 or more types.

  In addition, the glass transition temperature (Tg) of the polyester compound (a) is preferably 50 to 90 ° C., more preferably 60 to 80 ° C., considering the moldability to a practical form. When the glass transition temperature is not less than the above preferable range, the forming process into the multilayer bottomed tube becomes easier. The glass transition temperature here means a value measured by differential scanning calorimetry.

  All of the polyester compounds (a) described above have hydrogen at the benzylic position of the tetralin ring, and when used in combination with the transition metal catalyst described above, the hydrogen at the benzylic position is extracted, thereby providing an excellent oxygen absorption capacity. Is expressed.

  In addition, the oxygen-absorbing resin composition of the present embodiment is one in which the generation of low molecular weight compounds after oxygen absorption is suppressed. Although the reason is not clear, for example, the following oxidation reaction mechanism is assumed. That is, in the polyester compound (a), hydrogen at the benzyl position of the tetralin ring is first extracted to generate a radical, and then the carbon at the benzyl position is oxidized by the reaction between the radical and oxygen to produce a hydroxy group or a ketone group. Is considered to generate. Therefore, in the oxygen-absorbing resin composition of the present embodiment, the molecular chain is not broken by the oxidation reaction as in the above-described prior art, and the structure of the polyester compound (a) is maintained, so that the low molecular weight compound absorbs oxygen. It is difficult to produce later, and as a result, it is presumed that the low molecular weight compound is prevented from being mixed into the contents after oxygen absorption.

<Transition metal catalyst>
The transition metal catalyst used in the oxygen-absorbing resin composition of the present embodiment is appropriately selected from known ones as long as it can function as a catalyst for the oxidation reaction of the polyester compound (a). There is no particular limitation.

  Specific examples of the transition metal catalyst include, for example, organic acid salts, halides, phosphates, phosphites, hypophosphites, nitrates, sulfates, oxides and hydroxides of transition metals. Here, examples of the transition metal contained in the transition metal catalyst include, but are not limited to, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, and rhodium. Among these, manganese, iron, cobalt, nickel, and copper are preferable. Examples of organic acids include acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, Although capric acid and naphthenic acid are mentioned, it is not limited to these. The transition metal catalyst is preferably a combination of these transition metals and an organic acid, the transition metal is manganese, iron, cobalt, nickel or copper, and the organic acid is acetic acid, stearic acid, 2-ethylhexanoic acid, olein. A combination that is an acid or naphthenic acid is more preferred. In addition, a transition metal catalyst can be used individually by 1 type or in combination of 2 or more types.

  The compounding quantity of a transition metal catalyst can be suitably set according to the kind and desired performance of the said polyester compound (a) and transition metal catalyst to be used, and is not specifically limited. From the viewpoint of the oxygen absorption amount of the oxygen-absorbing resin composition, the blending amount of the transition metal catalyst is preferably 0.001 to 10 parts by mass as the transition metal amount with respect to 100 parts by mass of the polyester compound (a). More preferably, it is 0.002-2 mass parts, More preferably, it is 0.005-1 mass parts.

  The polyester compound (a) and the transition metal catalyst can be mixed by a known method, but can be preferably used as an oxygen-absorbing resin composition having good dispersibility by kneading with an extruder. Further, in the oxygen-absorbing resin composition, additives such as a desiccant, a pigment, a dye, an antioxidant, a slip agent, an antistatic agent, a stabilizer, etc., calcium carbonate, A filler such as clay, mica, and silica, a deodorant, and the like may be added, but various materials can be mixed without being limited to the above-described ones.

  Note that the oxygen-absorbing resin composition of the present embodiment may further contain a radical generator or a photoinitiator as necessary in order to promote the oxygen absorption reaction. Specific examples of the radical generator include various N-hydroxyimide compounds such as N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxyhexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3 -Hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxyphthalimide, 4-dimethylamino -N-hydroxyphthalimide, 4-carboxy-N-hydroxyhexahydrophthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide , N, N-dihydroxypyromellitic acid diimide and the like, but are not particularly limited thereto. Specific examples of the photoinitiator include, but are not limited to, benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, and the like. In addition, these radical generators and photoinitiators can be used individually by 1 type or in combination of 2 or more types.

<Other thermoplastic resins>
In addition, the oxygen-absorbing resin composition of the present embodiment can be kneaded with another thermoplastic resin and an extruder as long as the purpose of the present embodiment is not impaired. Examples of the thermoplastic resin used for kneading include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, polypropylene, poly-1-butene, and poly-4-methyl. -1-pentene, polyolefins such as random or block copolymers of α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, etc. Acid-modified polyolefin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene- (meth) acrylic acid copolymer and its ionic cross-linked product (ionomer), ethylene- Methyl methacrylate copolymer, etc. Styrene resins such as ethylene-vinyl compound copolymer, polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer, polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate, nylon 6, nylon 66, nylon 610, nylon 12, polyamide such as polymetaxylylene adipamide (MXD6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), glycol Modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkano Polyester over preparative like, polycarbonate, polyether, or mixtures thereof, such as polyethylene oxide.

  The thickness of the oxygen absorbing layer (layer A) is preferably from 1 to 1000 μm, more preferably from 50 to 900 μm, from the viewpoint of having oxygen absorption performance and ensuring various physical properties required for the multilayer bottomed tube. More preferably, it is 100-800 micrometers.

<Resin layer (layer B) containing polyester (b)>
The polyester (b) described here is a polyester that can be used for the resin layer (layer B), and is not a polyester compound (a) that is suitably used for the oxygen-absorbing layer of the present embodiment. In the present embodiment, the polyester (b) is one or more selected from a polyhydric carboxylic acid containing a dicarboxylic acid and one or more of these ester-forming derivatives and a polyhydric alcohol containing a glycol. Or consisting of a hydroxycarboxylic acid and an ester-forming derivative thereof, or consisting of a cyclic ester. The ethylene terephthalate-based thermoplastic polyester is composed of an ethylene terephthalate unit in the majority of ester repeating units, generally 70 mol% or more, and has a glass transition point (Tg) of 50 to 90 ° C. and a melting point (Tm) of 200 to 275. Those in the range of ° C. are preferred. Polyethylene terephthalate is particularly excellent as an ethylene terephthalate thermoplastic polyester in terms of pressure resistance, heat resistance, heat pressure resistance, etc. In addition to ethylene terephthalate units, dibasic acids such as isophthalic acid and naphthalenedicarboxylic acid and diols such as propylene glycol Copolyesters containing a small amount of ester units consisting of can also be used.

  A known polyester can be used for the polyester (b). Specific examples thereof include polyesters described in International Publication No. 2013/077436. Among them, a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol is preferable.

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

  The content of the polyester (b) in the layer B can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass with respect to the total amount of the layer B. %, More preferably 90 to 100% by mass.

  The multilayer bottomed tube of this embodiment may have a plurality of layers B, and the configurations of the plurality of layers B may be the same or different from each other. The thickness of the layer B can be appropriately determined according to the application and is not particularly limited, but is preferably 50 to 10,000 μm, more preferably 100 to 100 μm from the viewpoint of ensuring various physical properties required for the sample culture multilayer container. It is 7000 μm, more preferably 300 to 5000 μm.

<Adhesive layer>
The multilayer bottomed tube of this embodiment includes an arbitrary layer in addition to the above-described oxygen absorbing layer (layer A) and the resin layer (layer B) containing polyester (b), depending on the desired performance and the like. You may go out. Examples of such an arbitrary layer include an adhesive layer.

  For example, from the viewpoint of further increasing the interlayer adhesive strength between two adjacent layers, it is preferable to provide an adhesive layer (layer AD) between the two layers. The adhesive layer preferably contains a thermoplastic resin having adhesiveness. As the thermoplastic resin having adhesiveness, for example, an acid modification 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 Polyolefin resin; polyester-based thermoplastic elastomer mainly composed of a polyester-based block copolymer. The thickness of the adhesive layer is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 90 μm, and still more preferably from the viewpoint of ensuring molding processability while exhibiting practical adhesive strength. Is 10-80 μm.

<Manufacturing method of multilayer bottomed tube>
The manufacturing method of the multilayer bottomed tube of this embodiment can apply a well-known method according to the property of various materials, the target shape, etc., and is not specifically limited. For example, a multilayer container can be manufactured by applying various injection molding methods.

  The thickness of the multilayer bottomed tube of the present embodiment is not particularly limited, but is preferably 3 to 5000 μm, more preferably 5 to 5 μm from the viewpoint of enhancing oxygen absorption performance and ensuring various physical properties required for the sample culture vessel. It is 4500 micrometers, More preferably, it is 10-4000 micrometers.

  The injection molded body of this embodiment may itself be molded into a desired shape. Moreover, it can also shape | mold into a desired container shape by giving secondary processing to the obtained injection molded object. As the secondary processing, blow molding or the like can be applied.

  As a method other than the injection molding method, for example, a multilayer molded body can be obtained by a compression molding method. For example, an oxygen-absorbing composition is provided in a thermoplastic resin melt, and the molten mass is made into a male mold. While supplying, it compresses with a female type | mold, and a multilayer molded object can be obtained by cooling and solidifying a compression molding.

  Further, as a method other than the injection molding method and the compression molding method, a multilayer molded body can be obtained by an extrusion blow molding method. For example, a cylindrical parison using an extrusion blow device comprising a plurality of extruders and a cylindrical die. The parison is extruded into a tube shape, the parison is sandwiched between molds, the parison lower part is pinched off and fused, and blown by high-pressure air or the like before being cooled, to expand the parison A multilayer molded body can be obtained.

  For example, injection blow molding, extrusion blow molding or the like is suitable as a method for forming the multilayer bottomed tube of the present embodiment. As a specific example, an injection blow molding method is shown below. For example, using a molding machine equipped with two or more injection machines and an injection mold, the material constituting the layer A and the material constituting the layer B are passed through the mold hot runners from the respective injection cylinders, and the injection mold. By injecting into the cavity of the mold, a multilayer injection molded body having a three-layer structure B / A / B having a shape corresponding to the cavity shape of the injection mold can be manufactured. First, the material constituting the layer B is injected from the injection cylinder, then the material constituting the layer A is injected from another injection cylinder simultaneously with the resin constituting the layer B, and then the resin constituting the layer B By injecting a necessary amount of the solution to fill the cavity, a multilayer injection molded body having a three-layer structure B / A / B can be manufactured. Furthermore, by first injecting the material constituting the layer B, then injecting the material constituting the layer A alone, and finally injecting the necessary amount of the material constituting the layer B to fill the mold cavity, A multilayer injection molded article having a five-layer structure B / A / B / A / B can be produced. Still further, first, the material constituting the layer B1 is injected from the injection cylinder, then the material constituting the layer B2 is injected from another injection cylinder simultaneously with the resin constituting the layer B1, and then the layer A is constituted. By injecting the resin simultaneously with the resins constituting the layers B1 and B2, and then injecting a necessary amount of the resin constituting the layer B1 to fill the cavity, the five-layer structure B1 / B2 / A / B2 / B1 A multilayer injection molded article can be produced. In this injection blow molding, the multilayer injection molded body obtained by the above method is fitted in a final shape mold (blow mold) while being heated to some extent, and air is blown and inflated into the mold. It can be formed into a bottle shape by closely contacting and solidifying by cooling.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, NMR measurements were performed at room temperature. Moreover, the various physical-property values of the polymer obtained by the polymer manufacture example were measured with the following measuring methods and measuring apparatuses.

(Measurement method of glass transition temperature)
The glass transition temperature was measured according to JIS K7122. The measuring apparatus used was “DSC-60” manufactured by Shimadzu Corporation.

(Measuring method of melt viscosity)
The melt viscosity was obtained by drying the obtained tetralin ring-containing polyester compound (a) under reduced pressure for 24 hours at a temperature 10 ° C. lower than the glass transition temperature to remove moisture, and using a capillary rheometer “Capillograph 1D” manufactured by Toyo Seiki Seisakusho Co., Ltd. , Measured at a temperature of 260 ° C. and a shear rate of 1216 sec −1.

(Measuring method of melting point)
The melting point was determined by measuring the DSC melting point peak temperature according to ISO11357. The measuring apparatus used was “DSC-60” manufactured by Shimadzu Corporation.

(Measurement method of weight average molecular weight and number average molecular weight)
The weight average molecular weight and the number average molecular weight were measured by GPC-LALLS. The measuring device used was “HLC-8320GPC” manufactured by Tosoh Corporation.

<Example of monomer synthesis>
An autoclave having an internal volume of 18 L was charged with 2.20 kg of dimethyl naphthalene-2,6-dicarboxylate, 11.0 kg of 2-propanol, and 350 g (50 wt% water-containing product) of 5% palladium supported on activated carbon. Next, after the air in the autoclave was replaced with nitrogen, and further nitrogen was replaced with hydrogen, hydrogen was supplied until the pressure in the autoclave reached 0.8 MPa. Next, the agitator was started, the rotation speed was adjusted to 500 rpm, the internal temperature was raised to 100 ° C. over 30 minutes, and hydrogen was further supplied to make the pressure 1 MPa. Thereafter, the supply of hydrogen was continued to maintain 1 MPa in accordance with the pressure drop due to the progress of the reaction. Since the pressure drop disappeared after 7 hours, the autoclave was cooled, unreacted residual hydrogen was released, and then the reaction solution was taken out from the autoclave. The reaction solution was filtered to remove the catalyst, and then 2-propanol was evaporated from the separated filtrate with an evaporator. To the obtained crude product, 4.40 kg of 2-propanol was added and purified by recrystallization to obtain dimethyl tetralin-2,6-dicarboxylate in a yield of 80%. The NMR analysis results are as follows. 1H-NMR (400 MHz CDCl3) δ 7.76-7.96 (2H m), 7.15 (1H d), 3.89 (3H s), 3.70 (3H s), 2.70-3.09 (5H m), 1.80-1.95 (1H m) .

<Examples of polymer production>
(Production Example 1)
Tetralin-2,6-dicarboxylic acid obtained in the monomer synthesis example in a polyester resin production apparatus equipped with a fractionator, a total condenser, a cold trap, a stirrer, a heating device, and a nitrogen introduction pipe, etc. Dimethyl 543 g, ethylene glycol 217 g, 1.0 g of glycerin as a polyfunctional compound, 0.038 g of tetrabutyl titanate, and 0.15 g of zinc acetate were charged, and the temperature was raised to 230 ° C. in a nitrogen atmosphere to perform a transesterification reaction. After the reaction conversion rate of the dicarboxylic acid component was set to 90% or more, the temperature was increased and the pressure was gradually reduced over 90 minutes, and polycondensation was performed at 260 ° C. and 133 Pa or less for 1 hour to obtain a tetralin ring-containing polyester compound (a1). Obtained.

As a result of measuring the weight average molecular weight and number average molecular weight of the obtained polyester compound (a1) by GPC (gel permeation chromatography), the weight average molecular weight in terms of polystyrene was 7.0 × 10 ⁴ , and the number average molecular weight was It was 3.0 × 10 ⁴ . As a result of measuring the glass transition temperature and the melting point by DSC, the glass transition temperature was 69 ° C. and the melting point was not recognized because it was amorphous. Moreover, the melt viscosity of the polyester compound (a1) was measured. These results are shown in Table 1.

(Production Example 2)
A tetralin ring-containing polyester compound (a2) was synthesized in the same manner as in Example 1 except that the amount of glycerin was 2.0 g. The obtained polyester compound (a2) has a weight-average molecular weight in terms of polystyrene of 8.0 × 10 ⁴ , a number-average molecular weight of 3.1 × 10 ⁴ , a glass transition temperature of 67 ° C., and a melting point of amorphous. There wasn't. Moreover, the melt viscosity of the polyester compound (a2) was measured. The results are shown in Table 1.

(Production Example 3)
A tetralin ring-containing polyester compound (a3) was synthesized in the same manner as in Production Example 1 except that 0.6 g of pentaerythritol was used instead of glycerin. The obtained polyester compound (a3) has a polystyrene-equivalent weight average molecular weight of 7.1 × 10 ⁴ , a number average molecular weight of 3.4 × 10 ⁴ , a glass transition temperature of 68 ° C., and a melting point of amorphous. There wasn't. Moreover, the melt viscosity of the polyester compound (a3) was measured. The results are shown in Table 1.

(Production Example 4)
A tetralin ring-containing polyester compound (a4) was synthesized in the same manner as in Production Example 1 except that 2.3 g of trimellitic acid was used instead of glycerin. The obtained polyester compound (a4) has a polystyrene-equivalent weight average molecular weight of 6.9 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ , a glass transition temperature of 70 ° C., and a melting point of amorphous. There wasn't. Moreover, the melt viscosity of the polyester compound (a4) was measured. The results are shown in Table 1.

(Production Example 5)
150 g of ethylene glycol of Production Example 1 is further charged with 93 g of 1,4-butanediol, and in the same manner as in Production Example 1, a polyester compound (a5) having a molar ratio of ethylene glycol to 1,4-butanediol of 60:40 Was synthesized. The weight average molecular weight in terms of polystyrene of the polyester compound (a5) was 7.5 × 10 ⁴ , the number average molecular weight was 3.2 × 10 ⁴ , the glass transition temperature was 56 ° C., and the melting point was not recognized because it was amorphous. Moreover, the melt viscosity of the polyester compound (a5) was measured. The results are shown in Table 1.

(Production Example 6)
The amount of ethylene glycol of Production Example 1 was changed to 54 g, and further, 236 g of 1,4-butanediol was charged, and in the same manner as in Production Example 1, a polyester compound (a6) having a molar ratio of ethylene glycol to 1,4-butanediol of 10:90 Was synthesized. The polyester compound (a6) had a polystyrene equivalent weight average molecular weight of 7.8 × 10 ⁴ , a number average molecular weight of 2.9 × 10 ⁴ , a glass transition temperature of 39 ° C., and a melting point of 133 ° C. Moreover, the melt viscosity of the polyester compound (a6) was measured. The results are shown in Table 1.

(Production Example 7)
The ethylene glycol of Production Example 1 was changed to 1,4-butanediol, 315 g was charged, and a polyester compound (a7) was synthesized in the same manner as Production Example 1. The polyester compound (a7) had a polystyrene equivalent weight average molecular weight of 8.1 × 10 ⁴ , a number average molecular weight of 3.1 × 10 ⁴ , a glass transition temperature of 36 ° C., and a melting point of 145 ° C. Moreover, the melt viscosity of the polyester compound (a7) was measured. The results are shown in Table 1.

<Manufacture of multi-layered bottomed tube>

  Under the following conditions, the material constituting the layer B is injected from the injection cylinder, then the material constituting the layer A is injected from another injection cylinder at the same time as the resin constituting the layer B, and then the layer B is constituted. After injection of the required amount of resin to fill the cavity in the injection mold, an injection molded body having a three-layer structure of B / A / B is obtained, and then the injection molded body is cooled to a predetermined temperature, and a blow mold A multilayer bottomed tube (bottle part) was manufactured by performing blow molding after shifting to. The total mass of the multilayer bottomed tube was 20 g, and the mass of the layer A was 30% by mass of the total mass of the multilayer bottomed tube. Polyethylene terephthalate (manufactured by Nippon Unipet, trade name: BK-2180, hereinafter also referred to as PET (1)) was used as the resin constituting the layer B.

(Shape of multilayer bottomed tube)
The total length was 75 mm, the outer diameter was 12 mmφ, and the wall thickness was 1.2 mm. An injection molding machine (manufactured by UNILOY, model: IBS 85, 4 pieces) was used for the production of the multilayer bottomed tube.
(Conditions for multilayer bottomed tube)
Injection cylinder temperature for layer A: 260 ° C
Injection cylinder temperature for layer B: 300 ° C
Resin flow path temperature in injection mold: 300 ° C
Injection mold temperature: 30 ° C

<Evaluation of multilayer blood collection tubes>
The oxygen permeability and vacuum retention of the multilayer blood collection tubes obtained in Examples and Comparative Examples were measured and evaluated by the following methods.

(1) Oxygen transmission rate (OTR) of multilayer container
The oxygen permeability on the 30th day from the start of measurement was measured in an atmosphere of 23 ° C., 50% relative humidity outside the molded body, and 100% relative humidity inside. For the measurement, an oxygen permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2-21 ML) was used. The lower the measured value, the better the oxygen barrier property. The lower limit of detection of the measurement is oxygen permeability 5 × 10 ⁻⁵ mL / (0.21 atm · day · package).

(2) Measurement of vacuum retention rate A multilayer blood collection tube was prepared in which a stopper having a needle piercing portion through which a blood collection needle could be inserted was attached to the opening of the multilayer bottomed tube. The blood inside the multilayer blood collection tube was evacuated using a vacuum pump through the blood collection needle, and then the blood collection needle was pulled out. The multilayer blood collection tube was stored in an atmosphere of 23 ° C. and 50% relative humidity for 40 days, and then a blood collection needle having one end in water was pierced through the needle piercing portion, and the amount of water absorption was measured. Further, the amount of water absorption (0 hours of storage) immediately after the multilayer blood collection tube was exhausted was measured, and the vacuum retention rate was obtained from the following equation.

Vacuum retention rate = (suction amount after 40 days of storage) / (suction amount after 0 hours of storage)

Example 1
To 100 parts by mass of the polyester compound (a1), cobalt stearate (II) was dry blended so that the amount of cobalt was 0.02 parts by mass to obtain an oxygen-absorbing resin composition. A multilayer blood collection tube was manufactured and evaluated using the oxygen-absorbing resin composition as the resin constituting the layer A. The results are shown in Table 2.

(Examples 2 to 7)
A multilayer blood collection tube was produced and evaluated in the same manner as in Example 1 except that the polyester compound (a1) was changed to the polyester compound (a2) to the polyester compound (a7) shown in Table 1. The results are shown in Table 2.

(Comparative Example 1)
A single-layer blood collection tube having the same shape as in Example 1 was produced using PET (1) used in Layer B in Example 1, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

  As is clear from Table 2, it was confirmed that the multilayer blood collection tubes of Examples 1 to 7 have extremely low oxygen permeability and excellent gas barrier properties.

  The multilayer blood collection tube of the present invention can be effectively used because it has extremely low oxygen permeability and excellent vacuum resistance.

Claims (11)

It has at least three layers of a resin layer containing polyester (b), an oxygen absorbing layer containing an oxygen-absorbing resin composition, and a resin layer containing polyester (b) in this order, and has a multilayer having an opening. The bottom tube,
A stopper having a needle piercing portion through which a blood collection needle can be pierced;
A multilayer blood collection tube.   The multilayer blood collection tube according to claim 1, wherein the oxygen-absorbing resin composition contains a compound having a tetralin ring and a transition metal catalyst. The compound having the tetralin ring is represented by the following general formulas (1) to (4).

(In the formula, each R independently represents a monovalent substituent, and the monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, or a hydroxy group. At least selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group These may be further substituted, m represents an integer of 0 to 3, n represents an integer of 0 to 7, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring. X is selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. It represents a divalent group containing at least one group barrel.)
A structural unit (a) having at least one tetralin ring selected from the group consisting of:
A structural unit derived from at least one polyfunctional compound selected from the group consisting of a trihydric or higher polyhydric alcohol, a trivalent or higher polyvalent carboxylic acid and its derivative, and a trivalent or higher hydroxycarboxylic acid and its derivative. The multilayer blood collection tube according to claim 2, which is a polyester compound (a) having (b).   The polyester compound (a) contains the structural unit (a) represented by the general formula (1) and the structural unit (b) in a molar ratio of 99.99: 0.01 to 90:10. The multilayer blood collection tube according to claim 3.   The proportion of the structural unit (a) in which X in the general formula (1) is an ethylene group and / or a tetramethylene group is 95 mol% or more based on all the structural units (a) of the polyester compound (a). The multilayer blood collection tube according to any one of claims 3 and 4, wherein   The ratio of the structural unit (a) whose X in the said General formula (1) is an ethylene group is 60 mol% or more with respect to all the structural units (a) which the said polyester compound (a) has. The multilayer blood collection tube in any one of -5.   The ratio of the structural unit (a) in which X in the general formula (1) is an ethylene group to all the structural units (a) of the polyester compound (a) is 95 mol% or more. A multilayer blood collection tube according to any one of the above. The multilayer blood collection tube according to any one of claims 3 to 7, wherein the polyester compound (a) has a melt viscosity value at 150 ° C at a shear rate of 1216 sec ^-1 of 150 Pa · sec or more.   The multilayer blood collection tube according to any one of claims 3 to 8, wherein the polyester compound (a) has a glass transition temperature value of 50C or higher.   The multilayer blood collection tube according to any one of claims 2 to 9, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel and copper.   The multilayer blood collection tube according to any one of claims 2 to 10, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the polyester compound (a).