JPH10230160A - Oxygen absorptive resin composition and its molded body - Google Patents
Oxygen absorptive resin composition and its molded bodyInfo
- Publication number
- JPH10230160A JPH10230160A JP9347521A JP34752197A JPH10230160A JP H10230160 A JPH10230160 A JP H10230160A JP 9347521 A JP9347521 A JP 9347521A JP 34752197 A JP34752197 A JP 34752197A JP H10230160 A JPH10230160 A JP H10230160A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- resin composition
- resin
- oxygen absorbing
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、食品などの保存時
に用いられる酸素吸収体に成りうる酸素吸収性樹脂組成
物に関する。さらに詳しくは、酸素吸収性能に優れ、臭
気発生の少なく、食品などの香りを損なわない酸素吸収
体として有用な酸素吸収性樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-absorbing resin composition which can be used as an oxygen absorber for preserving foods and the like. More specifically, the present invention relates to an oxygen-absorbing resin composition having excellent oxygen-absorbing performance, generating less odor, and being useful as an oxygen absorber that does not impair the scent of foods and the like.
【０００２】[0002]
【従来の技術】食品をはじめ種々の製品の包装等におい
て、酸素の存在により品質等が変化するのを防止するた
めに、酸素除去を目的に酸素吸収剤が用いられる場合が
多い。酸素吸収剤の形態としては、粉末状、または粒状
酸素吸収剤を通気性を有する素材で包装した酸素吸収体
が用いられてきた。しかしながら、包装が完全ではない
と粉末状、粒状酸素吸収剤が漏れて飛散する等の問題が
あった。これらの問題を解決する目的で、例えば、樹脂
に酸素吸収剤を練込み、フィルム、シート、包装用容器
（特開平４−９０８４８）に成形した成形体が提案され
ている。2. Description of the Related Art In the packaging of various products including foods, an oxygen absorbent is often used for the purpose of removing oxygen in order to prevent a change in quality or the like due to the presence of oxygen. As a form of the oxygen absorber, an oxygen absorber obtained by packaging a powdery or granular oxygen absorber with a material having air permeability has been used. However, if the packaging is not complete, there is a problem that the powdery or granular oxygen absorbent leaks and scatters. For the purpose of solving these problems, there has been proposed, for example, a molded product obtained by kneading an oxygen absorbent into a resin and molding it into a film, a sheet, or a packaging container (Japanese Patent Application Laid-Open No. 4-90848).
【０００３】[0003]
【発明が解決しようとする課題】上記のような酸素吸収
性フィルム等を成形する際には、樹脂の劣化を防止する
ために酸化防止剤を添加して酸素吸収性樹脂組成物を作
製しており、その中でもヒンダードフェノール系酸化防
止剤を用いるのが一般的であった。しかしながら、従来
の酸素吸収性樹脂組成物を作製すると樹脂の分解等に起
因すると考えられる臭気が発生する場合があり、これを
成形した酸素吸収体と共に食品を包装すると、この酸素
吸収性樹脂組成物由来の臭気成分が食品に移行し、包装
された食品自体の味や香味を損なう場合があり、問題と
なっていた。When the above-described oxygen-absorbing film is formed, an oxygen-absorbing resin composition is prepared by adding an antioxidant to prevent deterioration of the resin. Among them, a hindered phenol-based antioxidant is generally used. However, when a conventional oxygen-absorbing resin composition is produced, an odor which may be caused by decomposition of the resin may be generated. When food is packaged together with an oxygen absorber molded from the resin, the oxygen-absorbing resin composition Odor components derived from the foodstuffs migrate to the food, which may impair the taste and flavor of the packaged food itself, which has been a problem.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
に鑑み、高い酸素吸収性能を有しかつ臭気発生の少ない
酸素吸収体、あるいは酸素吸収性容器と成りうる酸素吸
収樹脂組成物の開発について鋭意検討した結果、熱可塑
性樹脂と酸素吸収剤との混練時の熱劣化を防止するため
に添加する酸化防止剤の中でヒンダードフェノール系酸
化防止剤を使用した場合、金属系酸素吸収剤との相互作
用により酸化防止剤の分解が起こり、この分解物が、酸
素吸収性樹脂組成物由来の臭気成分の一つと成りうるこ
とを見出し、本発明に至った。すなわち、本発明は、金
属系酸素吸収剤と熱可塑性樹脂組成物とを混練してなる
酸素吸収性樹脂組成物であって、ヒンダードフェノール
系酸化防止剤を実質的に含有しないことを特徴とする酸
素吸収性樹脂組成物およびそれを成形してなる酸素吸収
性樹脂成形体に関するものである。Means for Solving the Problems In view of the above problems, the present inventors have developed an oxygen-absorbing resin composition having high oxygen-absorbing performance and low odor generation, or an oxygen-absorbing resin composition which can be used as an oxygen-absorbing container. As a result of intensive studies on the development, when a hindered phenol-based antioxidant is used as an antioxidant to prevent thermal deterioration during kneading of a thermoplastic resin and an oxygen absorber, the metal-based oxygen absorber It has been found that the antioxidant is decomposed by the interaction with the agent, and that the decomposed product can be one of the odor components derived from the oxygen-absorbing resin composition, and the present invention has been accomplished. That is, the present invention is an oxygen-absorbing resin composition obtained by kneading a metal-based oxygen absorber and a thermoplastic resin composition, and is characterized by substantially not containing a hindered phenol-based antioxidant. The present invention relates to an oxygen-absorbing resin composition to be formed and an oxygen-absorbing resin molded article obtained by molding the same.
【０００５】[0005]
【発明の実施の形態】以下本発明について詳細に説明す
る。本発明の特徴は、酸素吸収剤と熱可塑性樹脂とを混
練する際に、酸素吸収剤と樹脂との混練成形中における
樹脂の熱劣化が起こりにくい場合には、酸化防止剤を使
用しなくてよく、熱可塑性樹脂の熱劣化を防止するため
に酸化防止剤を添加する場合には、ヒンダードフェノー
ル系酸化防止剤以外の酸化防止剤を使用することであ
る。本発明の酸素吸収性樹脂成形体とは、特に限定され
るものではないが、酸素吸収樹脂組成物を例えば、フィ
ルム、シート、容器等に成形した成形体である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The feature of the present invention is that, when kneading the oxygen absorbent and the thermoplastic resin, when the resin hardly deteriorates during the kneading and molding of the oxygen absorbent and the resin, it is not necessary to use an antioxidant. When adding an antioxidant to prevent thermal deterioration of the thermoplastic resin, an antioxidant other than a hindered phenol-based antioxidant is often used. The oxygen-absorbing resin molded article of the present invention is not particularly limited, but is a molded article obtained by molding the oxygen-absorbing resin composition into, for example, a film, a sheet, a container, or the like.
【０００６】本発明でいうヒンダードフェノール系酸化
防止剤とは、フェノール骨格中の水酸基のオルト位のど
ちらか一方、または両方に、嵩高い置換基、例えば、t-
ブチル基等が置換されているフェノール系酸化防止剤を
意味する。例示するならば、２−t-ブチル−４−メトキ
シフェノール、２，４−ジメチル−６−t-ブチルフェノ
ール、２，６−ジ−t-ブチル−ｐ−クレゾール、ｎ−オ
クタドデシル−β−（４’−ヒドロキシ−３’，５’−
t-ブチルフェニル）プロピオネート、スチレン化フェノ
ール、２，２’−メチレンビス（４−メチル−６−t-ブ
チルフェノール）、２，２’−メチレンビス（４−メチ
ル−シクロヘキシルフェノール）、２，２’−チオビス
（４−メチル−６−t-ブチルフェノール）、２，５−ジ
−t-アミルヒドロキノン、テトラキス[メチレン−３−
（３’，５’−ジ−t-ブチル−４−ヒドロキシフェニ
ル）プロピオネート]メタン、等が挙げられる。[0006] The hindered phenolic antioxidant referred to in the present invention is a bulky substituent, for example, t-substituted at one or both of the ortho positions of the hydroxyl group in the phenol skeleton.
It means a phenolic antioxidant in which a butyl group or the like is substituted. For example, 2-t-butyl-4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol, n-octadodecyl-β- ( 4'-hydroxy-3 ', 5'-
(t-butylphenyl) propionate, styrenated phenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-cyclohexylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane.
【０００７】本発明は、金属系酸素吸収剤と熱可塑性樹
脂とを混錬してなる組成物であって、ヒンダードフェノ
ール系酸化防止剤を実質的に含有しないことを特徴とす
る酸素吸収性樹脂組成物であるが、ヒンダードフェノー
ル系酸化防止剤は、原料の熱可塑性樹脂を重合後、長期
間保管する間の劣化を防止するために、極少量（１００
ｐｐｍ前後）添加しておくことが慣用的に行われている
が、この程度の酸化防止剤の添加量は、本発明では許容
できるものである。本発明でヒンダードフェノール系酸
化防止剤を実質的に含有しないとは、この程度の酸化防
止剤の添加量は、許容できるものであり、実質的に含有
しないとは、例えば、金属系酸素吸収剤と熱可塑性樹脂
とを混錬する際に新たにヒンダードフェノール系酸化防
止剤を添加しないことも含まれるものである。The present invention provides a composition obtained by kneading a metal-based oxygen absorbent and a thermoplastic resin, wherein the composition is substantially free of a hindered phenol-based antioxidant. Although it is a resin composition, the hindered phenolic antioxidant is used in a very small amount (100%) in order to prevent deterioration during long-term storage after polymerization of the raw material thermoplastic resin.
(about ppm) is conventionally added, but such an amount of the antioxidant is acceptable in the present invention. In the present invention, "substantially not containing a hindered phenolic antioxidant" means that the addition amount of an antioxidant of this level is acceptable, and "substantially not containing" means, for example, that of a metal-based oxygen absorbing agent. This does not include the addition of a new hindered phenolic antioxidant when kneading the agent and the thermoplastic resin.
【０００８】また、本発明では、必要に応じてヒンダー
ドフェノール系酸化防止剤以外の酸化防止剤を添加する
ことができるが、熱可塑性樹脂に対する熱劣化防止効
果、安全性、より臭気発生を低減させるためには、トコ
フェロールを用いることが好ましい。トコフェロールの
立体構造はｄ体、ｌ体どちらでも良い。また、単一組成
物である必要はなく、混合物でも良い。また、トコフェ
ロールの同族体としてはα、β、γ、δいずれでも良
く、さらに、かならずしも単一組成物である必要はな
く、2種以上の同族体の混合物でもよい。これらの中で
もα体単一組成が好ましい。In the present invention, an antioxidant other than the hindered phenolic antioxidant can be added as necessary, but the effect of preventing thermal deterioration of the thermoplastic resin, safety, and further reducing odor generation are provided. To do so, it is preferable to use tocopherol. The three-dimensional structure of tocopherol may be either d-form or l-form. Further, the composition need not be a single composition, but may be a mixture. Further, homologues of tocopherol may be any of α, β, γ, and δ, and need not necessarily be a single composition, and may be a mixture of two or more homologues. Among them, a single α-form composition is preferable.
【０００９】本発明に用いられる金属系酸素吸収剤とは
通常、鉄粉、亜鉛末、銅末、アルミニウム末等が用いら
れる。なかでも、酸素吸収性能、ハンドリング性の面よ
り鉄系が好ましく用いられる。さらに、鉄系において
も、還元鉄、あるいは部分酸化された鉄粉がより好まし
く用いられるが、還元鉄と比較して酸素吸収速度の観点
から、部分酸化鉄粉がさらに好ましい。なお、還元鉄と
は後述するような元素分析的手法により求められる酸素
組成比が０．８ｗｔ％未満の鉄をいい、部分酸化鉄と
は、同様にして求められる酸素組成比が０．８ｗｔ％以
上１０ｗｔ％未満のものであり、酸素組成比が５ｗｔ％
未満がより好ましい。また、これら酸素吸収剤の形状に
ついて、その粒径は、取り扱い易さの点より５μｍ以上
が好ましく、得られる酸素吸収体の酸素吸収性能の点よ
り２００μｍ以下が好ましい。また、金属系酸素吸収剤
の酸素吸収速度を促進させるために酸素吸収体に電解質
を含有させてもよい。かかる電解質としては、例えば、
アルカリ金属、アルカリ土類金属のハロゲン化物、炭酸
塩、硫酸塩、または水酸化物等が挙げられる。これら塩
類の中でも ハロゲン化物が好ましく、ＣａＣｌ2、Ｍ
ｇＣｌ2、ＮａＣｌ等がさらに好ましい。これら電解質
の添加量は、適宜選択すればよいが、通常、酸素吸収剤
に対して１〜１０重量％である。酸素吸収体に電解質を
含有させる方法としては、電解質を酸素吸収剤と別に樹
脂に混合しても良いし、酸素吸収剤の表面にあらかじめ
コーティングしておいても良い。特に、得られる酸素吸
収体の酸素吸収性能の面より、電解質を酸素吸収剤にあ
らかじめコーティングしたものの方が好ましい。例えば
部分酸化鉄粉にコーティングする場合、あらかじめ部分
酸化した鉄粉を用いてもよいし、コーティング中または
コーティング後に部分酸化させてもよい。As the metal-based oxygen absorbent used in the present invention, iron powder, zinc powder, copper powder, aluminum powder and the like are usually used. Of these, iron is preferably used in terms of oxygen absorption performance and handling properties. Further, in the iron system, reduced iron or partially oxidized iron powder is more preferably used, but partially iron oxide powder is more preferable from the viewpoint of oxygen absorption rate as compared with reduced iron. Note that reduced iron refers to iron having an oxygen composition ratio of less than 0.8 wt% determined by an elemental analysis method as described later, and partial iron oxide has an oxygen composition ratio of 0.8 wt% similarly determined. Not less than 10 wt% and the oxygen composition ratio is 5 wt%
Less than is more preferable. The particle size of these oxygen absorbents is preferably 5 μm or more from the viewpoint of ease of handling, and is preferably 200 μm or less from the viewpoint of the oxygen absorbing performance of the obtained oxygen absorber. Further, an electrolyte may be contained in the oxygen absorber in order to promote the oxygen absorption rate of the metal-based oxygen absorber. As such an electrolyte, for example,
Examples include alkali metal, alkaline earth metal halides, carbonates, sulfates, and hydroxides. Of these salts, halides are preferred, and CaCl 2 , M
gCl 2 , NaCl and the like are more preferred. The addition amount of these electrolytes may be appropriately selected, and is usually 1 to 10% by weight based on the oxygen absorbent. As a method for allowing the oxygen absorber to contain the electrolyte, the electrolyte may be mixed with the resin separately from the oxygen absorber, or the surface of the oxygen absorber may be coated in advance. In particular, from the viewpoint of the oxygen absorption performance of the obtained oxygen absorber, those obtained by coating the electrolyte with an oxygen absorbent in advance are preferable. For example, when coating the partially oxidized iron powder, the partially oxidized iron powder may be used in advance, or the partially oxidized powder may be partially oxidized during or after coating.
【００１０】本発明の酸素吸収性樹脂組成物に用いられ
る熱可塑性樹脂としては、例えば、高圧重合等で得られ
る長鎖分岐を有する低密度ポリエチレン、チーグラー法
等による高密度ポリエチレン、ポリプロピレン、ポリブ
テン、ポリメチルペンテン等のエチレンまたは炭素数３
〜１２のα−オレフィンのホモポリマー、またはエチレ
ンと炭素数３〜１２のα−オレフィンとの共重合により
得られる線状中密度、線状低密度ポリエチレン、プロピ
レン−エチレン共重合体、プロピレン−ブテン共重合
体、エチレン−プロピレン−ブテン共重合体等のエチレ
ン、または炭素数４〜１２のα−オレフィンの少なくと
も１種とプロピレンとのランダム共重体、プロピレン単
独重合等を行った後、連続してプロピレンとエチレンと
を重合して得られるブロック共重合体、エチレンと酢酸
ビニルおよび／または（メタ）アクリル酸エステルとの
共重合体、エチレンとアクリル酸との共重合体の金属
塩、などのオレフィン系樹脂や、ポリエステル系樹脂、
ポリアミド系樹脂等が挙げられる。本発明に用いられる
熱可塑性樹脂は、２種以上の混合物であっても良い。上
記例示した熱可塑性樹脂の中でも、ポリオレフィン系樹
脂が好ましい。ポリオレフィン系樹脂のなかでも得られ
る酸素吸収体の臭気がより制御されるという点では、１
９０℃でのメルトフローレートが０．１〜２０ｇ／１０
分である線状中密度、線状高密度ポリエチレン、２３０
℃でのメルトフローレートが１〜２０ｇ／１０分のポリ
プロピレン系樹脂が好ましい。The thermoplastic resin used in the oxygen-absorbing resin composition of the present invention includes, for example, low-density polyethylene having long-chain branches obtained by high-pressure polymerization, high-density polyethylene by Ziegler method, polypropylene, polybutene, and the like. Ethylene such as polymethylpentene or carbon number 3
To α-olefins having a homogeneity of from 1 to 12, or a linear medium density, linear low-density polyethylene, propylene-ethylene copolymer, propylene-butene obtained by copolymerizing ethylene with an α-olefin having 3 to 12 carbon atoms Copolymer, ethylene such as ethylene-propylene-butene copolymer, or a random copolymer of propylene with at least one kind of α-olefin having 4 to 12 carbon atoms, propylene homopolymerization and the like, and then continuously. Olefins such as block copolymers obtained by polymerizing propylene and ethylene, copolymers of ethylene with vinyl acetate and / or (meth) acrylate, and metal salts of copolymers of ethylene with acrylic acid Resin, polyester resin,
Polyamide-based resins and the like can be mentioned. The thermoplastic resin used in the present invention may be a mixture of two or more kinds. Among the thermoplastic resins exemplified above, a polyolefin-based resin is preferable. In that the odor of the oxygen absorber obtained among the polyolefin resins is more controlled,
Melt flow rate at 90 ° C. is 0.1 to 20 g / 10
Linear medium density, linear high density polyethylene, 230
A polypropylene resin having a melt flow rate at 1 ° C. of 1 to 20 g / 10 minutes is preferred.
【００１１】本発明における酸素吸収性樹脂組成物中の
酸素吸収剤の含有量は２０〜８０重量％であり、より好
ましくは３０〜７０重量％である。酸素吸収剤が８５重
量％を超えると、酸素吸収剤の熱可塑性樹脂への分散性
が悪化する。例えば、酸素吸収剤が８５重量％を超える
本樹脂組成物を押出成形機等によりシート加工する場
合、加工性が悪化する。また、酸素吸収剤の量が２０重
量％未満の場合は得られる酸素吸収体の酸素吸収性能が
不十分である。[0011] The content of the oxygen absorbent in the oxygen-absorbing resin composition of the present invention is from 20 to 80% by weight, more preferably from 30 to 70% by weight. When the amount of the oxygen absorbent exceeds 85% by weight, the dispersibility of the oxygen absorbent in the thermoplastic resin deteriorates. For example, when the present resin composition in which the oxygen absorbent exceeds 85% by weight is processed into a sheet by an extruder or the like, the processability deteriorates. When the amount of the oxygen absorbent is less than 20% by weight, the oxygen absorbing performance of the obtained oxygen absorber is insufficient.
【００１２】本発明の酸素吸収性樹脂組成物は、酸素吸
収剤と熱可塑性樹脂と、必要により酸化防止剤等の添加
剤とを既存の混合方法により混合することにより得られ
る。混合方法としては、ロール型、バンバリー型混練
機、一軸または、二軸押出機などを用いる通常の方法を
用いることができる。臭気発生防止の点より、より好ま
しくは、ヘンシェルミキサー等を使用してのゲレーショ
ン法により熱可塑性樹脂と酸素吸収剤とを融着させる方
法が用いられる。The oxygen-absorbing resin composition of the present invention can be obtained by mixing an oxygen-absorbing agent, a thermoplastic resin and, if necessary, additives such as an antioxidant by an existing mixing method. As a mixing method, an ordinary method using a roll type, a Banbury type kneader, a single screw or twin screw extruder, or the like can be used. From the viewpoint of preventing odor generation, more preferably, a method of fusing a thermoplastic resin and an oxygen absorbent by a gelation method using a Henschel mixer or the like is used.
【００１３】上記方法により得られた酸素吸収性樹脂組
成物は、そのままでフィルム、シート、容器等に成形し
ても良い。また、他の樹脂と積層し、容器等に加工する
ことも好ましい。または、Ｔ−ダイ法、イフレーション
法等によりシート状に成形した後、一軸、または二軸に
延伸加工しても良く、この延伸シートも単層でも多層で
よい。酸素吸収性能の点からは、好ましくは後者のシー
ト状成形品を延伸加工した方が良い。The oxygen-absorbing resin composition obtained by the above method may be directly formed into a film, sheet, container or the like. It is also preferable to laminate with another resin and process it into a container or the like. Alternatively, after being formed into a sheet by a T-die method, an inflation method or the like, the sheet may be monoaxially or biaxially stretched, and the stretched sheet may be a single layer or a multilayer. From the viewpoint of oxygen absorption performance, it is preferable to stretch the latter sheet-like molded product.
【００１４】[0014]
【発明の効果】本発明によれば、樹脂の熱劣化と酸化防
止剤の分解による臭気原因物質の生成を効果的に押える
ことのできる酸素吸収性樹脂組成物が得られる。さら
に、その樹脂組成物を使用すれば、臭気発生の少ない、
食品等の風味を損ねることの無い酸素吸収体を作製で
き、得られた酸素吸収体は食品等の保存に極めて有効で
ある。According to the present invention, there can be obtained an oxygen-absorbing resin composition capable of effectively suppressing thermal deterioration of the resin and generation of odor-causing substances due to decomposition of the antioxidant. Furthermore, if the resin composition is used, less odor is generated,
An oxygen absorber that does not impair the flavor of food or the like can be produced, and the obtained oxygen absorber is extremely effective for preserving food or the like.
【００１５】[0015]
【実施例】以下実施例を用いて、本発明を詳細に説明す
るが、本発明はこれらによって限定されるものではな
い。The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００１６】酸素組成比分析法：不活性ガス−インパル
ス加熱融解法により、下記条件で分析した。 条件：常温から２５００℃までを１５０／ｍｉｎで昇温 検出：ＮＤＩＲ（非分散赤外吸収）Oxygen composition ratio analysis method: Analysis was carried out by an inert gas-impulse heating melting method under the following conditions. Conditions: Temperature rise from normal temperature to 2500 ° C at 150 / min Detection: NDIR (Non-dispersive infrared absorption)
【００１７】臭気の評価方法：バリア包装体に酸素吸収
体０．９ｇと１０ｍｌの蒸留水を含侵させた脱脂綿を同
封し、空気２５０ｍｌを充填する。これを室温２５℃
下、２日間放置後、この包装体を開封し、官能試験を実
施した。臭気評価は、以下評点とした。 評点：５（無臭）＞４＞３＞２＞１（異臭）Odor evaluation method: 0.9 g of an oxygen absorber and absorbent cotton impregnated with 10 ml of distilled water are enclosed in a barrier package and filled with 250 ml of air. This is at room temperature 25 ° C
After standing for 2 days, the package was opened and a sensory test was performed. The odor evaluation was evaluated as follows. Rating: 5 (odorless)>4>3>2> 1 (offensive odor)
【００１８】〔実施例１〕熱可塑性樹脂として、１９０
℃でのＭＦＲが６．０ｇ／１０ｍｉｎ、真密度０．９５
８ｇ／ｃｍ3の高密度ポリエチレン（以下、樹脂Ａとす
る）を使用した。酸素吸収剤として、平均粒径１００μ
ｍの還元鉄に塩化カルシウムを２重量％をコーティング
したもの（以下、酸素吸収剤Ａとする）を使用した。こ
の酸素吸収剤Ａの酸素組成比は０．６ｗｔ％であった。
この樹脂Ａと酸素吸収剤Ａを３０／７０重量比で、酸化
防止剤は全く添加せず混合し酸素吸収性樹脂組成物を得
た。この組成物を押出機およびＴ−ダイ加工法によりシ
ーティングし、厚み１．５ｍｍのシートを得た。さら
に、このシートをロール一軸延伸機を用いて延伸し、酸
素吸収体を得た。この酸素吸収体を官能法による臭気評
価を行った。評点は４であった。Example 1 As a thermoplastic resin, 190
MFR at 6.0 ° C / 10 g, true density 0.95
8 g / cm 3 of high-density polyethylene (hereinafter referred to as resin A) was used. As oxygen absorber, average particle size 100μ
m reduced iron coated with 2% by weight of calcium chloride (hereinafter referred to as oxygen absorbent A) was used. The oxygen composition ratio of the oxygen absorbent A was 0.6% by weight.
This resin A and oxygen absorber A were mixed at a 30/70 weight ratio without adding any antioxidant to obtain an oxygen-absorbing resin composition. The composition was sheeted by an extruder and a T-die processing method to obtain a sheet having a thickness of 1.5 mm. Further, this sheet was stretched using a roll uniaxial stretching machine to obtain an oxygen absorber. This oxygen absorber was evaluated for odor by a sensory method. The score was 4.
【００１９】〔実施例２〕樹脂Ａ／酸素吸収剤Ａ＝３０
／７０重量比で、ｄ，ｌ−α−トコフェロール（理研ビ
タミン製Ｅオイル１０００）を樹脂Ａに対し３００ｐｐ
ｍ添加した、以外は実施例１と同様に行い、酸素吸収体
を得た。その臭気評価を行った。評点は５であった。Example 2 Resin A / Oxygen absorbent A = 30
/ 70 weight ratio, d, l-α-tocopherol (E oil 1000 manufactured by Riken Vitamin) was added to resin A at 300 pp
An oxygen absorber was obtained in the same manner as in Example 1 except that m was added. The odor was evaluated. The score was 5.
【００２０】〔実施例３〕酸素吸収剤には、平均１００
μｍの鉄粉に塩化カルシウム２重量％をコーティングさ
せながら酸化させたもの（以下、酸素吸収剤Ｂとする）
を使用した。この酸素吸収剤Ｂの酸素組成比は１．０ｗ
ｔ％であった。樹脂Ａ／酸素吸収剤Ｂ＝３０／７０重量
比で、酸化防止剤を添加せず、以下実施例１と同様に行
い、酸素吸収体を得た。その臭気評価を行った。評点は
５であった。Example 3 The oxygen absorber had an average of 100
μm iron powder oxidized while coating with 2% by weight of calcium chloride (hereinafter referred to as oxygen absorbent B)
It was used. The oxygen composition ratio of the oxygen absorbent B is 1.0 w
t%. The same procedure was followed as in Example 1 to obtain an oxygen absorber at a resin A / oxygen absorbent B = 30/70 weight ratio without adding an antioxidant. The odor was evaluated. The score was 5.
【００２１】〔比較例１〕樹脂Ａ／酸素吸収剤Ａ＝３０
／７０重量比で、酸化防止剤にテトラキス[メチレン−
３−（３’，５’−ジ−trt-ブチル−４−ヒドロキシフ
ェニル）プロピオネート]メタン（住友化学製ＢＰ−１
０１）を樹脂Ａに対し３０００ｐｐｍを添加する以外
は、実施例１と同様に行い、酸素吸収体を得た。その臭
気評価を行った。評点は３であった。Comparative Example 1 Resin A / Oxygen Absorbent A = 30
/ 70 weight ratio, tetrakis [methylene-
3- (3 ', 5'-di-trt-butyl-4-hydroxyphenyl) propionate] methane (BP-1 manufactured by Sumitomo Chemical Co., Ltd.)
01) was added in the same manner as in Example 1 except that 3000 ppm was added to Resin A, to obtain an oxygen absorber. The odor was evaluated. The score was 3.
【００２２】〔比較例２〕樹脂Ａ／酸素吸収剤Ｂ＝３０
／７０重量比で、酸化防止剤にテトラキス[メチレン−
３−（３’，５’−ジ−ｔ-ブチル−４−ヒドロキシフ
ェニル）プロピオネート]メタン（住友化学製ＢＰ−１
０１）を樹脂Ａに対し３０００ｐｐｍ添加する以外は、
実施例１と同様に行い酸素吸収体を得た。その臭気評価
を行った。評点は２であった。Comparative Example 2 Resin A / Oxygen absorbent B = 30
/ 70 weight ratio, tetrakis [methylene-
3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane (BP-1 manufactured by Sumitomo Chemical Co., Ltd.)
01) to resin A, except that
An oxygen absorber was obtained in the same manner as in Example 1. The odor was evaluated. The score was 2.
Claims (6)
してなる組成物であって、ヒンダードフェノール系酸化
防止剤を実質的に使用しないことを特徴とする酸素吸収
性樹脂組成物。An oxygen-absorbing resin composition which is obtained by kneading a metal-based oxygen absorber and a thermoplastic resin, wherein the composition does not substantially use a hindered phenol-based antioxidant. Stuff.
る請求項１記載の酸素吸収性樹脂組成物。2. The oxygen-absorbing resin composition according to claim 1, comprising tocopherol.
請求項１また２記載の酸素吸収性樹脂組成物。3. The oxygen-absorbing resin composition according to claim 1, wherein the metal-based oxygen absorbent is an iron-based oxygen absorbent.
３記載の酸素吸収性樹脂組成物。4. The oxygen-absorbing resin composition according to claim 3, wherein the iron-based oxygen absorbent is a partial iron oxide.
成比が０．８ｗｔ％以上１０ｗｔ％未満である請求項4
記載の酸素吸収性樹脂組成物。5. The partial iron oxide has an oxygen composition ratio of 0.8 wt% or more and less than 10 wt% by an elemental analysis method.
The oxygen-absorbing resin composition according to the above.
吸収性樹脂組成物を成形してなる酸素吸収性樹脂成形
体。6. An oxygen-absorbing resin molded article obtained by molding the oxygen-absorbing resin composition according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34752197A JP3765355B2 (en) | 1996-12-20 | 1997-12-17 | Oxygen-absorbing resin composition and molded body thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-341986 | 1996-12-20 | ||
| JP34198696 | 1996-12-20 | ||
| JP34752197A JP3765355B2 (en) | 1996-12-20 | 1997-12-17 | Oxygen-absorbing resin composition and molded body thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10230160A true JPH10230160A (en) | 1998-09-02 |
| JP3765355B2 JP3765355B2 (en) | 2006-04-12 |
Family
ID=26577114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34752197A Expired - Lifetime JP3765355B2 (en) | 1996-12-20 | 1997-12-17 | Oxygen-absorbing resin composition and molded body thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3765355B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080647A (en) * | 2000-09-07 | 2002-03-19 | Mitsubishi Gas Chem Co Inc | Deoxidizing agent resin composition and sheet |
| JP2008156000A (en) * | 2001-07-26 | 2008-07-10 | M & G Polimeri Italia Spa | Oxygen-scavenging resin composition and container having low haze and related method |
| US7740926B2 (en) | 2001-07-26 | 2010-06-22 | M&G Usa Corporation | Oxygen-scavenging containers |
-
1997
- 1997-12-17 JP JP34752197A patent/JP3765355B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080647A (en) * | 2000-09-07 | 2002-03-19 | Mitsubishi Gas Chem Co Inc | Deoxidizing agent resin composition and sheet |
| JP2008156000A (en) * | 2001-07-26 | 2008-07-10 | M & G Polimeri Italia Spa | Oxygen-scavenging resin composition and container having low haze and related method |
| US7740926B2 (en) | 2001-07-26 | 2010-06-22 | M&G Usa Corporation | Oxygen-scavenging containers |
| JP4726912B2 (en) * | 2001-07-26 | 2011-07-20 | エンメ エ ジ・ポリメリ・イタリア・ソチエタ・ペル・アツィオーニ | Oxygen scavenging resin composition and containers having low haze and related methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3765355B2 (en) | 2006-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101056598B1 (en) | Oxygen-absorbing composition | |
| CN108367551A (en) | Deodorizing multilayer packaging film and package made therefrom | |
| JP6429778B2 (en) | Adsorbent composition, adsorbent-containing film and method for producing the same | |
| US6232402B1 (en) | Films based on three component polyolefin blend | |
| JP3927245B2 (en) | Improved packaging composition | |
| JP3410219B2 (en) | Multilayer sealant film for lamination | |
| JP2632530B2 (en) | Plastic film packaging material with excellent freshness retention and deodorization | |
| CA1188447A (en) | Film forming composition of pelletized ldpe | |
| JPH10230160A (en) | Oxygen absorptive resin composition and its molded body | |
| JP2006231899A (en) | Polypropylene based antifogging film | |
| EP0739398A1 (en) | Anti-fog film, method of packaging products having high moisture content and products thus packaged | |
| JP3403798B2 (en) | Oxygen-absorbing resin composition, sheet, film and oxygen-absorbing container | |
| JP2778074B2 (en) | Method for producing self-reactive oxygen absorbing sheet | |
| JP2728361B2 (en) | Radiation sterilization method for sealed packaging | |
| JP3081976B2 (en) | Oxygen absorbing multilayer sheet | |
| JP3460801B2 (en) | Deoxidizing multilayer or method for food heating | |
| JP2576646B2 (en) | Oxygen absorbing sheet | |
| JP4544377B2 (en) | Oxygen-absorbing multilayer | |
| EP3843991B1 (en) | Odor-managed ostomy film | |
| JPH03106950A (en) | Moisture-permeable film | |
| JP2003340274A (en) | Improved oxygen scavenger composition | |
| JPH10152596A (en) | Sealant film for retort | |
| JPH0195044A (en) | Oxygen absorbing composite film or sheet | |
| JPH0447936A (en) | Anti-fogging multilayer film | |
| JPH05318574A (en) | Production of oxygen absorbing sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040414 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20040401 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050928 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051005 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051202 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060105 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060118 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100203 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100203 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110203 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120203 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120203 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130203 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140203 Year of fee payment: 8 |
|
| EXPY | Cancellation because of completion of term |