JPH05237380A - Oxygen absorbing sheet - Google Patents
Oxygen absorbing sheetInfo
- Publication number
- JPH05237380A JPH05237380A JP4037746A JP3774692A JPH05237380A JP H05237380 A JPH05237380 A JP H05237380A JP 4037746 A JP4037746 A JP 4037746A JP 3774692 A JP3774692 A JP 3774692A JP H05237380 A JPH05237380 A JP H05237380A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- sheet
- absorbing sheet
- stretching
- iron
- 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
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gas Separation By Absorption (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸素吸収シートに関す
る。さらに詳しくは、取扱いが容易であり、酸素吸収能
力を制御した酸素吸収シートであり、さらに臭気が問題
とならない高性能酸素吸収シートに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen absorbing sheet. More specifically, the present invention relates to an oxygen absorbing sheet that is easy to handle and has a controlled oxygen absorbing ability, and further relates to a high performance oxygen absorbing sheet in which odor does not pose a problem.
【０００２】[0002]
【従来の技術】脱酸素剤は食品をはじめ、種々の製品の
保存に際して酸素が好まれないような場合に、酸素の除
去を目的として多方面において使用されている。通常使
用されている粉体の酸素吸収剤を通気度のある素材で包
装する方法は、素材の密封が完全でないと、粉体が外部
に漏れるという問題がある。また、本発明者らは取扱い
が容易であり酸素吸収能力を制御した酸素吸収シートと
して、酸素吸収剤を樹脂に充填して多孔質化する方法を
特開平２−２０３９３７号公報に提案しているが、ある
種の樹脂の場合、若干臭気に問題があり、食品分野等で
は、必ずしも充分なものとは言い難かった。2. Description of the Related Art Oxygen scavengers are used in various fields for the purpose of removing oxygen when oxygen is not preferred when storing various products such as foods. The commonly used method of packaging a powder oxygen absorber with a material having air permeability has a problem that the powder leaks to the outside unless the material is completely sealed. Further, the inventors of the present invention have proposed in JP-A-2-203937 a method of filling a resin with an oxygen absorbent to make it porous as an oxygen absorbent sheet which is easy to handle and whose oxygen absorption capacity is controlled. However, some resins have a problem of odor, which is not always sufficient in the food field.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
の種々の問題点を解決した優れた酸素吸収シートを提供
することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent oxygen absorbing sheet which solves the above various problems.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決するため、種々検討の結果、酸素吸収剤を分岐の少
ない線状ポリエチレン樹脂と混合し溶融成形して得られ
るシートを特定条件で延伸加工し多孔質シートとするこ
とにより、上記の種々の問題点を解決した優れた酸素吸
収シートが得られることを見出し本発明に至った。即ち
本発明は下記の酸素吸収シートである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted various studies and found that a sheet obtained by mixing an oxygen absorbent with a linear polyethylene resin having a small number of branches and melt-forming the mixture under specific conditions It was found that an excellent oxygen-absorbing sheet which solves the above-mentioned various problems can be obtained by stretching the porous sheet to give a porous sheet. That is, the present invention is the following oxygen absorbing sheet.
【０００５】１．密度が０．９４０g/cm3以上である線
状ポリエチレン樹脂１５〜７０重量％と、一次粒子径
０．０１〜２０μｍの粉体が５〜２００μｍに凝集した
鉄系酸素吸収剤３０〜８５重量％からなる樹脂組成物を
厚さ３０μｍ〜５ｍｍにシート加工した後、下記の式で
示される延伸温度で少なくとも一軸方向に１．５〜１
０．０倍の倍率で延伸された酸素吸収シート。 Ｔｍ−２０≦Ｔｋ≦Ｔｍ−２； ただし、Ｔｍ：線状ポリエチレンの融点（℃） Ｔｋ：延伸温度（℃）1. 15-70% by weight of linear polyethylene resin having a density of 0.940 g / cm 3 or more, and 30-85% by weight of iron-based oxygen absorbent in which powder having a primary particle diameter of 0.01-20 μm is aggregated to 5-200 μm The resin composition consisting of a sheet is processed into a sheet having a thickness of 30 μm to 5 mm, and then at a stretching temperature represented by the following formula, at least uniaxially 1.5 to 1
An oxygen absorbing sheet stretched at a magnification of 0.0 times. Tm-20 ≦ Tk ≦ Tm-2; where Tm: melting point of linear polyethylene (° C.) Tk: stretching temperature (° C.)
【０００６】本発明の酸素吸収シートは線状ポリエチレ
ン樹脂の中に酸素吸収剤を溶融混練により均一に分散さ
せ、得られたフィルムまたはシートを特定条件下で延伸
することによりミクロボイドを多数発生させて多孔質化
したものであって、該フィルムまたはシート中に均一に
分散させた酸素吸収剤はミクロボイドを通じて大気と接
触しており大気中の酸素を効果的に吸収し得る。In the oxygen-absorbing sheet of the present invention, an oxygen-absorbing agent is uniformly dispersed in a linear polyethylene resin by melt-kneading, and the obtained film or sheet is stretched under specific conditions to generate many microvoids. The oxygen absorbent, which is made porous and is uniformly dispersed in the film or sheet, is in contact with the atmosphere through microvoids and can effectively absorb oxygen in the atmosphere.
【０００７】本発明に用いられる樹脂としては、分岐の
少ない線状ポリエチレン樹脂が好ましく、特に混練冷却
後の分子運動性の観点から結晶化度の高い樹脂が好まし
い。線状ポリエチレン樹脂の場合は密度と結晶化度に相
関関係があるために、密度が０．９４０g/cm3以上であ
ることがより好ましい。また、延伸時の開孔率を高め、
高い酸素吸収能を獲得すること、および高開孔率性を有
することにより、樹脂と鉄粉との接触面積を少なくで
き、上記分解反応を抑制することができる点からも密度
が０．９４０g/cm3以上の樹脂を用いることが好まし
い。As the resin used in the present invention, a linear polyethylene resin having a small number of branches is preferable, and a resin having high crystallinity is particularly preferable from the viewpoint of molecular mobility after kneading and cooling. In the case of a linear polyethylene resin, the density is more preferably 0.940 g / cm 3 or more because there is a correlation between the density and the crystallinity. Also, increase the porosity during stretching,
By obtaining a high oxygen absorption capacity and having a high porosity, the contact area between the resin and the iron powder can be reduced, and the density of 0.940 g / It is preferable to use a resin of cm 3 or more.
【０００８】本発明の酸素吸収シートにおいて酸素吸収
剤の含有量が３０重量％未満の場合はミクロボイドの発
生が少ないため大気と連通するミクロボイドも少なくな
り、その結果大気中の酸素を吸収する能力が極めて低く
好ましくない。一方、８５重量％を超す場合は得られる
酸素吸収シートが著しく脆くなり好ましくない。In the oxygen absorbing sheet of the present invention, when the content of the oxygen absorbing agent is less than 30% by weight, the generation of microvoids is small and the number of microvoids communicating with the atmosphere is small, and as a result, the ability to absorb oxygen in the atmosphere is reduced. Very low and unfavorable. On the other hand, if it exceeds 85% by weight, the obtained oxygen-absorbing sheet becomes extremely brittle, which is not preferable.
【０００９】熱可塑性樹脂と酸素吸収剤からなる延伸前
の樹脂組成物のシート厚さは用途目的により様々である
が、３０μｍ未満の場合は所望の酸素吸収能力を得るた
めに非常に大面積の酸素吸収シートを使用しなければな
らないケースもあり包装される食品本体より大きく目立
ってしまうという問題が生じる。一方、５ｍｍを超す場
合は、シート加工後の延伸においてシートを均一な延伸
温度にすることが難しく均一な延伸ができなくなり好ま
しくない。得られたシートの延伸温度については線状ポ
リエチレン樹脂の融点−２０℃以上、該樹脂の融点−２
℃未満の温度で延伸することが必要である。該樹脂の融
点−２０℃未満で延伸する場合は、樹脂が伸びずに破断
してしまうために好ましくない。また、該樹脂の融点−
２℃以上で延伸する場合は樹脂が溶融して破断を生じる
ために好ましくない。延伸倍率については、１．５倍未
満ではミクロボイドの発生が少なく均一分散された酸素
吸収剤が大気と十分に接触できないため実用に十分な酸
素吸収能力を得ることができない。また、８．０倍を超
えると得られる酸素吸収シートは引裂などのフィルム強
度が著しく低下し、わずかな外力で破損するため好まし
くない。The sheet thickness of the resin composition before stretching comprising a thermoplastic resin and an oxygen absorber varies depending on the purpose of use, but if it is less than 30 μm, a very large area is required to obtain a desired oxygen absorption capacity. In some cases, it is necessary to use an oxygen absorbing sheet, which causes a problem that the oxygen absorbing sheet is more noticeable than the packaged food body. On the other hand, if it exceeds 5 mm, it is difficult to keep the sheet at a uniform stretching temperature in stretching after sheet processing, and uniform stretching cannot be performed, which is not preferable. Regarding the stretching temperature of the obtained sheet, the melting point of the linear polyethylene resin is −20 ° C. or higher, and the melting point of the resin is −2.
It is necessary to stretch at a temperature below ° C. When the resin is stretched at a melting point lower than -20 ° C, the resin is not stretched and is broken, which is not preferable. Also, the melting point of the resin-
Stretching at 2 ° C. or higher is not preferable because the resin melts and breaks. When the stretching ratio is less than 1.5 times, the generation of microvoids is small and the uniformly dispersed oxygen absorbent cannot sufficiently contact the atmosphere, so that the oxygen absorbing capacity for practical use cannot be obtained. On the other hand, if it exceeds 8.0 times, the obtained oxygen-absorbing sheet is not preferable because the film strength such as tearing is remarkably lowered, and it is damaged by a slight external force.
【００１０】本発明に用いられる酸素吸収剤である鉄粉
または鉄粉と電解質において、鉄粉には副成分として鉄
の酸化物や炭化鉄などを含んでいてもよく、該副成分の
含有量は、通常０．１〜２０重量％程度である。鉄粉の
形状は高い酸素吸収性能を得るために、一次粒子が凝集
してなる構造であることが好ましく、一次粒子径は通常
０．０１〜２０μｍのものが好ましい。また凝集粒子径
は通常０．１〜２００μｍであることが好ましく、より
好ましくは２０〜１５０μｍである。電解質は鉄粉の酸
素吸収速度を促進するものであり、例えばハロゲン化
物、炭酸塩、硫酸塩または水酸化物等である。これらの
種類の中で好ましいのはハロゲン化物であり、ＣａＣｌ
2、ＮａＣｌ、ＭｇＣｌ2等が例示できる。電解質は前記
鉄粉の粒子にコーティングして使用しても良いし、鉄粉
との単なるブレンドで使用しても良い。また、電解質の
添加量は０．１〜１０重量％が好ましい。In the iron powder or the iron powder and the electrolyte which are the oxygen absorbers used in the present invention, the iron powder may contain iron oxide, iron carbide and the like as a sub ingredient, and the content of the sub ingredient. Is usually about 0.1 to 20% by weight. The shape of the iron powder is preferably a structure in which primary particles are aggregated in order to obtain high oxygen absorption performance, and the primary particle diameter is usually preferably 0.01 to 20 μm. In addition, the aggregated particle size is usually preferably 0.1 to 200 μm, more preferably 20 to 150 μm. The electrolyte promotes the oxygen absorption rate of iron powder, and is, for example, a halide, carbonate, sulfate or hydroxide. Preferred among these types are the halides, CaCl
2 , NaCl, MgCl 2 and the like can be exemplified. The electrolyte may be used by coating the iron powder particles, or may be used by simply blending with the iron powder. The amount of electrolyte added is preferably 0.1 to 10% by weight.
【００１１】本発明の酸素吸収シートを得るための酸素
吸収剤含有樹脂組成物、多孔質樹脂組成物の中には、本
発明の効果を実質的に損なわない範囲で酸化防止剤、分
散剤、帯電防止剤、消臭剤等を配合させることができ
る。本発明の酸素吸収シートは、例えば、以下の製造方
法により得ることができる。まず、線状ポリエチレン樹
脂と酸素吸収剤、必要に応じては分散剤や安定剤など
を、ロール型またはバンバリー型の混練機あるいは一
軸、または二軸押出機などを用いる通常の方法で混合あ
るいは混練して組成物を得る。また、線状ポリエチレン
樹脂と充填剤、必要に応じては分散剤や安定剤などを同
様の方法で混練し組成物を得る。次いでこの組成物から
Ｔダイ加工等の通常の成形方法によってシートを製造
し、得られたシートを延伸するが、延伸は一軸または二
軸で行なう。一軸延伸の場合は通常ロール延伸が好まし
いがチューブラー延伸で行なってもよい。また、延伸は
一段でも二段以上でも可能であり、二軸延伸の場合は同
時二軸延伸でも可能であるし、縦方向の延伸を行なった
後に横方向を延伸する逐次二軸延伸でも可能である。The oxygen-absorbing agent-containing resin composition and the porous resin composition for obtaining the oxygen-absorbing sheet of the present invention include an antioxidant, a dispersant, and an antioxidant within a range that does not substantially impair the effects of the present invention. Antistatic agents, deodorants, etc. can be added. The oxygen absorbing sheet of the present invention can be obtained, for example, by the following manufacturing method. First, a linear polyethylene resin and an oxygen absorbent, and optionally a dispersant and a stabilizer are mixed or kneaded by a usual method using a roll type or Banbury type kneader or a single-screw or twin-screw extruder. To obtain a composition. Further, a linear polyethylene resin, a filler and, if necessary, a dispersant, a stabilizer and the like are kneaded by the same method to obtain a composition. Then, a sheet is produced from this composition by a usual forming method such as T-die processing, and the obtained sheet is stretched, but the stretching is carried out uniaxially or biaxially. In the case of uniaxial stretching, roll stretching is usually preferable, but tubular stretching may be performed. Further, the stretching can be performed in one step or in two or more steps, and in the case of biaxial stretching, simultaneous biaxial stretching is possible, or sequential biaxial stretching in which transverse stretching is carried out after longitudinal stretching is also possible. is there.
【００１２】[0012]
【発明の効果】本発明の酸素吸収シートは取扱性および
酸素吸収能力に優れ、臭気がほとんど無いので、特に食
品分野等での脱酸素剤用途に極めて有用である。The oxygen-absorbing sheet of the present invention is excellent in handleability and oxygen-absorbing ability and has almost no odor. Therefore, it is extremely useful for use as an oxygen scavenger especially in the food field.
【００１３】[0013]
【実施例】以下、実施例によって詳細に説明するが、本
発明はこれによって限定されるものではない。実施例お
よび比較例に示した物性の測定法は以下の通りである。
酸素吸収速度：酸素吸収速度は酸素１７０ｃｃに対し、
酸素吸収多層シートを３．７ｇの割合で密閉容器に存在
させ、５℃下での２４時間後の酸素吸収量を測定したも
のである。密閉容器とは、目盛り付きのガラス製の円筒
容器を水面上に立てたもので酸素が吸収されると減少し
た容量が水によって占有される仕組みとなっている。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. The methods for measuring physical properties shown in Examples and Comparative Examples are as follows.
Oxygen absorption rate: Oxygen absorption rate is 170cc for oxygen,
The oxygen absorption multilayer sheet was present in a closed container at a rate of 3.7 g, and the oxygen absorption amount after 24 hours at 5 ° C. was measured. An airtight container is a cylindrical glass container with a scale set up on the surface of the water. When oxygen is absorbed, the reduced capacity is occupied by water.
【００１４】融点：パーキンエルマー社製ＤＳＣ−２型
示差走査熱量計により１０℃／min の昇温速度で測定し
た。 密度：樹脂の密度はＪＩＳ Ｋ６７６０に準拠して密度
勾配管法により２３℃で測定した。 臭気強度： 臭気センサー法 ガラス製の容積５００ccのサンプル瓶に、０．５g の酸
素吸収シートを入れてアルミ箔で覆いをし、６０℃下で
１時間エージングを行なう。その後、２３℃下で３０分
冷却し内部の臭気強度を新コスモス電気社製臭気センサ
ー（ＸＰ−３２９型）にて５分間測定し、その時の最大
値を測定した。 官能評価法：臭気センサー法と同様に作成した臭気サン
プルで官能評価を行ない、臭気強度を判定した。官能評
価の判定基準は以下の通りである。 Ａ：無臭 Ｂ：ほとんど無臭 Ｃ：弱く臭う Ｄ：臭う Ｅ：かなり臭うMelting point: Measured with a DSC-2 type differential scanning calorimeter manufactured by Perkin Elmer at a temperature rising rate of 10 ° C./min. Density: The density of the resin was measured at 23 ° C. by the density gradient tube method according to JIS K6760. Odor strength: Odor sensor method A glass bottle with a volume of 500 cc was charged with 0.5 g of oxygen absorbing sheet, covered with aluminum foil, and aged at 60 ° C. for 1 hour. Then, the mixture was cooled at 23 ° C. for 30 minutes, and the internal odor intensity was measured with an odor sensor (XP-329 type) manufactured by New Cosmos Electric Co., Ltd. for 5 minutes, and the maximum value at that time was measured. Sensory evaluation method: Sensory evaluation was performed on an odor sample prepared in the same manner as in the odor sensor method to determine the odor intensity. The criteria for sensory evaluation are as follows. A: odorless B: almost odorless C: weakly odorous D: odorous E: quite odorous
【００１５】実施例１ 線状ポリエチレン樹脂（東洋曹達株式会社製 ニポロン
ハード４０１０ 密度０．９６３g/cm3 ＭＦＲ＝５．
５ 融点１３７℃）３０重量部と酸素吸収剤として鉄粉
（一次粒子径７μｍ、凝集粒子径１０６μｍ。電解質と
して塩化カルシウムを２重量％含み、鉄成分としては還
元鉄９５重量％および鉄の酸化物５重量％からなる）７
０重量％を神戸製鋼（株）製のＢＲ型バンバリーによっ
て１６０℃で２分間混練して組成物を得た。この組成物
をの田辺プラスチック社製３０ｍｍφ押出機により１６
０℃の加工温度にてＴダイ成形し、厚さ１ｍｍのシート
を得た。このシートを日本製鋼（株）のロール延伸機に
より１３０℃でたて方向に５．０倍に延伸し酸素吸収シ
ートが得られた。結果は表−１に示すように高い酸素吸
収能力を持ち、かつ臭気も問題とならない酸素吸収シー
トであった。Example 1 Linear polyethylene resin (manufactured by Toyo Soda Co., Ltd. Nipolon Hard 4010, density 0.963 g / cm 3 MFR = 5.
5 Melting point 137 ° C.) 30 parts by weight, iron powder (primary particle size 7 μm, aggregate particle size 106 μm) as oxygen absorber, containing 2% by weight of calcium chloride as electrolyte, 95% by weight of reduced iron and iron oxide as iron component 5% by weight) 7
0% by weight was kneaded by a BR type Banbury manufactured by Kobe Steel Ltd. at 160 ° C. for 2 minutes to obtain a composition. This composition was treated with a Tanabe Plastic Co., Ltd. 30 mmφ extruder for 16
T-die molding was performed at a processing temperature of 0 ° C. to obtain a sheet having a thickness of 1 mm. This sheet was stretched 5.0 times in the vertical direction at 130 ° C. by a roll stretching machine of Nippon Steel Co., Ltd. to obtain an oxygen absorbing sheet. As a result, as shown in Table-1, the oxygen absorption sheet had a high oxygen absorption capacity and odor was not a problem.
【００１６】実施例２ 線状ポリエチレン樹脂をショウレックス５０５０（昭和
電工株式会社製 密度０．９５０g/cm3 ＭＦＲ＝５
融点１３３℃）に代え、延伸温度を１２５℃に変更した
以外は実施例１と同様に加工し酸素吸収シートが得られ
た。結果として、実施例１と同様な酸素吸収性能をを持
ち、臭気もほとんど無い酸素吸収シートであった。Example 2 A linear polyethylene resin was used as Shorex 5050 (produced by Showa Denko KK, density 0.950 g / cm 3 MFR = 5).
Instead of the melting point of 133 ° C.), the oxygen absorbing sheet was obtained in the same manner as in Example 1 except that the stretching temperature was changed to 125 ° C. As a result, the oxygen absorption sheet had the same oxygen absorption performance as that of Example 1 and had almost no odor.
【００１７】実施例３ 延伸倍率を７．０倍にした以外は実施例１と同様に加工
を行ない酸素吸収能に優れた酸素吸収シートが得られ
た。Example 3 An oxygen absorbing sheet excellent in oxygen absorbing ability was obtained by performing the same processing as in Example 1 except that the stretching ratio was 7.0 times.
【００１８】実施例４ 酸素吸収剤中の電解質を塩化ナトリウムとした以外は実
施例１と同様に加工を行ない、酸素吸収能に優れ臭気も
問題とならない酸素吸収シートが得られた。Example 4 An oxygen absorbing sheet was obtained which was processed in the same manner as in Example 1 except that the electrolyte in the oxygen absorbent was sodium chloride, and which had an excellent oxygen absorbing ability and had no problem of odor.
【００１９】実施例５ 酸素吸収剤中の電解質を塩化ナトリウムとした以外は実
施例２と同様に加工を行ない、酸素吸収能に優れ臭気も
問題とならない酸素吸収シートが得られた。Example 5 An oxygen absorbing sheet was obtained which was processed in the same manner as in Example 2 except that the electrolyte in the oxygen absorbent was sodium chloride, and which had an excellent oxygen absorbing ability and no odor was a problem.
【００２０】比較例１ 延伸温度を１００℃にした以外は実施例１と同様に加工
を行ない酸素吸収シートを得ようとしたが、延伸中に破
断を起こし酸素吸収シートを作成することが出来なかっ
た。Comparative Example 1 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the stretching temperature was changed to 100 ° C., but an oxygen absorbing sheet could not be prepared due to breakage during stretching. It was
【００２１】比較例２ 延伸倍率を１１．０倍にした以外は実施例１と同様に加
工を行ない酸素吸収シートを得ようとしたが、延伸中に
破断を起こし酸素吸収シートを作成することが出来なか
った。Comparative Example 2 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the stretching ratio was set to 11.0. However, breakage occurred during stretching and an oxygen absorbing sheet could be prepared. I could not do it.
【００２２】比較例３ 延伸加工を行なわない以外は実施例１と同様に加工を行
ない酸素吸収シートを得たが、酸素吸収能が極めて劣る
シートとなった。Comparative Example 3 An oxygen absorbing sheet was obtained by the same process as in Example 1 except that the stretching process was not carried out, but the oxygen absorbing ability was extremely poor.
【００２３】比較例４ シート厚みを６．０mmとした以外は実施例１と同様に加
工を行ない酸素吸収シートを得ようとしたが、延伸中に
破断を起こし酸素吸収シートを作成することが出来なか
った。Comparative Example 4 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the sheet thickness was 6.0 mm. However, the oxygen absorbing sheet could be broken during stretching and an oxygen absorbing sheet could be prepared. There wasn't.
【００２４】比較例５ 線状ポリエチレンを１０重量部、酸素吸収剤を９０重量
部に変更した以外は実施例１と同様に加工を行ない酸素
吸収シートを得ようとしたが、すべての酸素吸収剤が線
状ポリエチレン中に分散せず酸素吸収シートを作成する
ことが出来なかった。Comparative Example 5 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the amount of linear polyethylene was changed to 10 parts by weight and the amount of oxygen absorbent was changed to 90 parts by weight. Was not dispersed in the linear polyethylene and an oxygen absorbing sheet could not be prepared.
【００２５】比較例６ 線状ポリエチレンの添加量を７５重量部、酸素吸収剤の
添加量を２５重量部に変更した以外は実施例１と同様に
加工を行ない酸素吸収シートを得たが、著しく酸素吸収
能に劣るシートとなった。Comparative Example 6 An oxygen absorbing sheet was obtained by carrying out the same processing as in Example 1 except that the amount of linear polyethylene added was changed to 75 parts by weight and the amount of oxygen absorbent added was changed to 25 parts by weight. It became a sheet with poor oxygen absorption capacity.
【００２６】比較例７ 線状ポリエチレンをスミカセン−Ｌ ＦＡ２０１−０
（住友化学工業株式会社製 密度 ０．９１９g/cm3
ＭＦＲ＝２．０ 融点１２３℃）とし、延伸温度を１１
６℃とした以外は実施例１と同様に加工を行ない酸素吸
収シートを得たが臭気があり、食品分野の酸素吸収剤と
しては不適切なものであった。Comparative Example 7 Linear polyethylene was added to Sumikasen-L FA201-0.
(Sumitomo Chemical Co., Ltd. Density 0.919g / cm 3
MFR = 2.0, melting point 123 ° C.) and stretching temperature 11
An oxygen absorbing sheet was obtained by performing the same processing as in Example 1 except that the temperature was 6 ° C. However, it had an odor and was unsuitable as an oxygen absorbent in the food field.
【００２７】比較例８ 線状ポリエチレンをエクセレンＶＬ２００（住友化学工
業株式会社製 密度０．９００g/cm3 ＭＦＲ＝２．
０）に変更し、線状ポリエチレンの添加量を２５重量
部、酸素吸収剤の添加量を７５重量部とし、延伸温度を
５０℃とした以外は実施例１と同様に加工を行ない酸素
吸収シートを得たが、臭気がかなりあり、食品分野の酸
素吸収剤としては不適切なものであった。Comparative Example 8 Linear polyethylene was replaced with Excellen VL200 (manufactured by Sumitomo Chemical Co., Ltd., density 0.900 g / cm 3 MFR = 2.
0), the linear polyethylene was added in an amount of 25 parts by weight, the oxygen absorbent was added in an amount of 75 parts by weight, and the stretching temperature was 50 ° C. However, it had a considerable odor and was unsuitable as an oxygen absorber in the food field.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年４月２２日[Submission date] April 22, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Name of item to be corrected] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 酸素吸収シートTitle of the invention Oxygen absorbing sheet
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、酸素吸収シートに関す
る。さらに詳しくは、取扱いが容易であり、酸素吸収能
力を制御した酸素吸収シートであり、さらに臭気が問題
とならない高性能酸素吸収シートに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen absorbing sheet. More specifically, the present invention relates to an oxygen absorbing sheet that is easy to handle and has a controlled oxygen absorbing ability, and further relates to a high performance oxygen absorbing sheet in which odor does not pose a problem.
【０００２】[0002]
【従来の技術】脱酸素剤は食品をはじめ、種々の製品の
保存に際して酸素が好まれないような場合に、酸素の除
去を目的として多方面において使用されている。通常使
用されている粉体の酸素吸収剤を通気度のある素材で包
装する方法は、素材の密封が完全でないと、粉体が外部
に漏れるという問題がある。また、本発明者らは取扱い
が容易であり酸素吸収能力を制御した酸素吸収シートと
して、酸素吸収剤を樹脂に充填して多孔質化する方法を
特開平２−２０３９３７号公報に提案しているが、ある
種の樹脂の場合、若干臭気に問題があり、食品分野等で
は、必ずしも充分なものとは言い難かった。2. Description of the Related Art Oxygen scavengers are used in various fields for the purpose of removing oxygen when oxygen is not preferred when storing various products such as foods. The commonly used method of packaging a powder oxygen absorber with a material having air permeability has a problem that the powder leaks to the outside unless the material is completely sealed. Further, the inventors of the present invention have proposed in JP-A-2-203937 a method of filling a resin with an oxygen absorbent to make it porous as an oxygen absorbent sheet which is easy to handle and whose oxygen absorption capacity is controlled. However, some resins have a problem of odor, which is not always sufficient in the food field.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
の種々の問題点を解決した優れた酸素吸収シートを提供
することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent oxygen absorbing sheet which solves the above various problems.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決するため、種々検討の結果、酸素吸収剤を分岐の少
ない線状ポリエチレン樹脂と混合し溶融成形して得られ
るシートを特定条件で延伸加工し多孔質シートとするこ
とにより、上記の種々の問題点を解決した優れた酸素吸
収シートが得られることを見出し本発明に至った。即ち
本発明は下記の酸素吸収シートである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted various studies and found that a sheet obtained by mixing an oxygen absorbent with a linear polyethylene resin having a small number of branches and melt-forming the mixture under specific conditions It was found that an excellent oxygen-absorbing sheet which solves the above-mentioned various problems can be obtained by stretching the porous sheet to give a porous sheet. That is, the present invention is the following oxygen absorbing sheet.
【０００５】密度が０．９４０g/cm3 以上である線状ポ
リエチレン樹脂１５〜７０重量％と、一次粒子径０．０
１〜２０μｍの粉体が５〜２００μｍに凝集した鉄系酸
素吸収剤３０〜８５重量％からなる樹脂組成物を厚さ３
０μｍ〜５ｍｍにシート加工した後、下記の式で示され
る延伸温度で少なくとも一軸方向に１．５〜９倍の倍率
で延伸された酸素吸収シート。 Ｔｍ−２０≦Ｔｋ≦Ｔｍ−２； ただし、Ｔｍ：線状ポリエチレンの融点（℃） Ｔｋ：延伸温度（℃）15 to 70% by weight of linear polyethylene resin having a density of 0.940 g / cm 3 or more and a primary particle diameter of 0.0
A resin composition consisting of 30 to 85% by weight of an iron-based oxygen absorber in which powder of 1 to 20 μm is aggregated to 5 to 200 μm is formed to a thickness of 3
An oxygen-absorbing sheet, which has been processed into a sheet having a thickness of 0 μm to 5 mm and then stretched at a stretching temperature of 1.5 to 9 times in at least one axial direction at a stretching temperature represented by the following formula. Tm-20 ≦ Tk ≦ Tm-2; where Tm: melting point of linear polyethylene (° C.) Tk: stretching temperature (° C.)
【０００６】以下、本発明を詳細に説明する。本発明の
酸素吸収シートは線状ポリエチレン樹脂の中に鉄系酸素
吸収剤を溶融混練により均一に分散させ、得られたフィ
ルムまたはシートを特定条件下で延伸することによりミ
クロボイドを多数発生させて多孔質化したものであっ
て、該フィルムまたはシート中に均一に分散させた鉄系
酸素吸収剤はミクロボイドを通じて大気と接触しており
大気中の酸素を効果的に吸収し得る。The present invention will be described in detail below. The oxygen-absorbing sheet of the present invention is obtained by uniformly dispersing an iron-based oxygen-absorbing agent in a linear polyethylene resin by melt-kneading, and stretching the obtained film or sheet under specific conditions to generate a large number of microvoids and to make them porous. The iron-based oxygen absorbent, which is qualitatively and uniformly dispersed in the film or sheet, is in contact with the atmosphere through microvoids and can effectively absorb oxygen in the atmosphere.
【０００７】本発明に用いられる樹脂は、分岐の少ない
線状ポリエチレン樹脂であり、特に混練冷却後の分子運
動性の観点から結晶化度の高い樹脂が好ましい。線状ポ
リエチレン樹脂の場合は密度と結晶化度に相関関係があ
り、密度が０．９４０g/cm3以上であることが必要であ
る。また、延伸時の開孔率を高め、高い酸素吸収能を獲
得すること、および高開孔率性を有することにより、樹
脂と鉄系酸素吸収剤との接触面積を少なくでき、分解反
応を抑制することができる点からも密度が０．９４０g/
cm3 以上の樹脂であることが必要である。The resin used in the present invention is a linear polyethylene resin having few branches, and a resin having a high degree of crystallinity is particularly preferable from the viewpoint of molecular mobility after kneading and cooling. In the case of a linear polyethylene resin, there is a correlation between the density and the crystallinity, and the density needs to be 0.940 g / cm 3 or more. Also, by increasing the porosity during stretching to obtain a high oxygen absorption capacity and by having a high porosity, it is possible to reduce the contact area between the resin and the iron-based oxygen absorbent, and suppress the decomposition reaction. The density is 0.940 g /
It is necessary that the resin is cm 3 or more.
【０００８】本発明の酸素吸収シートにおいて鉄系酸素
吸収剤の含有量は、樹脂組成物中、通常、３０〜８５重
量％であり、３０重量％未満の場合はミクロボイドの発
生が少ないため大気と連通するミクロボイドも少なくな
り、その結果大気中の酸素を吸収する能力が極めて低
く、一方、８５重量％を超える場合は得られる酸素吸収
シートが脆くなり本発明の目的を達成できない。The content of the iron-based oxygen absorbent in the oxygen absorbing sheet of the present invention is usually 30 to 85% by weight in the resin composition. The number of communicating microvoids is also reduced, and as a result, the ability to absorb oxygen in the atmosphere is extremely low. On the other hand, when it exceeds 85% by weight, the obtained oxygen absorbing sheet becomes brittle and the object of the present invention cannot be achieved.
【０００９】熱可塑性樹脂と鉄系酸素吸収剤からなる延
伸前の樹脂組成物のシートの厚さは、３０μｍ〜５ｍｍ
であることが必要であり、３０μｍ未満の場合は所望の
酸素吸収能力を得るために非常に大面積の酸素吸収シー
トを使用しなければならない場合もあり包装される食品
本体より大きく目立ってしまうという問題が生じる、一
方、５ｍｍを超す場合は、シート加工後の延伸において
シートを均一な延伸温度にすることが難しく、均一な延
伸ができなくなり実用的でない。得られたシートの延伸
温度については線状ポリエチレン樹脂の（融点−２０
℃）以上、該樹脂の（融点−２℃）以下の温度で延伸す
ることが必要である。該樹脂の（融点−２０℃）未満で
延伸する場合は、樹脂が伸びずに破断してしまい、ま
た、該樹脂の（融点−２℃）より高い温度で延伸する場
合にも樹脂が破断してしまい、本発明の目的を達成でき
ない。延伸倍率は、１．５〜９倍であり、１．５倍未満
ではミクロボイドの発生が少なく均一分散された鉄系酸
素吸収剤が大気と十分に接触できないため実用に十分な
酸素吸収能力を得ることができない。また、９倍を超え
ると得られる酸素吸収シートは引裂などのフィルム強度
が低下し、わずかな外力で破損するため実用的でない。The thickness of the sheet of the resin composition before stretching, which comprises a thermoplastic resin and an iron-based oxygen absorber, is 30 μm to 5 mm.
If it is less than 30 μm, it may be necessary to use an oxygen absorbing sheet with a very large area in order to obtain the desired oxygen absorbing capacity, and it will be noticeably larger than the packaged food body. On the other hand, a problem occurs, but if it exceeds 5 mm, it is difficult to bring the sheet to a uniform stretching temperature in the stretching after sheet processing, and uniform stretching cannot be performed, which is not practical. Regarding the stretching temperature of the obtained sheet, the linear polyethylene resin (melting point −20
It is necessary to stretch at a temperature not lower than (.degree. C.) and not higher than (melting point-2.degree. C.) of the resin. When the resin is stretched at a temperature lower than (melting point -20 ° C), the resin does not stretch and breaks. Also, when the resin is stretched at a temperature higher than the resin (melting point-2 ° C), the resin breaks. Therefore, the object of the present invention cannot be achieved. The draw ratio is 1.5 to 9 times, and if it is less than 1.5 times, the generation of microvoids is small and the uniformly dispersed iron-based oxygen absorbent cannot sufficiently contact with the atmosphere, so that a sufficient oxygen absorption capacity for practical use is obtained. I can't. Further, if it exceeds 9 times, the oxygen absorbing sheet obtained is not practical because the film strength such as tearing is lowered and the oxygen absorbing sheet is broken by a slight external force.
【００１０】本発明に用いられる鉄系酸素吸収剤として
は、一般に酸素吸収剤として使用されているものを用い
ることができ、例えば、鉄、還元鉄が挙げられ、これら
には副成分として鉄の酸化物や炭化鉄などを含んでいて
もよく、該副成分の含有量は、通常０．１〜２０重量％
程度である。鉄系酸素吸収剤は、通常、粉末で用いら
れ、その形状は高い酸素吸収性能を得るために、一次粒
子が凝集してなる構造であることが好ましく、一次粒子
径は通常、０．０１〜２０μｍであり、また凝集粒子径
は通常、５〜２００μｍであり、より好ましくは１０〜
１５０μｍである。本発明の鉄系酸素吸収剤には、電解
質を併用することが好ましい。電解質は鉄系酸素吸収剤
の酸素吸収速度を促進するものであり、例えばハロゲン
化物、炭酸塩、硫酸塩または水酸化物等である。これら
の種類の中で好ましいのはハロゲン化物であり、ＣａＣ
ｌ2 、ＮａＣｌ、ＭｇＣｌ2 等が例示できる。電解質は
鉄系酸素吸収剤にコーティングして使用しても良いし、
鉄系酸素吸収剤との単なるブレンドで使用しても良い。
また、電解質の添加量は、通常、鉄系酸素吸収剤に対
し、０．１〜１０重量％の範囲である。As the iron-based oxygen absorbent used in the present invention, those generally used as oxygen absorbents can be used. Examples thereof include iron and reduced iron, and these include iron as a sub-component. It may contain oxides, iron carbide, etc., and the content of the accessory component is usually 0.1 to 20% by weight.
It is a degree. The iron-based oxygen absorber is usually used in the form of powder, and its shape is preferably a structure in which primary particles are agglomerated in order to obtain high oxygen absorption performance. 20 μm, and the aggregate particle size is usually 5 to 200 μm, more preferably 10 to 200 μm.
It is 150 μm. An electrolyte is preferably used in combination with the iron-based oxygen absorber of the present invention. The electrolyte promotes the oxygen absorption rate of the iron-based oxygen absorber, and is, for example, a halide, carbonate, sulfate or hydroxide. Preferred among these types are the halides, CaC
Examples include l 2 , NaCl, MgCl 2 and the like. The electrolyte may be used by coating it with an iron-based oxygen absorber,
It may be used as a mere blend with an iron-based oxygen absorber.
The amount of electrolyte added is usually in the range of 0.1 to 10% by weight based on the iron-based oxygen absorber.
【００１１】本発明の酸素吸収シートを得るための鉄系
酸素吸収剤含有樹脂組成物、多孔質樹脂組成物に、本発
明の効果を実質的に損なわない範囲で一般に用いられる
酸化防止剤、分散剤、帯電防止剤、消臭剤等を配合させ
ることができる。本発明の酸素吸収シートは、例えば、
以下の製造方法により得ることができる。まず、線状ポ
リエチレン樹脂と鉄系酸素吸収剤、必要に応じては分散
剤や安定剤などを、ロール型またはバンバリー型の混練
機あるいは一軸、または二軸押出機などを用いる通常の
方法で混合あるいは混練して組成物を得る。また、線状
ポリエチレン樹脂と充填剤、必要に応じては分散剤や安
定剤などを同様の方法で混練し組成物を得る。次いでこ
の組成物からＴダイ加工等の通常の成形方法によってシ
ートを製造し、得られたシートを延伸するが、延伸は一
軸または二軸で行なう。一軸延伸の場合は通常ロール延
伸が好ましいがチューブラー延伸で行なってもよい。ま
た、延伸は一段でも二段以上でも可能であり、二軸延伸
の場合は同時二軸延伸でも可能であるし、縦方向の延伸
を行なった後に横方向を延伸する逐次二軸延伸でも可能
である。In the iron-based oxygen absorbent-containing resin composition and porous resin composition for obtaining the oxygen-absorbing sheet of the present invention, an antioxidant and a dispersion generally used within a range that does not substantially impair the effects of the present invention. Agents, antistatic agents, deodorants, etc. can be added. The oxygen absorbing sheet of the present invention, for example,
It can be obtained by the following manufacturing method. First, a linear polyethylene resin and an iron-based oxygen absorber, and optionally a dispersant and a stabilizer are mixed by a usual method using a roll-type or Banbury-type kneader or a single-screw or twin-screw extruder. Alternatively, the composition is obtained by kneading. Further, a linear polyethylene resin, a filler and, if necessary, a dispersant, a stabilizer and the like are kneaded by the same method to obtain a composition. Then, a sheet is produced from this composition by a usual forming method such as T-die processing, and the obtained sheet is stretched. The stretching is carried out uniaxially or biaxially. In the case of uniaxial stretching, roll stretching is usually preferable, but tubular stretching may be performed. Further, the stretching can be performed in one step or in two or more steps, and in the case of biaxial stretching, simultaneous biaxial stretching is possible, or sequential biaxial stretching in which transverse stretching is carried out after longitudinal stretching is also possible. is there.
【００１２】[0012]
【発明の効果】本発明の酸素吸収シートは取扱性および
酸素吸収能力に優れ、臭気がほとんど無いので、特に食
品分野等での脱酸素剤用途に極めて有用である。The oxygen-absorbing sheet of the present invention is excellent in handleability and oxygen-absorbing ability and has almost no odor. Therefore, it is extremely useful for use as an oxygen scavenger especially in the food field.
【００１３】[0013]
【実施例】以下、実施例によって詳細に説明するが、本
発明はこれによって限定されるものではない。実施例お
よび比較例に示した物性の測定法は以下の通りである。 酸素吸収速度：酸素吸収速度は酸素１７０ｃｃに対し、
酸素吸収多層シートを３．７ｇの割合で密閉容器に存在
させ、５℃下での２４時間後の酸素吸収量を測定したも
のである。密閉容器とは、目盛り付きのガラス製の円筒
容器を水面上に立てたもので酸素が吸収されると減少し
た容量が水によって占有される仕組みとなっている。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. The methods for measuring physical properties shown in Examples and Comparative Examples are as follows. Oxygen absorption rate: Oxygen absorption rate is 170cc for oxygen,
The oxygen absorption multilayer sheet was present in a closed container at a rate of 3.7 g, and the oxygen absorption amount after 24 hours at 5 ° C. was measured. An airtight container is a cylindrical glass container with a scale set up on the surface of the water. When oxygen is absorbed, the reduced capacity is occupied by water.
【００１４】融点：パーキンエルマー社製ＤＳＣ−２型
示差走査熱量計により１０℃／min の昇温速度で測定し
た。 密度：樹脂の密度はＪＩＳ Ｋ６７６０に準拠して密度
勾配管法により２３℃で測定した。 臭気強度： 臭気センサー法 ガラス製の容積５００ccのサンプル瓶に、０．５g の酸
素吸収シートを入れてアルミ箔で覆いをし、６０℃下で
１時間エージングを行なう。その後、２３℃下で３０分
冷却し内部の臭気強度を新コスモス電気社製臭気センサ
ー（ＸＰ−３２９型）にて５分間測定し、その時の最大
値を測定した。 官能評価法：臭気センサー法と同様に作成した臭気サ
ンプルで官能評価を行ない、臭気強度を判定した。官能
評価の判定基準は以下の通りである。 Ａ：無臭 Ｂ：ほとんど無臭 Ｃ：弱く臭う Ｄ：臭う Ｅ：かなり臭うMelting point: Measured with a DSC-2 type differential scanning calorimeter manufactured by Perkin Elmer at a temperature rising rate of 10 ° C./min. Density: The density of the resin was measured at 23 ° C. by the density gradient tube method according to JIS K6760. Odor strength: Odor sensor method A glass bottle with a volume of 500 cc was charged with 0.5 g of oxygen absorbing sheet, covered with aluminum foil, and aged at 60 ° C. for 1 hour. Then, the mixture was cooled at 23 ° C. for 30 minutes, and the internal odor intensity was measured with an odor sensor (XP-329 type) manufactured by New Cosmos Electric Co., Ltd. for 5 minutes, and the maximum value at that time was measured. Sensory evaluation method: Sensory evaluation was performed on an odor sample prepared in the same manner as in the odor sensor method to determine the odor intensity. The criteria for sensory evaluation are as follows. A: odorless B: almost odorless C: weakly odorous D: odorous E: quite odorous
【００１５】実施例１ 線状ポリエチレン樹脂（東洋曹達株式会社製 ニポロン
ハード４０１０ 密度０．９６３g/cm3 、ＭＦＲ＝５．
５、融点１３７℃）３０重量部と鉄系酸素吸収剤（一次
粒子径７μｍ、凝集粒子径１０６μｍの鉄粉であり、電
解質として塩化カルシウムを２重量％含み、鉄成分とし
ては還元鉄９５重量％および鉄の酸化物５重量％からな
る）７０重量部を神戸製鋼（株）製のＢＲ型バンバリー
によって１６０℃で２分間混練して組成物を得た。この
組成物をの田辺プラスチック社製３０ｍｍφ押出機によ
り１６０℃の加工温度にてＴダイ成形し、厚さ１ｍｍの
シートを得た。このシートを日本製鋼（株）のロール延
伸機により１３０℃でたて方向に５．０倍に延伸し酸素
吸収シートが得られた。結果は表−１に示すように高い
酸素吸収能力を持ち、かつ臭気も問題とならない酸素吸
収シートであった。Example 1 Linear polyethylene resin (manufactured by Toyo Soda Co., Ltd. Nipolon Hard 4010, density 0.963 g / cm 3 , MFR = 5.
5, iron powder having 30 parts by weight of melting point 137 ° C. and iron-based oxygen absorber (primary particle diameter 7 μm, aggregate particle diameter 106 μm, containing 2% by weight of calcium chloride as an electrolyte and 95% by weight of reduced iron as an iron component). 70 parts by weight (comprising 5% by weight of iron oxide) were kneaded with a BR Banbury manufactured by Kobe Steel, Ltd. at 160 ° C. for 2 minutes to obtain a composition. This composition was T-die molded at a processing temperature of 160 ° C. using a 30 mmφ extruder manufactured by Tanabe Plastic Co., Ltd. to obtain a sheet having a thickness of 1 mm. This sheet was stretched 5.0 times in the vertical direction at 130 ° C. by a roll stretching machine of Nippon Steel Co., Ltd. to obtain an oxygen absorbing sheet. As a result, as shown in Table-1, the oxygen absorption sheet had a high oxygen absorption capacity and odor was not a problem.
【００１６】実施例２ 線状ポリエチレン樹脂をショウレックス５０５０（昭和
電工株式会社製 密度０．９５０g/cm3 、ＭＦＲ＝５、
融点１３３℃）に代え、延伸温度を１２５℃に変更し
た以外は実施例１と同様に加工し酸素吸収シートが得ら
れた。結果として、実施例１と同様な酸素吸収性能をを
持ち、臭気もほとんど無い酸素吸収シートであった。Example 2 A linear polyethylene resin was used as Sholex 5050 (Showa Denko KK density 0.950 g / cm 3 , MFR = 5,
Instead of the melting point of 133 ° C.), the oxygen absorbing sheet was obtained in the same manner as in Example 1 except that the stretching temperature was changed to 125 ° C. As a result, the oxygen absorption sheet had the same oxygen absorption performance as that of Example 1 and had almost no odor.
【００１７】実施例３ 延伸倍率を７．０倍にした以外は実施例１と同様に加工
を行ない酸素吸収能に優れた酸素吸収シートが得られ
た。Example 3 An oxygen absorbing sheet excellent in oxygen absorbing ability was obtained by performing the same processing as in Example 1 except that the stretching ratio was 7.0 times.
【００１８】実施例４ 酸素吸収剤中の電解質を塩化ナトリウムとした以外は実
施例１と同様に加工を行ない、酸素吸収能に優れ臭気も
問題とならない酸素吸収シートが得られた。Example 4 An oxygen absorbing sheet was obtained which was processed in the same manner as in Example 1 except that the electrolyte in the oxygen absorbent was sodium chloride, and which had an excellent oxygen absorbing ability and had no problem of odor.
【００１９】実施例５ 酸素吸収剤中の電解質を塩化ナトリウムとした以外は実
施例２と同様に加工を行ない、酸素吸収能に優れ臭気も
問題とならない酸素吸収シートが得られた。Example 5 An oxygen absorbing sheet was obtained which was processed in the same manner as in Example 2 except that the electrolyte in the oxygen absorbent was sodium chloride, and which had an excellent oxygen absorbing ability and no odor was a problem.
【００２０】比較例１ 延伸温度を１００℃にした以外は実施例１と同様に加工
を行ない酸素吸収シートを得ようとしたが、延伸中に破
断を起こし酸素吸収シートを作成することが出来なかっ
た。Comparative Example 1 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the stretching temperature was changed to 100 ° C., but an oxygen absorbing sheet could not be prepared due to breakage during stretching. It was
【００２１】比較例２ 延伸倍率を１１．０倍にした以外は実施例１と同様に加
工を行ない酸素吸収シートを得ようとしたが、延伸中に
破断を起こし酸素吸収シートを作成することが出来なか
った。Comparative Example 2 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the stretching ratio was set to 11.0. However, breakage occurred during stretching and an oxygen absorbing sheet could be prepared. I could not do it.
【００２２】比較例３ 延伸加工を行なわない以外は実施例１と同様に加工を行
ない酸素吸収シートを得たが、酸素吸収能が極めて劣る
シートとなった。Comparative Example 3 An oxygen absorbing sheet was obtained by the same process as in Example 1 except that the stretching process was not carried out, but the oxygen absorbing ability was extremely poor.
【００２３】比較例４ シート厚みを６．０mmとした以外は実施例１と同様に加
工を行ない酸素吸収シートを得ようとしたが、延伸中に
破断を起こし酸素吸収シートを作成することが出来なか
った。Comparative Example 4 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the sheet thickness was 6.0 mm. However, the oxygen absorbing sheet could be broken during stretching and an oxygen absorbing sheet could be prepared. There wasn't.
【００２４】比較例５ 線状ポリエチレンを１０重量部、酸素吸収剤を９０重量
部に変更した以外は実施例１と同様に加工を行ない酸素
吸収シートを得ようとしたが、すべての酸素吸収剤が線
状ポリエチレン中に分散せず酸素吸収シートを作成する
ことが出来なかった。Comparative Example 5 An oxygen absorbing sheet was prepared in the same manner as in Example 1 except that the amount of linear polyethylene was changed to 10 parts by weight and the amount of oxygen absorbent was changed to 90 parts by weight. Was not dispersed in the linear polyethylene and an oxygen absorbing sheet could not be prepared.
【００２５】比較例６ 線状ポリエチレンの添加量を７５重量部、酸素吸収剤の
添加量を２５重量部に変更した以外は実施例１と同様に
加工を行ない酸素吸収シートを得たが、著しく酸素吸収
能に劣るシートとなった。Comparative Example 6 An oxygen absorbing sheet was obtained by carrying out the same processing as in Example 1 except that the amount of linear polyethylene added was changed to 75 parts by weight and the amount of oxygen absorbent added was changed to 25 parts by weight. It became a sheet with poor oxygen absorption capacity.
【００２６】比較例７ 線状ポリエチレンをスミカセン−Ｌ ＦＡ２０１−０
（住友化学工業株式会社製 密度 ０．９１９g/cm3 、
ＭＦＲ＝２．０、融点１２３℃）とし、延伸温度を１１
６℃とした以外は実施例１と同様に加工を行ない酸素吸
収シートを得たが臭気があり、食品分野の酸素吸収剤と
しては不適切なものであった。Comparative Example 7 Linear polyethylene was added to Sumikasen-L FA201-0.
(Sumitomo Chemical Co., Ltd. density 0.919 g / cm 3 ,
MFR = 2.0, melting point 123 ° C.) and stretching temperature 11
An oxygen absorbing sheet was obtained by performing the same processing as in Example 1 except that the temperature was 6 ° C. However, it had an odor and was unsuitable as an oxygen absorbent in the food field.
【００２７】比較例８ 線状ポリエチレンをエクセレンＶＬ２００（住友化学工
業株式会社製 密度０．９００g/cm3 、ＭＦＲ＝２．
０）に変更し、線状ポリエチレンの添加量を２５重量
部、酸素吸収剤の添加量を７５重量部とし、延伸温度を
５０℃とした以外は実施例１と同様に加工を行ない酸素
吸収シートを得たが、臭気がかなりあり、食品分野の酸
素吸収剤としては不適切なものであった。Comparative Example 8 Linear polyethylene was used as Excellen VL200 (manufactured by Sumitomo Chemical Co., Ltd., density 0.900 g / cm 3 , MFR = 2.
0), the linear polyethylene was added in an amount of 25 parts by weight, the oxygen absorbent was added in an amount of 75 parts by weight, and the stretching temperature was 50 ° C. However, it had a considerable odor and was unsuitable as an oxygen absorber in the food field.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｋ 3/08 ＫＤＺ 7167−4Ｊ 3/14 ＫＥＡ 7167−4Ｊ 3/20 ＫＥＢ 7167−4Ｊ // Ｃ０８Ｌ 23/06 ＬＤＣ 7107−4Ｊ Ｂ２９Ｋ 23:00 Ｂ２９Ｌ 7:00 4Ｆ Ｃ０８Ｌ 23:10 (72)発明者 久米 孝典 大阪府高槻市塚原２丁目10番１号 住友化 学工業株式会社内 (72)発明者 榊原 孝 大阪府高槻市塚原２丁目10番１号 住友化 学工業株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08K 3/08 KDZ 7167-4J 3/14 KEA 7167-4J 3/20 KEB 7167-4J // C08L 23/06 LDC 7107-4J B29K 23:00 B29L 7:00 4F C08L 23:10 (72) Inventor Takanori Kume 2-10-10 Tsukahara, Takatsuki City, Osaka Prefecture (72) Inventor Takashi Sakakibara 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Industry Co., Ltd.
Claims (1)
リエチレン樹脂１５〜７０重量％と、一次粒子径０．０
１〜２０μｍの粉体が５〜２００μｍに凝集した鉄系酸
素吸収剤３０〜８５重量％からなる樹脂組成物を厚さ３
０μｍ〜５ｍｍにシート加工した後、下記の式で示され
る延伸温度で少なくとも一軸方向に１．５〜１０．０倍
の倍率で延伸された酸素吸収シート。 Ｔｍ−２０≦Ｔｋ≦Ｔｍ−２； ただし、Ｔｍ：線状ポリエチレンの融点（℃） Ｔｋ：延伸温度（℃）1. A linear polyethylene resin having a density of 0.940 g / cm 3 or more and 15 to 70% by weight, and a primary particle diameter of 0.0.
A resin composition consisting of 30 to 85% by weight of an iron-based oxygen absorber in which powder of 1 to 20 μm is aggregated to 5 to 200 μm is formed to a thickness of 3
An oxygen-absorbing sheet that is sheet-processed to have a thickness of 0 μm to 5 mm and then stretched at a stretching temperature represented by the following formula in at least a uniaxial direction at a magnification of 1.5 to 10.0 times. Tm-20 ≦ Tk ≦ Tm-2; where Tm: melting point of linear polyethylene (° C.) Tk: stretching temperature (° C.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03774692A JP3168436B2 (en) | 1992-02-25 | 1992-02-25 | Oxygen absorbing sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03774692A JP3168436B2 (en) | 1992-02-25 | 1992-02-25 | Oxygen absorbing sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05237380A true JPH05237380A (en) | 1993-09-17 |
| JP3168436B2 JP3168436B2 (en) | 2001-05-21 |
Family
ID=12506046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03774692A Expired - Lifetime JP3168436B2 (en) | 1992-02-25 | 1992-02-25 | Oxygen absorbing sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3168436B2 (en) |
-
1992
- 1992-02-25 JP JP03774692A patent/JP3168436B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3168436B2 (en) | 2001-05-21 |
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