JPH05295171A - Oxygen-absorbent composition and molded article thereof - Google Patents
Oxygen-absorbent composition and molded article thereofInfo
- Publication number
- JPH05295171A JPH05295171A JP12807292A JP12807292A JPH05295171A JP H05295171 A JPH05295171 A JP H05295171A JP 12807292 A JP12807292 A JP 12807292A JP 12807292 A JP12807292 A JP 12807292A JP H05295171 A JPH05295171 A JP H05295171A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸素吸収機能を有する
組成物及び該組成物を用いて種々の成形法により形成し
た成形体に関するものである。そして本発明の主な利用
分野は、酸素吸収機能及び酸素バリアー機能を必要とす
る分野であり、具体的には、食品保存、酸素によるさま
ざまな不具合を生ずる製品の保存を利用可能としたもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having an oxygen absorbing function and a molded product formed by various molding methods using the composition. The main application field of the present invention is a field that requires an oxygen absorption function and an oxygen barrier function, and specifically, it makes it possible to use food storage, storage of products that cause various problems due to oxygen. is there.
【０００２】[0002]
【従来の技術】酸素吸収機能を持つ組成物の代表的なも
のとしては、鉄粉系の脱酸素剤組成物が知られている。
この鉄粉系の脱酸素剤組成物は、特開昭５９−２９０３
３号公報等で公知の通り、顆粒状や粉体のものが多く、
その為にこのまま使用すると酸素から保護すべき製品
（被酸化性製品）に組成物が付着したり、保護すべき製
品を変質する等の汚染を発生させる原因となる。また、
この組成物は酸素吸収速度が極めて早いので、吸収能力
を制御する為に酸素透過性の不織紙等の包装袋に入れる
必要がある。2. Description of the Related Art An iron powder-based oxygen absorber composition is known as a typical composition having an oxygen absorbing function.
This iron powder-based oxygen absorber composition is disclosed in JP-A-59-2903.
As is known in Japanese Patent No. 3, etc., many are granular or powder,
Therefore, if it is used as it is, the composition may adhere to the product to be protected from oxygen (oxidizable product), or the product to be protected may be deteriorated, causing contamination. Also,
Since this composition has an extremely high oxygen absorption rate, it is necessary to put it in a packaging bag such as an oxygen-permeable nonwoven paper in order to control the absorption capacity.
【０００３】このように鉄粉系を代表とする従来の脱酸
素剤組成物は、それ自身のみの状態で使用することが出
来ず、常に脱酸素剤を包装する工程が必要となる。ま
た、無機化合物が主体である為に任意の成形体とするこ
とが出来ず、その適用範囲が限定されている。As described above, the conventional oxygen scavenger composition represented by iron powder cannot be used in its own state, and a step of always packaging the oxygen scavenger is required. Further, since the inorganic compound is the main component, it cannot be formed into an arbitrary molded body, and its applicable range is limited.
【０００４】[0004]
【発明が解決しようとする課題】本発明の第１の課題
は、上記鉄粉系の脱酸素剤組成物が使用する際に包装工
程を必要としていたのに対し、脱酸素剤の包装工程を必
要としないで任意の酸素吸収能力の制御を行い、しかも
被酸化性製品を汚染することのない酸素吸収機能を有す
る組成物を提供するものである。また、本発明の第２の
課題は、前記組成物を用いて種々の成形法により任意の
形状にすることの出来る酸素吸収機能を有する成形体を
提供するものである。The first object of the present invention is to provide a packaging process for the oxygen scavenger, while a packaging process is required when the iron powder type oxygen absorber composition is used. It is intended to provide a composition having an oxygen-absorbing function which does not require any oxygen-absorbing ability control and does not contaminate an oxidizable product. A second object of the present invention is to provide a molded article having an oxygen absorbing function, which can be formed into an arbitrary shape by various molding methods using the composition.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、酸素から
保護すべき製品、すなわち食品保護や酸素によるさまざ
まな不具合を生じる製品である被酸化性製品に直接接触
しても毒性や製品の変質等の汚染の恐れがなく、酸素と
の反応速度及び反応開始時間を任意にコントロールする
ことのできる種々の組成物を鋭意検討した結果、本発明
を完成するに至った。The inventors of the present invention have found that even if the product to be protected from oxygen, that is, an oxidizable product that causes various problems due to food protection and oxygen, is directly contacted with the product, toxicity and product The present invention has been completed as a result of earnestly studying various compositions capable of arbitrarily controlling the reaction rate with oxygen and the reaction initiation time without fear of contamination such as alteration.
【０００６】すなわち、本発明は、 炭素−炭素不飽和結合を有する成分及び遷移金属化
合物の酸素吸収機能組成物 及び熱可塑性樹脂からなる酸素吸収機能組成物 又は及び酸素吸収機能調節剤からなる酸素吸収
機能組成物 、又はの該酸素吸収機能組成物をそれぞれ成
形してなる成形体 を特徴とするものである。That is, the present invention relates to an oxygen-absorption functional composition comprising a component having a carbon-carbon unsaturated bond and a transition metal compound, an oxygen-absorption functional composition comprising a thermoplastic resin, and an oxygen-absorption functional composition comprising an oxygen-absorption function modifier. The functional composition, or a molded product obtained by molding the oxygen-absorbing functional composition.
【０００７】本発明の炭素−炭素不飽和結合を有する成
分とは、ゴム状重合体及び該ゴム状重合体と共重合可能
なモノマーとの共重合体である高分子化合物、又は高級
不飽和脂肪酸及びその誘導体並びにこれらの混合物を指
すものである。The component having a carbon-carbon unsaturated bond of the present invention means a polymer compound which is a rubber-like polymer and a copolymer of a monomer copolymerizable with the rubber-like polymer, or a higher unsaturated fatty acid. And its derivatives and mixtures thereof.
【０００８】本発明の炭素−炭素不飽和結合を有する成
分である高分子化合物としてのゴム状重合体としては、
ジエン系の例えば、ブタジエン、イソプレン、２−クロ
ロ−１，３−ブタジエン、１−クロロ−１，３−ブタジ
エン、ピペリジン、２，３−ジメチル−１，３−ブタジ
エン、１−フェニル−１，３−ブタジエン等のゴム状重
合体が好ましく、より好ましいジエン系重合体として
は、ブタジエン重合体である。そしてゴム状重合体は、
単独で使用してもよく、他の熱可塑性樹脂との混合物と
して使用してもよい。The rubbery polymer as a polymer compound which is a component having a carbon-carbon unsaturated bond of the present invention is
Diene-based, for example, butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene, piperidine, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3 -A rubbery polymer such as butadiene is preferable, and a more preferable diene polymer is a butadiene polymer. And the rubbery polymer is
It may be used alone or as a mixture with another thermoplastic resin.
【０００９】また、高分子化合物であるジエン系重合体
を他のモノマー成分と共重合させたものとしては、例え
ば、共重合体全体に対してジエン系重合体が２〜７０重
量部含有するスチレン−ブタジエン共重合体、アクリロ
ニトリル−スチレン−ブタジエン共重合体（以下ＡＢＳ
樹脂という）、メタクリル酸メチル−スチレン−ブタジ
エン共重合体（以下ＭＢＳ樹脂という）アクリロニトリ
ル−メタクリル酸メチル−スチレン−ブタジエン共重合
体（以下ＭＡＢＳ樹脂という）及びスチレン−ブタジエ
ン−スチレンブロック共重合体（以下ＳＢＳ樹脂とい
う）等の少なくとも１種が挙げられる。The diene polymer, which is a high molecular compound, is copolymerized with other monomer components. For example, styrene containing the diene polymer in an amount of 2 to 70 parts by weight based on the whole copolymer. -Butadiene copolymer, acrylonitrile-styrene-butadiene copolymer (hereinafter ABS
Resin), methyl methacrylate-styrene-butadiene copolymer (hereinafter referred to as MBS resin) acrylonitrile-methyl methacrylate-styrene-butadiene copolymer (hereinafter referred to as MABS resin) and styrene-butadiene-styrene block copolymer (hereinafter referred to as MABS resin). SBS resin) and the like.
【００１０】そして、ＡＢＳ樹脂、ＭＢＳ樹脂及びＭＡ
ＢＳ樹脂は、比較的熱酸化劣化安定性が高く単味の酸化
防止剤の添加量が少ない点でより最適である。And ABS resin, MBS resin and MA
BS resin is more optimal because it has relatively high stability against thermal oxidative deterioration and a small amount of plain antioxidant is added.
【００１１】本発明に用いる上記樹脂の製造方法は、従
来から知られている製法で得られるものであればよく、
また各種製法によって得られる樹脂は、粒子径、架橋
度、モノマーの構成比や重合度等の諸特性を特定の範囲
に限定するものではない。The method for producing the above-mentioned resin used in the present invention may be any one obtained by a conventionally known production method,
Further, the resins obtained by various production methods are not limited to various properties such as particle diameter, degree of crosslinking, monomer composition ratio and degree of polymerization within a specific range.
【００１２】次に、炭素−炭素不飽和結合を有する成分
の高級不飽和脂肪酸及びその誘導体としては、リノール
酸、リノエライジン酸及びオレイン酸等が挙げられる。Next, examples of the higher unsaturated fatty acid and its derivative having a carbon-carbon unsaturated bond include linoleic acid, linoelaidic acid and oleic acid.
【００１３】本発明に用いる炭素−炭素不飽和結合を有
する成分は、組成物全体を１００重量部とした際に、ジ
エン系重合体又は高級不飽和脂肪酸及びその誘導体が、
２重量部〜７０重量部である。含有量が２重量部未満で
は、酸素吸収機能が低く、７０重量部を越えると、成形
加工安定性が著しく低下することになる。The component having a carbon-carbon unsaturated bond used in the present invention is a diene polymer or a higher unsaturated fatty acid and its derivative, when the total composition is 100 parts by weight.
It is 2 to 70 parts by weight. If the content is less than 2 parts by weight, the oxygen absorption function is low, and if it exceeds 70 parts by weight, the molding processing stability is significantly lowered.
【００１４】本発明に用いる熱可塑性樹脂としては、ポ
リエチレン、ポリプロピレン、１−ブテン、又はポリス
チレン、ポリメタクリル酸メチル、ポリメタクリル酸エ
チル、ポリアクリロニトリル及びポリ塩化ビニル樹脂並
びにこれらの共重合体樹脂等種々のものが使用できる。As the thermoplastic resin used in the present invention, various resins such as polyethylene, polypropylene, 1-butene, polystyrene, polymethylmethacrylate, polyethylmethacrylate, polyacrylonitrile and polyvinyl chloride resins and copolymer resins thereof can be used. Can be used.
【００１５】しかし、特に炭素−炭素不飽和結合を有す
る成分との親和性を考慮すると、ポリスチレン、ポリメ
タクリル酸メチル、ポリメタクリル酸エチル及びポリア
クリロニトリル樹脂及びその共重合体樹脂が好ましい。However, polystyrene, polymethylmethacrylate, polyethylmethacrylate, polyacrylonitrile resins and copolymer resins thereof are preferable, especially in consideration of the affinity with the component having a carbon-carbon unsaturated bond.
【００１６】上述の熱可塑性樹脂は、一般的には塊状重
合、溶液重合、懸濁重合等の製法によって得られるもの
であれば、モノマーの構成比、重合度、架橋度等の諸特
性を特定の範囲に限定するものではない。The above-mentioned thermoplastic resin is generally obtained by a production method such as bulk polymerization, solution polymerization, suspension polymerization, etc., and various characteristics such as monomer composition ratio, degree of polymerization and degree of crosslinking are specified. It is not limited to the range of.
【００１７】本発明の酸素吸収機能組成物と混合する熱
可塑性樹脂の割合は、炭素−炭素不飽和結合を有する成
分のジエン系重合体及びその共重合体又は高級不飽和脂
肪酸及びその誘導体との混合物において、混合物全体を
１００重量部とした際に、炭素−炭素不飽和結合を有す
るジエン系重合体又は高級不飽和脂肪酸及びその誘導体
が、２〜７０重量部となる割合にすればよい。The proportion of the thermoplastic resin to be mixed with the oxygen-absorbing functional composition of the present invention is such that the diene polymer and its copolymer or the higher unsaturated fatty acid and its derivative which are components having a carbon-carbon unsaturated bond. In the mixture, when the total amount of the mixture is 100 parts by weight, the proportion of the diene polymer having a carbon-carbon unsaturated bond or the higher unsaturated fatty acid and its derivative may be 2 to 70 parts by weight.
【００１８】本発明に用いる遷移金属化合物としては、
種々のものが使用できるが、酸素吸収機能を特に考慮す
ると、Ｆｅ、Ｎｉ、Ｃｏ及びＭｎを金属種とした金属塩
及びそれら金属を配位した金属化合物を使用することが
より好ましい。The transition metal compound used in the present invention is
Although various substances can be used, it is more preferable to use a metal salt containing Fe, Ni, Co, and Mn as a metal species and a metal compound in which those metals are coordinated, in view of the oxygen absorption function.
【００１９】また、本発明に用いる炭素−炭素不飽和結
合を有する成分及び熱可塑性樹脂との親和性を考慮する
と、上記金属と有機アニオンとの塩及び有機金属配位化
合物がより好ましい。Considering the affinity with the component having a carbon-carbon unsaturated bond and the thermoplastic resin used in the present invention, a salt of the above metal and an organic anion and an organic metal coordination compound are more preferable.
【００２０】具体的には、酢酸、酪酸、ヘプタン酸、オ
クタン酸、オクチル酸及びステアリン酸等のカルボン酸
とＦｅ、Ｎｉ、Ｃｏ及びＭｎを金属種とした金属とから
なる金属塩が挙げられる。また、有機金属配位化合物と
しては、Ｆｅ、Ｎｉ、Ｃｏ及びＭｎを金属種とした金属
のアセチルアセトネート等が挙げられる。Specific examples thereof include metal salts of carboxylic acids such as acetic acid, butyric acid, heptanoic acid, octanoic acid, octylic acid and stearic acid, and metals containing Fe, Ni, Co and Mn as metal species. Examples of the organic metal coordination compound include acetylacetonate, which is a metal containing Fe, Ni, Co, and Mn as metal species.
【００２１】本発明において、組成物中への遷移金属化
合物の含有量は、酸素吸収速度、吸収能力をどの程度に
するかによって変化するが、酸素吸収機能組成物に占め
る炭素−炭素不飽和結合を有する成分のジエン系重合体
又は高級不飽和脂肪酸及びその誘導体１００重量部に対
して、金属分重量比で０．００５〜５重量部とすること
が好ましく、更に好ましくは、０．０１〜１重量部であ
る。含有量が０．００５重量部未満では、酸素吸収機能
が非常に低くなり、５重量部を越えると、酸素吸収反応
速度が高くなりすぎて、成形加工性が著しく劣ることに
なる。In the present invention, the content of the transition metal compound in the composition varies depending on the oxygen absorption rate and the absorption capacity, but the carbon-carbon unsaturated bond contained in the oxygen absorbing functional composition. With respect to 100 parts by weight of the diene polymer or higher unsaturated fatty acid and its derivative as a component having a metal content of 0.005 to 5 parts by weight, and more preferably 0.01 to 1 part by weight. Parts by weight. If the content is less than 0.005 parts by weight, the oxygen absorption function is very low, and if it exceeds 5 parts by weight, the oxygen absorption reaction rate becomes too high, resulting in a markedly poor moldability.
【００２２】本発明の酸素吸収機能調節剤としては、有
極性の樹脂及び酸化防止剤を用いることができる。本発
明の酸素吸収機能調節剤は、酸素吸収機能組成物及びそ
の成形体に含まれる炭素−炭素不飽和結合を有する成分
に対しては、その成分中の炭素−炭素不飽和結合の含有
量、熱可塑性樹脂に対しては、該樹脂自体の酸素透過
率、また遷移金属化合物に対しては、錯体形成に必要な
含有量との関係から組成物全体に含有する量を調整する
ことが好ましい。As the oxygen absorbing function controlling agent of the present invention, a polar resin and an antioxidant can be used. The oxygen-absorption function regulator of the present invention, for the component having a carbon-carbon unsaturated bond contained in the oxygen-absorption functional composition and the molded body thereof, the content of the carbon-carbon unsaturated bond in the component, For a thermoplastic resin, it is preferable to adjust the oxygen content of the resin itself, and for the transition metal compound, the amount contained in the entire composition is adjusted in relation to the content necessary for complex formation.
【００２３】酸素吸収機能調節剤は、該調節剤の構成と
その作用効果の点から大きく３点に分けられることが考
えられる。It is considered that the oxygen-absorption function regulator is roughly classified into three points from the viewpoint of the constitution of the regulator and its action and effect.
【００２４】まず、有極性を有する樹脂の場合の作用効
果は、炭素−炭素不飽和結合を有する成分との接触、酸
素と遷移金属との接触及び酸素と炭素−炭素不飽和結合
を有する成分との接触頻度を調節することにより酸素吸
収機能の調節（ここでは、酸素吸収機能寿命の調節）を
行うものと考えられる。First, the action and effect in the case of a resin having a polarity is as follows: contact with a component having a carbon-carbon unsaturated bond, contact between oxygen and a transition metal, and contact with a component having oxygen and a carbon-carbon unsaturated bond. It is considered that the oxygen absorption function is adjusted (here, the oxygen absorption function life is adjusted) by adjusting the contact frequency of.
【００２５】有極性の樹脂として具体的には、ポリエス
テル、ポリカーボネート及びポリアミド樹脂等が挙げら
れるが、特にポリアミド樹脂が好適に使用される。Specific examples of the polar resin include polyester, polycarbonate and polyamide resins, and polyamide resin is particularly preferably used.
【００２６】これらの樹脂含有量は、酸素吸収機能組成
物及び成形体とする時の加工性により任意に調節される
が、酸素吸収機能を有する成分のジエン系重合体又は高
級不飽和脂肪酸及びその誘導体１００重量部に対して、
５〜５，０００重量部含有することが好ましく、更に好
ましくは、１０〜２，０００重量部である。含有量が５
重量部未満では、酸素吸収反応に介在する成分の接触頻
度を調節するに至らず、５，０００重量部を越えると、
酸素吸収反応に介在する成分の接触頻度を極端に制限し
てしまい、調節機能が得られないことになる。The content of these resins is arbitrarily adjusted by the oxygen-absorbing functional composition and the processability when forming a molded product, but the diene polymer or the higher unsaturated fatty acid and the component thereof having an oxygen-absorbing function. With respect to 100 parts by weight of the derivative,
The content is preferably 5 to 5,000 parts by weight, more preferably 10 to 2,000 parts by weight. Content is 5
If it is less than 5,000 parts by weight, the contact frequency of the components intervening in the oxygen absorption reaction cannot be adjusted.
The contact frequency of the components intervening in the oxygen absorption reaction is extremely limited, and the regulation function cannot be obtained.
【００２７】酸素吸収機能調節剤の２つ目の酸化防止剤
の場合の作用効果は、遷移金属によって活性化した酸素
ラジカルの捕捉と失活、炭素−炭素不飽和結合を含有す
る成分が酸素によって酸化された後に生じる、過酸化ラ
ジカルを捕捉して失活させることにより酸素吸収機能の
調節（ここでは、酸素吸収開始時期の調節）を行うもの
であると考えられる。In the case of the second antioxidant of the oxygen absorption function controlling agent, the action and effect are as follows: capture and deactivation of oxygen radicals activated by a transition metal, and a component containing a carbon-carbon unsaturated bond is caused by oxygen. It is considered that the oxygen absorption function is regulated (here, the oxygen absorption start time is regulated) by trapping and deactivating the peroxide radical generated after being oxidized.
【００２８】この酸化防止剤としては、ラジカル捕捉能
を持つ一般的に一次酸化防止剤と総称されているものが
挙げられ、特にこの捕捉能の高いヒンダードフェノール
を基本骨格とする化合物が有効である。Examples of the antioxidant include those generally referred to as primary antioxidants having a radical scavenging ability, and compounds having a hindered phenol having a high scavenging ability as a basic skeleton are particularly effective. is there.
【００２９】該化合物としては、例えばｎ−オクタデシ
ル−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、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、２，６−ジ−ｔ−ブチル−４
−メチルフェノール、２，２’−メチレンビス（４−メ
チル−６−ｔ−ブチルフェノール）、４−４’−ブチリ
デンビス（３−メチル−６−ｔ−ブチルフェノール）及
び１，３，５−トリス（３’５’−ジ−ｔ−ブチル−
４’−ヒドロキシベンジル）−ｓ−トリアジン−２，
４，６−（１Ｈ，３Ｈ，５Ｈ）トリオン等のものが挙げ
られる。Examples of the compound include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and tetrakis [methylene-3-].
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, 2,6-di-t-butyl-4
-Methylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-4'-butylidenebis (3-methyl-6-t-butylphenol) and 1,3,5-tris (3 ') 5'-di-t-butyl-
4'-hydroxybenzyl) -s-triazine-2,
Examples include 4,6- (1H, 3H, 5H) trione and the like.
【００３０】酸化防止剤の添加量は、要求される酸素吸
収機能のレベルによって任意に調節することが可能であ
るが、酸素吸収機能を有する成分のジエン系重合体又は
高級不飽和脂肪酸及びその誘導体１００重量部に対し
て、１０〜４，０００重量部含有することが好ましく、
更に好ましくは、１０〜１，０００重量部である。含有
量が１０重量部未満では、ラジカル捕捉程度が低くて調
節機能が得られないし、４，０００重量部を越えると、
酸素吸収反応を著しく抑制するために、酸素吸収機能を
得ることが困難となる。The amount of the antioxidant added can be arbitrarily adjusted according to the level of oxygen absorption function required, but a diene polymer or a higher unsaturated fatty acid and its derivative as a component having an oxygen absorption function. It is preferable to contain 10 to 4,000 parts by weight with respect to 100 parts by weight,
More preferably, it is 10 to 1,000 parts by weight. When the content is less than 10 parts by weight, the degree of radical scavenging is too low to obtain a regulating function, and when it exceeds 4,000 parts by weight,
Since the oxygen absorption reaction is remarkably suppressed, it becomes difficult to obtain the oxygen absorption function.
【００３１】酸素吸収機能調節剤の３つ目は、遷移金属
化合物と配位可能な化合物であり、その作用効果は、遷
移金属の配位座を特定数に制限することにより酸素吸収
機能の調節（ここでは、酸素吸収機能活性の増加／減
少）を行うものであると考えられる。この配位可能な化
合物としては、含窒素系のキレート形成剤が挙げられ、
具体的にはエチレンジアミン、ジエチレントリアミン及
びテトラエチレンペンタミン等のアミン化合物、ｏ−フ
ェナントロリン及び２，２’−ビピリジン等の含窒素芳
香族化合物が挙げられる。The third oxygen absorbing function controlling agent is a compound capable of coordinating with a transition metal compound, and its action and effect is to control the oxygen absorbing function by limiting the coordination number of the transition metal to a specific number. (Here, increase / decrease of oxygen absorption function activity) is considered to be performed. Examples of the compound capable of coordinating include a nitrogen-containing chelating agent,
Specific examples include amine compounds such as ethylenediamine, diethylenetriamine and tetraethylenepentamine, and nitrogen-containing aromatic compounds such as o-phenanthroline and 2,2′-bipyridine.
【００３２】これら配位可能な化合物の含有量は、酸素
吸収機能のレベルと製造時の操作性によって異なるが、
遷移金属化合物の金属分１００重量部に対して、１０〜
１０，０００重量部含有することが好ましく、更に好ま
しくは、１０〜４，０００重量部である。含有量が１０
重量部未満では、金属との配位頻度が低くて調節機能が
得られないし、１０，０００重量部を越えると、金属と
の配位頻度が高く、酸素吸収反応を極端に抑制してしま
うので、調節機能が得られないことになる。The contents of these coordinating compounds vary depending on the level of oxygen absorption function and operability during production.
10 to 10 parts by weight of the metal content of the transition metal compound
The content is preferably 10,000 parts by weight, more preferably 10 to 4,000 parts by weight. Content is 10
If it is less than 10 parts by weight, the coordination frequency with the metal is low and the regulating function cannot be obtained. If it exceeds 10,000 parts by weight, the coordination frequency with the metal is high and the oxygen absorption reaction is extremely suppressed. , The adjustment function will not be obtained.
【００３３】上記の酸素吸収機能調節剤は、その目的と
する酸素吸収機能のレベルに応じて各々の種類のものを
２種以上併用してもかまわない。The above oxygen absorption function regulators may be used in combination of two or more of each kind according to the intended level of oxygen absorption function.
【００３４】また、本発明においては、酸素吸収機能を
妨げないのであれば、顔料等の着色剤や加工安定剤等を
酸素吸収機能組成物の助剤として使用することを限定す
るものではない。Further, in the present invention, use of a colorant such as a pigment or a processing stabilizer as an auxiliary agent of the oxygen absorbing functional composition is not limited as long as it does not interfere with the oxygen absorbing function.
【００３５】次に本発明の酸素吸収機能を有する組成物
の製造方法は、特に限定するものではないが、簡便な方
法としては、押出機を用いて組成物の配合物を溶融混練
後、冷却してペレット状にして取り出す方法が一般的に
挙げられる。Next, the method for producing the composition having an oxygen absorbing function of the present invention is not particularly limited, but a simple method is to melt and knead the composition mixture using an extruder and then cool it. In general, a method of forming pellets and taking them out can be mentioned.
【００３６】本発明の酸素吸収機能組成物を用いて成形
体を得る方法としては、成形体の形状にもよるが、一般
的に知られる熱可塑性樹脂の種々の成形法、例えば射出
成形、押出・吹込み成形、射出・吹込み成形、真空・圧
空成形及びプレス成形等によって成形することができる
が、特にその成形方法および成形体の形状を特定するも
のではない。The method for obtaining a molded article using the oxygen-absorbing functional composition of the present invention depends on the shape of the molded article, but various commonly known molding methods for thermoplastic resins such as injection molding and extrusion. It can be molded by blow molding, injection / blow molding, vacuum / pressure molding, press molding, etc., but the molding method and the shape of the molded body are not particularly specified.
【００３７】また成形体を得る最も簡便な方法として
は、酸素吸収機能組成物を押出機の先端に所定の形状の
ダイスを取り付けてフィルム又はシートを成形し、真空
及び／又は圧空成形機で２次加工して種々の成形体を成
形することができる。As the simplest method for obtaining a molded product, the oxygen-absorbing functional composition is attached to the tip of an extruder with a die having a predetermined shape to form a film or sheet, and the film is formed by a vacuum and / or pressure forming machine. Subsequent processing can form various molded bodies.
【００３８】[0038]
【実施例】以下実施例により本発明を詳細に説明する。 １．炭素−炭素不飽和結合を有する成分 ＭＢＳ樹脂：ジエン重合体を１５重量部含有する共
重合体樹脂 ＡＢＳ樹脂：ジエン重合体を２０重量部含有する共
重合体樹脂 高級不飽和脂肪酸エステル：リノール酸エチル ２．熱可塑性樹脂 メタクリル酸メチル−スチレン樹脂（ＭＳ樹脂）：
電気化学工業（株）製、商品名、ＴＸ−１００The present invention will be described in detail with reference to the following examples. 1. Component having carbon-carbon unsaturated bond MBS resin: Copolymer resin containing 15 parts by weight of diene polymer ABS resin: Copolymer resin containing 20 parts by weight of diene polymer Higher unsaturated fatty acid ester: Ethyl linoleate 2. Thermoplastic resin Methyl methacrylate-styrene resin (MS resin):
Denki Kagaku Kogyo KK, trade name, TX-100
【００３９】３．遷移金属化合物 ステアリン酸コバルト：（コバルトを約１０重量％
含有） ニッケルアセチルアセトネート：（ニッケルを約２
３％含有） 酢酸マンガン：（マンガンを約２２％含有） 鉄アセチルアセトネート：（鉄を約１６％含有） ４．酸素吸収機能調節剤 ヒンダードフェノール系酸化防止剤：旭電化製、商
品名、ＡＯ−２０ ポリアミド樹脂−１：三菱ガス化学製、商品名、Ｍ
ＸＤ６ ６００１ ポリアミド樹脂−２：宇部興産製、商品名、ポリア
ミド６−１０３０Ｂ3. Transition metal compounds Cobalt stearate: (Cobalt about 10% by weight
Nickel acetylacetonate: (contains about 2 nickel
3. Manganese acetate: (containing about 22% manganese) Iron acetylacetonate: (containing about 16% of iron) 4. Oxygen absorption function regulator Hindered phenolic antioxidant: Asahi Denka, trade name, AO-20 Polyamide resin-1: Mitsubishi Gas Chemical Co., trade name, M
XD6 6001 Polyamide resin-2: Ube Industries, trade name, polyamide 6-1030B
【００４０】実施例１〜１１及び比較例１〜２ 炭素−炭素不飽和結合を有する成分のジエン重合体を１
５重量部含有するＭＢＳ樹脂及びジエン重合体を２０重
量部含有するＡＢＳ樹脂、熱可塑性樹脂、遷移金属化合
物及び酸素吸収機能調節剤を表１に示す割合として、単
軸押出機（Ｌ／Ｄ＝２４）を用いてシリンダー温度２５
０℃以下で溶融混練後、溶融物を冷却して３mm角ペレッ
トの酸素吸収機能組成物を得た。得られた該各々の組成
物の酸素吸収機能評価は、３mm角ペレット８ｇを大気中
に１日及び１４日放置後各々を４０ccのガラスビンに入
れて密栓し、ガスクロマトグラフィーにより７日経過後
のガラスビン中の酸素濃度の減少を測定して判定した。
その測定結果は、表２に示す。Examples 1 to 11 and Comparative Examples 1 to 2 A diene polymer as a component having a carbon-carbon unsaturated bond was used.
MBS resin containing 5 parts by weight and ABS resin containing 20 parts by weight of diene polymer, thermoplastic resin, transition metal compound and oxygen absorbing function modifier are shown in Table 1 as a ratio, and the single screw extruder (L / D = 24) using a cylinder temperature of 25
After melt-kneading at 0 ° C. or lower, the melt was cooled to obtain a 3 mm square pellet oxygen-absorbing functional composition. The evaluation of the oxygen absorption function of each of the obtained compositions was carried out by leaving 8 g of 3 mm square pellets in the atmosphere for 1 day and 14 days, placing each in a 40 cc glass bottle, and sealingly sealing the glass bottle. It was determined by measuring the decrease in oxygen concentration in the medium.
The measurement results are shown in Table 2.
【００４１】比較例１及び２の組成物は、全く酸素吸収
機能を示さないのに対して、実施例１〜１０の組成物
は、いずれも酸素吸収機能を示した。また、酸素吸収機
能調節剤を配合している実施例７〜９の組成物は、酸素
吸収機能調節剤を配合していない実施例１の樹脂組成物
に比較して酸素吸収機能調節作用のあることを示してい
る。The compositions of Comparative Examples 1 and 2 did not exhibit an oxygen absorbing function at all, whereas the compositions of Examples 1 to 10 all exhibited an oxygen absorbing function. Further, the compositions of Examples 7 to 9 containing the oxygen absorption function modifier have an oxygen absorption function adjusting action as compared with the resin composition of Example 1 containing no oxygen absorption function modifier. It is shown that.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】実施例１２〜１６及び比較例３〜４ 炭素−炭素不飽和結合を有する成分のジエン重合体１５
重量部含有するＭＢＳ樹脂及びジエン重合体２０重量部
含有するＡＢＳ樹脂、熱可塑性樹脂、遷移金属化合物及
び酸素吸収機能調節剤を表３に示す割合として、先端に
コートハンガーダイを取り付けた単軸押出機（Ｌ／Ｄ＝
２４）でシリンダー温度２５０℃以下で溶融混練押出し
を行い、肉厚0.2 mmのシート成形品とした。得られた該
各々のシート状成形体の酸素吸収機能評価は、0.2 mm厚
シートを７日間大気中に放置後、酸素透過率測定機（Ｍ
ＯＣＯＮ社製：商品名、ＯＸＴＲＡＮ１０／５０Ａに取
り付けて酸素透過率を測定した。その測定結果は表４に
示す。Examples 12 to 16 and Comparative Examples 3 to 4 Diene polymer 15 as a component having a carbon-carbon unsaturated bond.
MBS resin containing 20 parts by weight of ABS resin, thermoplastic resin, transition metal compound and oxygen absorbing function modifier containing 20 parts by weight of the diene polymer in the proportions shown in Table 3, and a single screw extrusion with a coat hanger die attached to the tip. Machine (L / D =
In 24), melt-kneading and extruding were performed at a cylinder temperature of 250 ° C. or lower to obtain a sheet molded product having a wall thickness of 0.2 mm. The oxygen absorption function of each of the obtained sheet-shaped molded products was evaluated by leaving a 0.2 mm thick sheet in the atmosphere for 7 days and then measuring the oxygen permeability (M
OCON: product name, attached to OXTRAN10 / 50A to measure oxygen permeability. The measurement results are shown in Table 4.
【００４５】比較例３及び４のシート成形品の酸素透過
率は高く、酸素吸収機能を持たないのに対し、実施例１
２〜１６のシート成形品は、酸素透過率が著しく低下し
て酸素吸収機能を有することを示している。The sheet molded articles of Comparative Examples 3 and 4 have a high oxygen permeability and do not have an oxygen absorbing function, whereas Example 1
It is shown that the sheet molded products of Nos. 2 to 16 have an oxygen absorption function by significantly reducing the oxygen permeability.
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【表４】 [Table 4]
【００４８】[0048]
【発明の効果】以上のとおり、本発明の酸素吸収機能組
成物及びその成形体は、固形物又は種々の形状に成形が
可能であり、しかも被酸化性製品に直接接触しても毒性
や製品の変質等の汚染を発生させる恐れがないので、種
々の包装体からの酸素の除去及び抑制用としての用途に
使用することができる。INDUSTRIAL APPLICABILITY As described above, the oxygen-absorbing functional composition of the present invention and the molded article thereof can be molded into a solid material or various shapes, and further, even if they are directly contacted with an oxidizable product, the toxicity and the product can be reduced. Since there is no risk of causing contamination such as alteration of the above, it can be used for the purpose of removing and suppressing oxygen from various packages.
Claims (4)
遷移金属化合物の酸素吸収機能組成物。1. An oxygen absorbing functional composition of a component having a carbon-carbon unsaturated bond and a transition metal compound.
吸収機能組成物。2. An oxygen absorbing functional composition comprising the thermoplastic resin according to claim 1.
調節剤からなる酸素吸収機能組成物。3. An oxygen absorbing functional composition comprising the oxygen absorbing function controlling agent according to claim 1 or 2.
酸素吸収機能組成物を成形してなる成形体。4. A molded product obtained by molding the oxygen-absorbing functional composition according to claim 1, claim 2, or claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12807292A JPH05295171A (en) | 1992-04-21 | 1992-04-21 | Oxygen-absorbent composition and molded article thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12807292A JPH05295171A (en) | 1992-04-21 | 1992-04-21 | Oxygen-absorbent composition and molded article thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05295171A true JPH05295171A (en) | 1993-11-09 |
Family
ID=14975756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12807292A Pending JPH05295171A (en) | 1992-04-21 | 1992-04-21 | Oxygen-absorbent composition and molded article thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05295171A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002018496A1 (en) * | 2000-09-01 | 2002-03-07 | Kuraray Co., Ltd. | Resin composition and multilayered container |
| JP2002069320A (en) * | 2000-09-01 | 2002-03-08 | Kuraray Co Ltd | Resin composition excellent in gas barrier property |
| JP2002069319A (en) * | 2000-09-01 | 2002-03-08 | Kuraray Co Ltd | Resin composition having gas barrier property |
| JP2002241608A (en) * | 2000-12-08 | 2002-08-28 | Toyo Seikan Kaisha Ltd | Oxygen-absorbing resin composition, packaging material and multi-layered container for package |
| WO2004018556A1 (en) * | 2002-08-23 | 2004-03-04 | Toyo Seikan Kaisha,Ltd. | Oxygen-absorbing resin composition and layered product |
| JP2004123970A (en) * | 2002-10-04 | 2004-04-22 | Toyo Seikan Kaisha Ltd | Oxygen absorbing resin pellet, its manufacturing method, and multilayer container using the same |
| JP2006028524A (en) * | 1996-03-07 | 2006-02-02 | Cryovac Inc | Functional barrier in oxygen scavenging film |
| US7255904B2 (en) | 2000-09-01 | 2007-08-14 | Kuraray Co., Ltd. | Polyvinyl alcohol resin composition and multilayer packages |
| JP2009179672A (en) * | 2008-01-30 | 2009-08-13 | Mitsubishi Gas Chem Co Inc | Oxygen absorbing resin composition |
| JP2009298889A (en) * | 2008-06-11 | 2009-12-24 | Kyoraku Co Ltd | Oxygen-absorbing polyamide-based resin composition and method for producing the same |
| JP2010070765A (en) * | 1998-03-25 | 2010-04-02 | Cryovac Inc | Oxygen scavenger with reduced oxidation product for use in plastic film and beverage and food container |
-
1992
- 1992-04-21 JP JP12807292A patent/JPH05295171A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028524A (en) * | 1996-03-07 | 2006-02-02 | Cryovac Inc | Functional barrier in oxygen scavenging film |
| JP2010070765A (en) * | 1998-03-25 | 2010-04-02 | Cryovac Inc | Oxygen scavenger with reduced oxidation product for use in plastic film and beverage and food container |
| US7255904B2 (en) | 2000-09-01 | 2007-08-14 | Kuraray Co., Ltd. | Polyvinyl alcohol resin composition and multilayer packages |
| JP2002069320A (en) * | 2000-09-01 | 2002-03-08 | Kuraray Co Ltd | Resin composition excellent in gas barrier property |
| JP2002069319A (en) * | 2000-09-01 | 2002-03-08 | Kuraray Co Ltd | Resin composition having gas barrier property |
| WO2002018496A1 (en) * | 2000-09-01 | 2002-03-07 | Kuraray Co., Ltd. | Resin composition and multilayered container |
| US7820261B2 (en) | 2000-09-01 | 2010-10-26 | Kuraray Co., Ltd. | Polyvinyl alcohol resin composition and multilayer packages |
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| JP2002241608A (en) * | 2000-12-08 | 2002-08-28 | Toyo Seikan Kaisha Ltd | Oxygen-absorbing resin composition, packaging material and multi-layered container for package |
| WO2004018556A1 (en) * | 2002-08-23 | 2004-03-04 | Toyo Seikan Kaisha,Ltd. | Oxygen-absorbing resin composition and layered product |
| AU2003262283B2 (en) * | 2002-08-23 | 2007-03-22 | Toyo Seikan Kaisha, Ltd. | Oxygen-absorbing resin composition and layered product |
| JP2008195949A (en) * | 2002-08-23 | 2008-08-28 | Toyo Seikan Kaisha Ltd | Oxygen-absorbing resin composition and laminated body |
| JPWO2004018556A1 (en) * | 2002-08-23 | 2005-12-08 | 東洋製罐株式会社 | Oxygen-absorbing resin composition and laminate |
| US8592522B2 (en) | 2002-08-23 | 2013-11-26 | Toyo Seikan Kaisha, Ltd. | Oxygen-absorbing resin composition and laminate |
| JP2004123970A (en) * | 2002-10-04 | 2004-04-22 | Toyo Seikan Kaisha Ltd | Oxygen absorbing resin pellet, its manufacturing method, and multilayer container using the same |
| JP2009179672A (en) * | 2008-01-30 | 2009-08-13 | Mitsubishi Gas Chem Co Inc | Oxygen absorbing resin composition |
| JP2009298889A (en) * | 2008-06-11 | 2009-12-24 | Kyoraku Co Ltd | Oxygen-absorbing polyamide-based resin composition and method for producing the same |
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