JP3405408B2 - Oxygen scavenging composition - Google Patents
Oxygen scavenging compositionInfo
- Publication number
- JP3405408B2 JP3405408B2 JP2000330302A JP2000330302A JP3405408B2 JP 3405408 B2 JP3405408 B2 JP 3405408B2 JP 2000330302 A JP2000330302 A JP 2000330302A JP 2000330302 A JP2000330302 A JP 2000330302A JP 3405408 B2 JP3405408 B2 JP 3405408B2
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- resin composition
- compound
- phosphorus
- transition metal
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は酸素捕捉性組成物、及び
酸素捕捉性シートに関するものであり、有機物の酸化防
止、あるいは腐敗防止、包装材等、種々の分野で利用で
きる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen scavenging composition and an oxygen scavenging sheet, which can be used in various fields such as oxidation prevention or decay prevention of organic substances and packaging materials.
【０００２】[0002]
【従来の技術】空気中に存在する酸素が金属を酸化した
り、有機物を酸化、劣化させることは良く知られてい
る。これらの障害を防ぐ手段としては、例えば、有機物
の場合であれば、フェノール化合物、アミン化合物、硫
黄化合物などのいわゆる、酸化防止剤を添加する方法が
よく知られている。一方、金属の酸化を防ぐ方法として
は、金属表面を酸化され難い他の金属、有機高分子材
料、例えば、塗料、プラスチックスフィルムなどで被覆
することによって、物理的に水や酸素を遮断する方法、
よりイオン化傾向の大きい金属で被覆して保護する方法
などがとられている。2. Description of the Related Art It is well known that oxygen existing in air oxidizes metals and oxidizes and deteriorates organic substances. As a means for preventing these obstacles, for example, in the case of an organic substance, a method of adding a so-called antioxidant such as a phenol compound, an amine compound or a sulfur compound is well known. On the other hand, as a method of preventing metal oxidation, a method of physically blocking water or oxygen by coating the metal surface with another metal that is difficult to be oxidized, an organic polymer material, such as a paint or a plastics film, is used. ,
For example, a method of covering with a metal having a greater ionization tendency to protect it has been adopted.
【０００３】上記目的のため使用されているプラスチッ
クスフィルムとしては、ポリエチレン、ポリプロピレ
ン、ナイロン、ポリエステル、ポリ塩化ビニリデン、ポ
リ塩化ビニールなどがそれぞれ、単独あるいは組合せで
用いられている。また、特開平２−５００８４６号公報
において、酸素を遮蔽するための高分子材料、特に酸化
を受けやすい高分子材料に金属触媒を添加して酸素遮蔽
効果を高める方法も提案されている。一方、特定の金属
が酸素によって酸化されやすいことを利用して、これら
金属を粉末状にして酸素透過性の低い材料でつくられた
容器に入れて食品の保存、防虫、防黴などの目的に利用
されている。また、同様な目的に、特定のグリコ−ルと
アルカリ性化合物および遷移金属化合物からなる脱酸素
剤も提案されている。As the plastic film used for the above purpose, polyethylene, polypropylene, nylon, polyester, polyvinylidene chloride, polyvinyl chloride, etc. are used alone or in combination. Further, Japanese Patent Laid-Open No. 2-500846 proposes a method of enhancing the oxygen shielding effect by adding a metal catalyst to a polymer material for shielding oxygen, particularly a polymer material which is easily oxidized. On the other hand, taking advantage of the fact that certain metals are easily oxidized by oxygen, put these metals into powder and put them in a container made of a material with low oxygen permeability for the purpose of food preservation, insect repellent, mildew proof, etc. It's being used. Further, for the same purpose, an oxygen scavenger composed of a specific glycol, an alkaline compound and a transition metal compound has also been proposed.
【０００４】[0004]
【発明が解決しようとする課題】上記のように、種々の
産業分野における、酸素によってもたらされる障害を防
ぐ数多くの手段が実用化され、提案されているが、それ
ぞれ、解決すべき課題を有する。As described above, various means for preventing the damage caused by oxygen in various industrial fields have been put into practical use and proposed, but each has problems to be solved.
【０００５】一方、食品を中心とする酸化劣化や細菌、
黴などの発生を防ぐ目的で酸素バリヤー性容器に鉄粉を
主剤にした脱酸素剤を存在させて容器内を無酸素状態に
する方法も知られているが、バリヤー材の酸素遮蔽効果
が充分でないとか、脱酸素剤については水の併用が不可
欠であるほか鉄粉による内容物の汚染が問題になる場合
がある。特開平２−５００８４６号公報における特に酸
化を受けやすい高分子材料に金属触媒を添加して酸素遮
蔽効果を高める方法は使用目的によっては、酸素の捕捉
性能が十分でないという問題点がある。本発明は上記従
来技術の課題を解決することのできる酸素吸収能に優れ
た組成物を提供するものである。On the other hand, oxidative deterioration and bacteria mainly in foods,
There is also known a method in which an oxygen scavenger containing iron powder as a main component is present in an oxygen barrier container to prevent the formation of mold and the like to make the inside of the container oxygen-free, but the oxygen shielding effect of the barrier material is sufficient. Otherwise, it is indispensable to use water in combination with the oxygen scavenger, and the contamination of the contents with iron powder may become a problem. The method of adding a metal catalyst to a polymer material which is particularly susceptible to oxidation in JP-A-2-500846 has a problem that the oxygen trapping performance is not sufficient depending on the purpose of use. The present invention provides a composition having excellent oxygen absorption ability, which can solve the above-mentioned problems of the prior art.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記の如き
課題を解決すべく酸素捕捉性樹脂組成物について鋭意研
究した結果、特定のポリアミドと遷移金属化合物に特定
割合のリン化合物を配合した樹脂組成物が著しく酸素捕
捉性に優れていることを見出し、本発明を完成させた。Means for Solving the Problems As a result of intensive studies on the oxygen scavenging resin composition to solve the above problems, the present inventors have blended a specific polyamide and a transition metal compound with a specific ratio of a phosphorus compound. The present invention has been completed by finding that the resin composition has a remarkably excellent oxygen scavenging property.
【０００７】すなわち、本発明は、キシリレン基含有ポ
リアミド、遷移金属化合物、及びリン化合物から成る樹
脂組成物であって、該樹脂組成物に対しリン化合物の配
合割合がリンとして１５０〜１０，０００質量ｐｐｍで
あることを特徴とする酸素捕捉性樹脂組成物、当該樹脂
組成物を成形して得たシート状成形物、及び当該樹脂組
成物を成形して得た酸素バリヤー性容器並びに、キシリ
レン基含有ポリアミド、遷移金属化合物、及びリン化合
物からなる樹脂組成物であって、該樹脂組成物に対しリ
ン化合物の配合割合がリンとして１５０〜１０，０００
質量ｐｐｍである組成物をシール袋内にいれて袋内の酸
素を吸収する酸素吸収方法に関するものである。That is, the present invention is a resin composition comprising a xylylene group-containing polyamide, a transition metal compound, and a phosphorus compound, wherein the phosphorus compound is contained in the resin composition in an amount of 150 to 10,000 mass as phosphorus. Oxygen-scavenging resin composition characterized by being in ppm, sheet-like molded product obtained by molding the resin composition, oxygen barrier container obtained by molding the resin composition, and xylylene group-containing A resin composition comprising a polyamide, a transition metal compound, and a phosphorus compound, wherein the compounding ratio of the phosphorus compound to the resin composition is 150 to 10,000 as phosphorus.
The present invention relates to an oxygen absorption method in which a composition having a mass ppm is put in a sealed bag to absorb oxygen in the bag.
【０００８】本発明で用いられるキシリレン基含有ポリ
アミドとは、メタキシリレンジアミン又はパラキシリレ
ンジアミンと有機ジカルボン酸、例えば、アジピン酸、
セバシン酸、ダイマー酸などを重縮合して得られるポリ
アミドである。The xylylene group-containing polyamide used in the present invention means metaxylylenediamine or paraxylylenediamine and an organic dicarboxylic acid such as adipic acid,
It is a polyamide obtained by polycondensing sebacic acid, dimer acid and the like.
【０００９】本発明で用いられる遷移金属化合物として
は、コバルト、マンガン、銅、鉄、ニッケル、ロジウム
等の遷移金属の酢酸塩、ステアリン酸塩、ナフテン酸塩
等のモノカルボン酸、ジカルボン酸、及びキレート化合
物などが挙げられる。上記の中でも好ましい遷移金属化
合物は、酢酸コバルト、ステアリン酸コバルト、アセチ
ルアセトンコバルト、アセチルアセトン鉄、酢酸マンガ
ンである。これらの遷移金属化合物は一種もしくは二種
以上併用することができ、全樹脂組成物に対して金属成
分として１〜１０，０００質量ｐｐｍの範囲、好ましく
は、１０〜１，０００質量ｐｐｍの範囲で添加される。Examples of the transition metal compound used in the present invention include acetates of transition metals such as cobalt, manganese, copper, iron, nickel and rhodium, monocarboxylic acids such as stearates and naphthenates, dicarboxylic acids, and Examples thereof include chelate compounds. Among the above, preferable transition metal compounds are cobalt acetate, cobalt stearate, acetylacetone cobalt, acetylacetone iron, and manganese acetate. These transition metal compounds can be used alone or in combination of two or more, and in the range of 1 to 10,000 mass ppm, preferably 10 to 1,000 mass ppm as a metal component with respect to the total resin composition. Is added.
【００１０】本発明で用いられるリン化合物としては、
リン酸塩、亜リン酸塩、次亜リン酸塩が挙げられる。具
体例としてはリン酸三ナトリウム、リン酸三カリウム、
リン酸水素二ナトリウム、リン酸水素二カリウム、リン
酸二水素ナトリウム、リン酸二水素カリウム、亜リン酸
ナトリウム、亜リン酸カリウム、次亜リン酸ナトリウ
ム、次亜リン酸カリウム、リン酸鉄などが挙げられる。
これらリン化合物はそれぞれ一種もしくは二種以上併用
することが出来、全樹脂組成物に対してリン成分として
１５０〜１０，０００質量ｐｐｍ、好ましくは１５０〜
１，０００質量ｐｐｍの範囲で添加される。As the phosphorus compound used in the present invention,
Phosphates, phosphites and hypophosphites are mentioned. Specific examples include trisodium phosphate, tripotassium phosphate,
Disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium phosphite, potassium phosphite, sodium hypophosphite, potassium hypophosphite, iron phosphate, etc. Is mentioned.
These phosphorus compounds may be used either individually or in combination of two or more, and are used as a phosphorus component in the total resin composition in an amount of 150 to 10,000 mass ppm, preferably 150 to 10,000 mass ppm.
It is added in the range of 1,000 mass ppm.
【００１１】本発明の酸素捕捉性樹脂組成物をポリプロ
ピレン、ポリエチレン、マレイン酸変性ポリプロピレ
ン、マレイン酸変性ポリエチレン、ポリ−４−メチルペ
ンテン−１等のポリオレフィン、ナイロン６、ナイロン
６６等のポリアミド、ポリカーボネート、ポリ塩化ビニ
ール、ポリビニルアセテート等の熱可塑性樹脂、又は、
エポキシ樹脂、フェノール樹脂、メラミン樹脂、不法和
ポリエステル樹脂、ポリウレタン等の熱硬化性樹脂に配
合して使用することもでき、更に本発明の組成物中に酸
素との接触性、流動性の向上を図るため、及び液体の担
体として種々の無機・有機化合物を配合して使用するこ
とができる。The oxygen-scavenging resin composition of the present invention is prepared by using polypropylene, polyethylene, maleic acid-modified polypropylene, maleic acid-modified polyethylene, polyolefin such as poly-4-methylpentene-1, polyamide such as nylon 6 and nylon 66, polycarbonate, Thermoplastic resin such as polyvinyl chloride, polyvinyl acetate, or
Epoxy resin, phenol resin, melamine resin, illegal polyester resin, it can also be used by blending with thermosetting resins such as polyurethane, further improve the contact with oxygen and fluidity in the composition of the present invention. Various inorganic / organic compounds can be mixed and used for the purpose and as a liquid carrier.
【００１２】本発明において使用される遷移金属化合物
およびリン化合物はキシリレン基含有ポリアミドに混合
して共存させることが必要であり、以下にその製造方法
を例示するがこれらの方法に限定されるものではない。
本発明における組成物の調製方法は組成物の性状によっ
て若干異なるが、基本的には、遷移金属化合物およびり
ん化合物の添加は別々であっても、それぞれ単独であっ
ても良く、また、その添加順序も任意に選べる。例え
ば、キシリレン基含有ポリアミドに遷移金属化合物およ
びリン化合物を両樹脂の溶融温度以下で混合（ドライブ
レンド）した後、押出機、ニーダー等により溶融混合す
ることも可能である。但し、遷移金属化合物および／も
しくはリン化合物をキシリレン基含有ポリアミド以外の
他の熱可塑性樹脂に予め溶融混練した後、キシリレン基
含有ポリアミドと溶融混練することは両樹脂が十分に混
合し難いため適当ではない。The transition metal compound and the phosphorus compound used in the present invention must be mixed and coexisted in the xylylene group-containing polyamide, and the production method thereof will be exemplified below, but the method is not limited to these methods. Absent.
The method for preparing the composition in the present invention is slightly different depending on the properties of the composition, but basically, the addition of the transition metal compound and the phosphorus compound may be separate or may be independent of each other. The order can be selected arbitrarily. For example, it is also possible to mix (dry blend) the transition metal compound and the phosphorus compound with the xylylene group-containing polyamide at a temperature not higher than the melting temperature of both resins, and then melt-mix with an extruder, a kneader, or the like. However, it is not suitable to melt-knead the transition metal compound and / or the phosphorus compound with a thermoplastic resin other than the xylylene group-containing polyamide in advance and then melt-knead the same with the xylylene group-containing polyamide because it is difficult to sufficiently mix both resins. Absent.
【００１３】本発明の酸素捕捉性組成物は、シート状に
成形して使用することができ、同様に種々の成形方法に
より酸素バリヤー性容器に成形して使用することもでき
る。又、本発明は、本発明の酸素捕捉性組成物をシール
袋内にいれて袋内の酸素を吸収する方法にも使用するこ
とができる。この場合、当該組成物をシート状に成形し
て使用することもできる。以下に本発明の特徴および効
果を実施例をもって示す。The oxygen-scavenging composition of the present invention can be molded into a sheet and used, and similarly, it can be molded into an oxygen barrier container by various molding methods and used. The present invention can also be used in a method for absorbing oxygen in a bag by putting the oxygen-scavenging composition of the present invention in a sealed bag. In this case, the composition can be molded into a sheet and used. The features and effects of the present invention will be shown below with examples.
【００１４】実施例 1
ポリメタキシリレンアジパミド（以下、ＮＭＸＤ６とい
う、相対粘度：２．０）のペレットと次亜リン酸ナトリ
ウム１水和物をＮＭＸＤ６中のリン濃度で２３０ｐｐｍ
になるように混合、溶融し、２６０〜２７０℃の温度条
件下で押出しを行うことにより再度ペレット化した。次
いで、リンを含むＮＭＸＤ６のペレット２５質量部とス
テアリン酸コバルト、および低密度ポリエチレン( 日本
石油化学（株）製、商品名 :三井日石ポリエチレン、グ
レードＦ４１）７５質量部を、全樹脂量（以下、シート
中という）を基準にしたコバルトの濃度が２００質量ｐ
ｐｍになるような割合で混合し、押出し機（東洋精機
（株) 製、型式：ラボプラストミル、シリンダー直径：
２０ｍｍ、スクリュウ形状: フルフライト、単軸）を用
いて、２６０〜２７０℃の温度でシート化した。Example 1 Pellets of polymeta-xylylene adipamide (hereinafter referred to as NMXD6, relative viscosity: 2.0) and sodium hypophosphite monohydrate were added at a phosphorus concentration of 230 ppm in NMXD6.
Were mixed and melted so as to be, and extruded under a temperature condition of 260 to 270 ° C. to pelletize again. Next, 25 parts by mass of NMXD6 pellets containing phosphorus, cobalt stearate, and 75 parts by mass of low-density polyethylene (manufactured by Nippon Petrochemical Co., Ltd., trade name: Mitsui Nisseki Polyethylene, Grade F41) were added to the total resin amount (hereinafter , In the sheet) the cobalt concentration is 200 mass p
Extruder (manufactured by Toyo Seiki Co., Ltd., model: Labo Plastomill, cylinder diameter:
20 mm, screw shape: full flight, uniaxial), a sheet was formed at a temperature of 260 to 270 ° C.
【００１５】得られたＮＭＸＤ６、リン化合物、コバル
ト化合物およびポリエチレンからなる厚さ４００μｍの
シートを、幅１２０ｍｍ、長さ１５０ｍｍに切り取っ
た。上記切り取った５枚のシートをヒートシール層を有
する長さ２５０ｍｍ、幅２００ｍｍの３方シール袋（内
層：ポリエチレン、外層：アルミ箔）に入れ、袋内の空
気量を２５０ｍｌに調整した後、袋の一方をシールし
た。２３℃の温度条件下で３０日経過後に袋内の気体を
注射器でサンプリングし、酸素濃度計（東レエンジニア
リング（株）製、型式：ＬＣ−７００Ｆ）で袋内の酸素
濃度を測定した。尚、酸素吸収量（ｍｌ／ｍ2 ）の計算
は、以下の方法によった。
酸素吸収量＝〔Ｖ1 ×（Ｃ1 −Ｃ2 ）〕／〔（１−
Ｃ2 ）×Ｓ〕
但し、Ｖ1 ：初期空気量（ｍｌ）
Ｃ1 ：初期酸素濃度（０．２０５ｍｌ／ｍｌ）
Ｃ2 ：一定時間後の酸素濃度（ｍｌ／ｍｌ）
Ｓ ：シート表面積（ｍ2 ）
表１に３０日後の酸素濃度とシートの酸素吸収量を示
す。A 400 μm-thick sheet made of NMXD6, a phosphorus compound, a cobalt compound and polyethylene thus obtained was cut into a piece having a width of 120 mm and a length of 150 mm. The above-mentioned five cut sheets were put into a three-side sealed bag having a heat-sealing layer and having a length of 250 mm and a width of 200 mm (inner layer: polyethylene, outer layer: aluminum foil), and after adjusting the air amount in the bag to 250 ml, the bag One side was sealed. After the lapse of 30 days under the temperature condition of 23 ° C., the gas in the bag was sampled with a syringe, and the oxygen concentration in the bag was measured by an oxygen concentration meter (Toray Engineering Co., Ltd., model: LC-700F). The oxygen absorption amount (ml / m 2 ) was calculated by the following method. Oxygen absorption amount = [V 1 × (C 1 -C 2 )] / [(1-
C 2 ) × S] However, V 1 : initial air amount (ml) C 1 : initial oxygen concentration (0.205 ml / ml) C 2 : oxygen concentration after a certain time (ml / ml) S: sheet surface area (m 2 ) Table 1 shows the oxygen concentration after 30 days and the oxygen absorption amount of the sheet.
【００１６】実施例２
次亜リン酸ナトリウム１水和物をＮＭＸＤ６中のリン濃
度で２３０質量ｐｐｍ含むＮＭＸＤ６のペレット５０質
量部とアセチルアセトン鉄、および低密度ポリエチレン
( 日本石油化学（株）製、商品名 :三井日石ポリエチレ
ン、グレードＦ４１）５０質量部を、シート中の鉄濃度
が１９０質量ｐｐｍになるような割合で配合し、押出し
機を用いて、実施例１と同様な方法で２６０〜２７０℃
の温度条件でシート化した。得られたＮＭＸＤ６、リン
化合物、鉄化合物およびポリエチレンからなるシートに
ついて、実施例１と同様な方法によりシートの酸素吸収
性を調べた。測定結果を表2 に示す。Example 2 50 parts by mass of NMXD6 pellets containing sodium hypophosphite monohydrate containing 230 ppm by mass of phosphorus in NMXD6, iron acetylacetone, and low-density polyethylene
(Nippon Petrochemical Co., Ltd., trade name: Mitsui Nisseki Polyethylene, Grade F41) 50 parts by mass were blended in such a proportion that the iron concentration in the sheet would be 190 ppm by mass and carried out using an extruder. 260-270 ° C. in the same manner as in Example 1.
Sheets were formed under the temperature conditions of. With respect to the obtained sheet of NMXD6, phosphorus compound, iron compound and polyethylene, the oxygen absorption of the sheet was examined by the same method as in Example 1. Table 2 shows the measurement results.
【００１７】比較例１
実施例１で得られたリン化合物を混合する前のＮＭＸＤ
６のペレット２５重量部とステアリン酸コバルトおよび
低密度ポリエチレン( 日本石油化学（株）製、商品名 :
三井日石ポリエチレン、グレードＦ４１）７５重量部
を、シート中のコバルトの濃度が２００質量ｐｐｍにな
るような割合で混合し、実施例１と同様の方法で、２６
０〜２７０℃の温度条件でシート化した。得られたＮＭ
ＸＤ６、コバルト化合物およびポリエチレンからなる厚
さ４００μｍのシートを幅１２０ｍｍ、長さ１５０ｍｍ
のサイズに切り取った。上記シートを、ヒートシール層
を有する長さ２５０ｍｍ、幅２００ｍｍの３方シール袋
（内層：ポリエチレン、外層：アルミ箔）に入れ、袋内
の空気量を２５０ｍｌに調整した後、袋の一方をシール
した。３０日後に袋内の気体を注射器でサンプリング
し、酸素濃度計で酸素濃度を測定した。表１に３０日後
の袋内の酸素濃度とシートの酸素吸収量を示す。表１か
ら、このシートは酸素の吸収量が極めて少ないことがわ
かる。Comparative Example 1 NMXD before mixing with the phosphorus compound obtained in Example 1
25 parts by weight of pellets of 6 and cobalt stearate and low density polyethylene (manufactured by Nippon Petrochemical Co., Ltd., trade name:
75 parts by weight of Mitsui Nisseki Polyethylene, Grade F41) were mixed in a ratio such that the concentration of cobalt in the sheet was 200 mass ppm, and the same method as in Example 1 was used to prepare 26
A sheet was formed under a temperature condition of 0 to 270 ° C. Obtained NM
A sheet with a thickness of 400 μm made of XD6, a cobalt compound, and polyethylene is 120 mm wide and 150 mm long.
Cut to size. The above sheet was placed in a 250 mm long, 200 mm wide three-side sealed bag (inner layer: polyethylene, outer layer: aluminum foil) having a heat-sealing layer, and after adjusting the amount of air in the bag to 250 ml, one side of the bag was sealed. did. After 30 days, the gas in the bag was sampled with a syringe and the oxygen concentration was measured with an oximeter. Table 1 shows the oxygen concentration in the bag and the oxygen absorption amount of the sheet after 30 days. From Table 1, it can be seen that this sheet has an extremely small amount of oxygen absorbed.
【００１８】[0018]
【本発明の効果】本発明のキシリレン基含有ポリアミ
ド、遷移金属化合物、及びリン化合物からなる酸素捕捉
性樹脂組成物を使用することにより、従来知られていた
酸素捕捉性樹脂組成物の酸素捕捉性能を大幅に増加させ
ることができ、酸素による金属の発錆防止、有機物の酸
化防止、あるいは腐敗防止、防虫、防黴などを必要とす
る広い分野で利用可能となった。EFFECT OF THE INVENTION By using the oxygen-scavenging resin composition of the present invention, which comprises a xylylene group-containing polyamide, a transition metal compound, and a phosphorus compound, the oxygen-scavenging performance of a conventionally known oxygen-scavenging resin composition is improved. It can be used in a wide range of fields that require rust prevention of metals due to oxygen, oxidation prevention of organic substances, decay prevention, insect repellent, mildew proof, etc.
【００１９】 表１実施例・比較例番号 実施例１ 実施例２ 比較例１ シート中の遷移金属濃度 コバルト濃度（質量ｐｐｍ） ２００ − ２００ 鉄濃度（質量ｐｐｍ） − １９０ − ＮＭＸＤ６中のリン濃度（質量ｐｐｍ） ２３０ ２３０ − 袋内酸素濃度（％） ２．１ １１．２ ２０．３ シートの酸素吸収量（ｍｌ／ｍ 2 ） ２６０ １４３ ３ Table 1 Example / Comparative Example Number Example 1 Example 2 Comparative Example 1 Transition metal concentration in sheet Cobalt concentration (mass ppm) 200-200 Iron concentration (mass ppm) -190-Phosphorus concentration in NMXD6 ( Mass ppm) 230 230-Oxygen concentration in bag (%) 2.1 11.2 20.3 Oxygen absorption of sheet (ml / m 2 ) 260 143 3
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西村 敏秋 神奈川県平塚市東八幡５丁目６番２号 三菱瓦斯化学株式会社 平塚研究所内 (56)参考文献 特開 平５−140555（ＪＰ，Ａ) 特開 平６−41422（ＪＰ，Ａ) 特開 平４−45152（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 69/00 - 69/50 C08L 77/00 - 77/12 C09K 15/00 - 15/34 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiaki Nishimura 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Mitsubishi Gas Chemical Co., Ltd. Hiratsuka Research Laboratory (56) Reference JP-A-5-140555 (JP, A) Kaihei 6-41422 (JP, A) JP-A-4-45152 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08G 69/00-69/50 C08L 77/00- 77/12 C09K 15/00-15/34
Claims (9)
合物、及びリン化合物から成る樹脂組成物であって、該
樹脂組成物に対しリン化合物の配合割合がリンとして１
５０〜１０，０００質量ｐｐｍであることを特徴とする
酸素捕捉性樹脂組成物。1. A xylylene group-containing polyamide, a transition metal compound, and a resin composition comprising a phosphorus compound, the
The phosphorus compound content in the resin composition is 1 as phosphorus.
An oxygen-scavenging resin composition, which is 50 to 10,000 mass ppm.
シリレンアジパミドである請求項１記載の酸素捕捉性樹
脂組成物。Wherein oxygen scavenging resin composition of claim 1, wherein a xylylene group-containing polyamide is a poly-m-xylylene adipamide Mi de.
リン酸塩の少なくとも１種以上である請求項１又は２に
記載の酸素捕捉性樹脂組成物。3. The phosphorus compound is hypophosphite, phosphite,
The oxygen-scavenging resin composition according to claim 1 or 2, which is at least one kind of phosphate.
ト化合物又は鉄化合物である請求項１又は２のいずれか
に記載の酸素捕捉性樹脂組成物。4. The oxygen-scavenging resin composition according to claim 1, wherein at least one transition metal compound is a cobalt compound or an iron compound.
の遷移金属成分として１〜１０，０００質量ｐｐｍであ
る請求項１又は２に記載の酸素捕捉性樹脂組成物。5. The oxygen-scavenging resin composition according to claim 1 or 2, wherein the blending ratio of the transition metal compound is 1 to 10,000 mass ppm as a transition metal component in the resin composition.
合物、及びリン化合物から成る樹脂組成物であって、該
樹脂組成物に対しリン化合物の配合割合がリンとして１
５０〜１０，０００質量ｐｐｍである酸素捕捉性樹脂組
成物を成形して得たシート状成形物。6. xylylene group-containing polyamide, a transition metal compound, and a resin composition comprising a phosphorus compound, the
The phosphorus compound content in the resin composition is 1 as phosphorus.
A sheet-shaped molded product obtained by molding an oxygen-scavenging resin composition having a content of 50 to 10,000 mass ppm.
合物、及びリン化合物から成る樹脂組成物であって、該
樹脂組成物に対しリン化合物の配合割合がリンとして１
５０〜１０，０００質量ｐｐｍである酸素捕捉性樹脂組
成物を成形した得た酸素バリヤー性容器。7. The xylylene group-containing polyamide, a transition metal compound, and a resin composition comprising a phosphorus compound, the
The phosphorus compound content in the resin composition is 1 as phosphorus.
An oxygen barrier container obtained by molding an oxygen scavenging resin composition having a content of 50 to 10,000 mass ppm.
合物、及びリン化合物からなる樹脂組成物であって、該
樹脂組成物に対しリン化合物の配合割合がリンとして１
５０〜１０，０００質量ｐｐｍである組成物をシール袋
内にいれて袋内の酸素を吸収する酸素吸収方法。8. xylylene group-containing polyamide, a transition metal compound, and a resin composition comprising a phosphorus compound, the
The phosphorus compound content in the resin composition is 1 as phosphorus.
An oxygen absorption method in which a composition of 50 to 10,000 mass ppm is put in a sealed bag to absorb oxygen in the bag.
る請求項８に記載の酸素吸収方法。9. The oxygen absorption method according to claim 8, wherein the resin composition is formed into a sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000330302A JP3405408B2 (en) | 2000-10-30 | 2000-10-30 | Oxygen scavenging composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000330302A JP3405408B2 (en) | 2000-10-30 | 2000-10-30 | Oxygen scavenging composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30061891A Division JP3183300B2 (en) | 1991-11-15 | 1991-11-15 | Oxygen scavenging composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001226585A JP2001226585A (en) | 2001-08-21 |
| JP3405408B2 true JP3405408B2 (en) | 2003-05-12 |
Family
ID=18806850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000330302A Expired - Lifetime JP3405408B2 (en) | 2000-10-30 | 2000-10-30 | Oxygen scavenging composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3405408B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007223667A (en) * | 2006-02-27 | 2007-09-06 | Dainippon Printing Co Ltd | Plastic container having gas barrier layer |
| JP2007308155A (en) * | 2006-05-17 | 2007-11-29 | Dainippon Printing Co Ltd | Plastic container having gas barrier layer |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003335856A (en) * | 2002-03-11 | 2003-11-28 | Mitsubishi Gas Chem Co Inc | Method for producing oxygen-absorptive polyamide resin composition, and oxygen-absorptive polyamide resin composition obtained by the method |
| JP2003327715A (en) * | 2002-05-16 | 2003-11-19 | Mitsubishi Gas Chem Co Inc | Method of storing molded product |
| JP4321197B2 (en) * | 2002-10-03 | 2009-08-26 | 三菱瓦斯化学株式会社 | Method for producing polyamide composite material |
| JP4678141B2 (en) * | 2003-05-29 | 2011-04-27 | 三菱瓦斯化学株式会社 | Masterbatch and method for producing oxygen-absorbing molded body |
| AU2004202264B2 (en) * | 2003-05-29 | 2008-12-18 | Mitsubishi Gas Chemical Company, Inc. | Masterbatch and production method of oxygen-absorbing molded article |
| JP5200335B2 (en) * | 2006-05-31 | 2013-06-05 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| JP5315599B2 (en) * | 2006-08-30 | 2013-10-16 | 三菱瓦斯化学株式会社 | Resin composition and multilayer structure |
| EP2025718B1 (en) * | 2006-05-31 | 2017-02-15 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
| JP2011094021A (en) * | 2009-10-29 | 2011-05-12 | Mitsubishi Gas Chemical Co Inc | Oxygen absorbing resin composition |
| US20150225541A1 (en) * | 2012-08-31 | 2015-08-13 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition and method for producing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0445152A (en) * | 1990-06-11 | 1992-02-14 | Toppan Printing Co Ltd | Oxygen-absorbing resin composition |
| BE1004334A3 (en) * | 1991-01-08 | 1992-11-03 | Solvay | Polymer compositions properties and barrier packaging materials a shaped therefrom. |
| JP3183300B2 (en) * | 1991-11-15 | 2001-07-09 | 三菱瓦斯化学株式会社 | Oxygen scavenging composition |
-
2000
- 2000-10-30 JP JP2000330302A patent/JP3405408B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007223667A (en) * | 2006-02-27 | 2007-09-06 | Dainippon Printing Co Ltd | Plastic container having gas barrier layer |
| JP2007308155A (en) * | 2006-05-17 | 2007-11-29 | Dainippon Printing Co Ltd | Plastic container having gas barrier layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001226585A (en) | 2001-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3405408B2 (en) | Oxygen scavenging composition | |
| JPH05140555A (en) | Oxygen-capturing composition | |
| EP0507207B1 (en) | Compositions, articles and methods for scavenging oxygen | |
| US5274024A (en) | Oxygen-absorbing resin composition containing water-absorbing polymer, olefin resin and oxygen scavenger | |
| DE69631882T2 (en) | OXYGEN ABSORBENT COMPOSITION | |
| US5582820A (en) | Multilayered structure and colostomy bag made therefrom | |
| EP1029020A1 (en) | Oxygen-scavenging filled polymer blend for food packaging applications | |
| RU2572982C2 (en) | Layered plastic for protection of metals against corrosion-active gases | |
| JPH08502770A (en) | Polymer composition containing oxygen scavenging compound | |
| JP2001040350A (en) | Oxygen scavenger composition | |
| JPH0445152A (en) | Oxygen-absorbing resin composition | |
| US8728347B2 (en) | Oxygen absorber, oxygen absorbent resin composition, and oxygen absorbent film | |
| BR112016026345B1 (en) | PELLET RESIN COMPOSITION, ITS PRODUCTION METHODS, FILM, AND MOLDED ARTICLE | |
| US5284892A (en) | Aldehyde scavenging compositions and methods relating thereto | |
| JP5143322B2 (en) | Resin composition with excellent gas barrier properties | |
| JP3460789B2 (en) | Deoxidizing multilayer film | |
| JP2009215399A (en) | Oxygen absorbing resin composition | |
| JP5405021B2 (en) | Oxygen-absorbing composition and container using the same | |
| WO2016009975A1 (en) | Oxygen-absorbing resin composition | |
| JP2007137975A (en) | Oxygen-absorbing resin composition and film or sheet made of the composition | |
| JP2001347612A (en) | Multilayer structure | |
| JPH0593189A (en) | Oxygen scavenger | |
| WO1995004776A1 (en) | Oxygen scavenging thermoplastics | |
| JP2020158140A (en) | Deodorant package | |
| JP2003012940A (en) | Resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080307 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090307 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100307 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100307 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110307 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120307 Year of fee payment: 9 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120307 Year of fee payment: 9 |