JP2007144407A - Oxygen scavenger, oxygen scavenger intermediate, oxygen scavenger composite body and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen scavenger capable of obtaining a high deoxygenation performance in a quick time. <P>SOLUTION: In the oxygen scavenger, an electrolyte becoming an oxidation reaction auxiliary is contained in the oxygen scavenger intermediate obtained by drying a sheet forming body containing a metal to be oxidized, a water retaining agent and a fibrous substance. The oxygen scavenger contains 0.1-10 mass% of electrolyte and its water content is 5-70 mass%. CSF of the fibrous material is preferably 600 ml or less. An effective reaction ratio of the metal to be oxidized is preferably 75% or higher. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an oxygen scavenger, an oxygen scavenger intermediate, an oxygen scavenger complex, and a method for producing the same using an oxidation reaction between oxygen in the air and an oxidizable metal.

  As a conventional technique related to an oxygen scavenger using an oxidation reaction between oxygen in the air and oxidizable metal powder, for example, a technique described in Patent Document 1 below is known.

  In this technique, a mixture of a fibrous substance, iron powder, water and an electrolyte is formed into a sheet by paper making, and its Gurley air permeability is set to 50000 seconds / 100 ml or less.

  By the way, the oxygen scavenger produced by this technique is made into a sheet by paper making a mixture of fibrous material, iron powder, water and electrolyte. Since the electrolyte that serves as an oxidation reaction aid is added to the slurry, the oxidation reaction of the iron powder occurs during the preparation of the slurry, during the supply and / or during the sheet forming, and the performance of the resulting oxygen scavenger decreases. In particular, during the supply of the slurry, the oxidation reaction of the iron powder progressed over time, and the oxygen scavenger performance of the resulting oxygen scavenger deteriorated over time, and there was a problem that constant performance could not be obtained. . Therefore, a large amount of oxygen scavenger is required to guarantee the minimum oxygen scavenging performance required for the quality assurance of the oxygen scavenger. Furthermore, there is a problem that rust is easily generated in the manufacturing machine. Further, the obtained sheet also has a problem in storage stability due to the progress of oxidation. Furthermore, depending on the field of application of the oxygen scavenger, there is a field in which oxygen scavenging performance is desired in which high oxygen scavenging performance can be obtained in a quick time.

Japanese Patent Laid-Open No. 62-234544

  Accordingly, an object of the present invention is to provide an oxygen scavenger, oxygen scavenger intermediate, oxygen scavenger complex, and a method for producing the same, which can provide high oxygen scavenging performance in a quick time.

  The present invention is an oxygen scavenger comprising an oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material, and an electrolyte as an oxidation reaction aid, The object is achieved by providing an oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass.

  The present invention also relates to an oxygen scavenger intermediate used in the oxygen scavenger of the present invention, wherein the oxygen scavenger intermediate is formed by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material. Provide the body.

  The present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the present invention.

  The present invention also relates to a method for producing the oxygen scavenger according to the present invention, wherein an oxygen scavenger intermediate obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material is subjected to an oxidation reaction. The present invention provides a method for producing an oxygen scavenger containing an electrolyte as an auxiliary agent.

  Further, the present invention is a method for producing the oxygen scavenger complex of the present invention, wherein an oxygen scavenger intermediate formed by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material, After providing the said functional layer, the manufacturing method of the oxygen absorber complex which contains the electrolyte used as an oxidation reaction adjuvant is provided.

  Further, the present invention is a method for producing the oxygen scavenger complex of the present invention, wherein an oxygen scavenger intermediate formed by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material, The present invention provides a method for producing an oxygen scavenger complex in which an oxygen scavenger is produced by including an electrolyte as an oxidation reaction aid, and then the functional layer is provided on the oxygen scavenger.

  According to the oxygen scavenger of the present invention, high oxygen scavenging performance can be obtained in a quick time. Moreover, according to the oxygen scavenger complex of the present invention, various functions of the functional layer can be imparted to the oxygen scavenging performance of the oxygen scavenger. The manufacturing method of the oxygen scavenger and oxygen scavenger complex of the present invention does not include an electrolyte that is an oxidation reaction aid, and prepares and manufactures a slurry made of an oxidizable metal, a water retention agent, and a fibrous material. Thus, it is possible to minimize the deterioration of the oxygen removal performance due to oxidation of the oxidizable metal during slurry preparation, supply and / or molding, and the oxygen absorber and oxygen absorber complex are preferably produced. Can do.

  The present invention will be described below based on preferred embodiments with reference to the drawings.

  The oxygen scavenger of the present invention is an oxygen scavenger intermediate obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material, and an electrolyte serving as an oxidation reaction aid. . The oxygen scavenger of this embodiment is a so-called self-reactive oxygen scavenger in which an oxidation reaction of an oxidizable metal occurs with moisture contained in the oxygen scavenger itself.

The oxygen scavenger contains the electrolyte in an amount of 0.1 to 10% by mass, preferably 0.2 to 8% by mass, more preferably 0.3 to 6% by mass, and a moisture content of 5 to 70% by mass, preferably Is 7 to 60% by mass, more preferably 10 to 50% by mass.
When the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger are within such ranges, sufficient water can be secured to sustain the oxidation reaction, and the oxidation reaction proceeds sufficiently. Moreover, since water can be uniformly supplied to the oxygen scavenger, uniform oxygen scavenging performance can be obtained and the air permeability of the oxygen scavenger is not impaired, so that high oxygen scavenging performance can be obtained quickly. .

  As the electrolyte, an electrolyte that has been conventionally used for this type of oxygen scavenger can be used without particular limitation. Examples of the electrolyte include alkali metal, alkaline earth metal or heavy metal sulfates, carbonates, chlorides or hydroxides. Of these, various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride and ferric chloride are preferably used because of their excellent conductivity, chemical stability and production cost. These electrolytes can be used alone or in combination of two or more.

As the oxidizable metal, an oxidizable metal conventionally used in this type of oxygen scavenger can be used without particular limitation. As the form of the oxidizable metal, it is preferable to use a form having a powdery or fibrous form from the viewpoint of handleability and moldability.
Examples of the oxidizable metal having a powder form include iron powder, aluminum powder, zinc powder, manganese powder, magnesium powder, and calcium powder. Among these, handling property, safety, and manufacturing cost are included. Iron powder is preferably used. The oxidizable metal has a particle size (hereinafter referred to as the particle size, the maximum length in the form of powder, or dynamic light scattering because the fixability to a fibrous material and control of the reaction are good. The average particle diameter measured by a laser diffraction method, etc.) is preferably 0.1 to 300 μm, and the one having a particle diameter of 0.1 to 150 μm containing 50% by mass or more is used. It is more preferable.
Examples of the oxidizable metal having a fibrous form include steel fibers, aluminum fibers, and magnesium fibers. Among these, steel fibers, aluminum fibers, and the like are preferably used from the viewpoints of handleability, safety, and manufacturing cost. The oxidizable metal having a fibrous form has a fiber length of 0.1 to 50 mm and a thickness of 1 to 1000 μm in terms of moldability and mechanical strength of the obtained oxygen scavenger, surface smoothness, and oxygen scavenging performance. It is preferable to use one.

  The oxidizable metal in the oxygen scavenger preferably has an effective reaction rate of 75% or more, and more preferably 85% or more. When the effective reaction rate is within such a range, the oxidation reaction of the oxidizable metal is suppressed during the slurry preparation and paper making during the production of the oxygen scavenger. In addition to reducing the size and weight of the oxygen scavenger, the raw material cost of the oxygen scavenger can be reduced. Here, the effective reaction rate (%) is the ratio of the oxidizable metal effective for deoxygenation in the oxygen scavenger represented by the following formula 1, and the ratio of the oxidizable metal in the raw material stage represented by the following formula 2. It is a value obtained by the following formula 3 divided by the ratio. The upper limit of the effective reaction rate is 100%.

Mass of oxidizable metal effective for deoxidation / mass of oxygen scavenger = A Formula 1
Mass of oxidizable metal in raw material stage / mass of oxygen scavenger = B ... Formula 2
Effective reaction rate of oxygen scavenger (%) = (A / B) × 100 Formula 3
Here, the mass of the oxygen scavenger is the absolute dry mass obtained by heating the oxygen scavenger to near 100 ° C. in a nitrogen atmosphere to evaporate the moisture, but the mass in a state containing moisture may be used as it is. However, it is necessary to match the moisture state of the oxygen scavenger in Formula 1 and Formula 2.
In addition, the above packaging specification means that, for example, the thickness and weight of a product manufactured by filling a bag such as a pouch with the oxygen scavenger of the present application together with food etc. is too thick or too heavy for the oxygen scavenger. It is the deoxidation ability necessary for food preservation that can perform without any problems.

  The following is an example of an oxygen scavenger using iron powder as an oxidizable metal, activated carbon as a water retention agent, and wood pulp as a fibrous material, and thermogravimetry (abbreviated as TG) and a vibrating sample magnetometer (Vibrating Sample). A method for obtaining an effective reaction rate using a magnetometer (abbreviated as VSM) will be described.

  The mass ratio of iron powder at the raw material stage can be determined by thermogravimetry. When a sample was prepared from the oxygen scavenger and the sample was put in a sample container and gradually raised from room temperature in a nitrogen atmosphere, the water contained in the oxygen scavenger evaporated near 350 ° C., and 350 ° C. Mass decreases rapidly in the vicinity. This mass loss is the amount of cellulose degradation contained in the wood pulp. When the temperature is further raised and air is introduced from 550 ° C. and heated to 1000 ° C., the activated carbon and the wood pulp are burned, and finally only the ash derived from iron oxide and wood pulp remains in the sample container. Ash content derived from wood pulp can be determined by using thermogravimetry with wood pulp alone. By heating in the same manner as in the case of the oxygen scavenger, the relationship between the cellulose degradation amount and the ash content derived from wood pulp can be obtained. Therefore, the mass of iron oxide is obtained by subtracting the ash content derived from wood pulp calculated from the cellulose degradation amount from the sample container residue.

  Based on the mass of this iron oxide, the mass of the iron powder contained in the sample can be determined. The correction coefficient for obtaining the mass of the iron powder of the raw material from the mass of the iron oxide is generally obtained from the oxidation reaction formula of iron, but the iron powder supplied from the raw material manufacturer is usually pure iron 100 Since it is not%, the correction coefficient is obtained experimentally. A sample of iron powder is put in a sample container and dried in a nitrogen atmosphere up to 600 ° C., and then air is added and heated to 1000 ° C. to generate iron oxide. The correction coefficient can be obtained from the relationship between the mass of the generated iron oxide and the mass of the raw iron powder. Using the correction coefficient obtained by this experiment, the mass of the iron powder can be obtained from the mass of the iron oxide, and the mass ratio of the iron powder at the raw material stage (formula 5) can be obtained from the ratio to the mass of the sample. it can.

Next, a method for obtaining the mass of iron powder effective for deoxygenation in the oxygen absorber using a vibrating sample magnetometer will be described. When an external magnetic field is applied using a vibrating sample magnetometer using iron powder as a sample, the iron powder is magnetized. The magnetization amount of the iron powder is saturated when the external magnetic field is increased, and this saturation magnetization amount is proportional to the mass of the iron powder sample. In addition, when oxygen is absorbed into this iron powder sample, the iron powder is deactivated (losing the deoxygenation capacity), and the saturation magnetization decreases in proportion to the iron powder effective for deoxygenation,
When all of the iron powder is changed to iron oxide and deoxidation capability is lost, the saturation magnetization becomes almost zero. Therefore, by measuring the saturation magnetization of the oxygen scavenger sample, the mass of iron powder effective for oxygen scavenging contained in the oxygen scavenger sample can be determined. By dividing the mass of iron powder effective for deoxygenation by the mass of the sample, the proportion of iron powder effective for oxygen absorption in the oxygen absorber can be determined (Formula 4). The effective reaction rate of the oxygen scavenger sample is obtained by dividing the ratio of iron powder effective for deoxygenation in the oxygen scavenger represented by the following formula 4 by the ratio of iron powder in the raw material stage represented by the following formula 5. It is a value calculated | required by the following formula 6.

Mass of iron powder effective for deoxygenation / Sample mass of oxygen scavenger = C Formula 4
Mass of iron powder at raw material stage / sample mass of oxygen scavenger = D Equation 5
Effective reaction rate of oxygen scavenger (%) = (C / D) × 100 Equation 6

  The amount of the oxidizable metal in the oxygen scavenger intermediate is preferably 10 to 98% by mass, and more preferably 30 to 90% by mass. When the blending amount of the oxidizable metal is within such a range, desired deoxygenation performance can be obtained. Moreover, the increase of the below-mentioned fibrous substance and adhesive components (coagulant etc.) which comprise the said oxygen scavenger intermediate body can be suppressed, and it does not become hard but is excellent in usability. Further, when the obtained oxygen scavenger intermediate is used as a gas scavenger, even if an oxide film such as an oxidizable metal is formed on the surface thereof, the air permeability is not impaired. The reaction easily occurs until a high deoxygenation performance is obtained. In addition, the oxidizable metal does not expand and condense due to the oxidation reaction and does not become too hard. In addition, sufficient water supply by the water retention agent can be obtained, and the oxidizable metal can be prevented from falling off. Moreover, since the below-mentioned fibrous material and adhesive component forming the oxygen scavenger intermediate are sufficiently contained, it is possible to suppress a decrease in mechanical strength such as bending strength and tensile strength. Here, the blending amount of the oxidizable metal in the oxygen scavenger intermediate can be determined by an ash test according to JIS P8128 or the thermogravimetric measurement method. Further, for example, in the case of iron, it can be quantified by a sample-type magnetization measurement test or the like using the vibrating sample-type magnetometer utilizing the property that magnetization is generated when an external magnetic field is applied.

  As the water retention agent, a water retention agent conventionally used for oxygen scavengers can be used without particular limitation. In addition to acting as a moisture retention agent, the water retention agent also has a function as an oxygen retention / supply agent for the oxidizable metal. Examples of the water retention agent include activated carbon (coconut husk charcoal, charcoal powder, calendar bituminous coal, peat, lignite), carbon black, acetylene black, graphite, zeolite, perlite, vermiculite, silica, cancrinite, fluorite and the like. Among these, activated carbon is preferably used because it has water retention ability, oxygen supply ability, and catalytic ability. As the water retention agent, it is preferable to use a powdery material having a particle size of 0.1 to 500 μm from the viewpoint that an effective contact state with an oxidizable metal can be formed. It is more preferable to use a material containing at least mass%. As the water retention agent, a form other than the powder form as described above can be used. For example, a form of fiber form such as activated carbon fiber can also be used.

  The blending amount of the water retention agent in the oxygen scavenger intermediate is preferably 0.5 to 60% by mass, and more preferably 1 to 50% by mass. When the blending amount of the water retention agent is within such a range, moisture necessary for the oxidation reaction of the oxidizable metal for obtaining a desired deoxidation effect can be accumulated in the deoxidation agent. Further, the air permeability of the oxygen scavenger intermediate is not impaired, the oxygen supply is good, and the oxygen scavenging efficiency is excellent. Moreover, the occurrence of the water retention agent falling off can be suppressed. In addition, the fibrous materials and adhesive components described later constituting the oxygen scavenger intermediate are not reduced, and mechanical strength such as bending strength and tensile strength is also maintained.

  Examples of the fibrous material include, for example, plant fibers (cotton, kabok, wood pulp, non-wood pulp, peanut protein fiber, corn protein fiber, soybean protein fiber, mannan fiber, rubber fiber, hemp, Manila hemp , Sisal, New Zealand hemp, Rafu hemp, eggplant, rush, straw, etc.), animal fiber (wool, goat hair, mohair, cashmere, alkapa, Angola, camel, vicuña, silk, feathers, down, feather, algin fiber, chitin Fiber, casein fiber, etc.) and mineral fiber (asbestos, etc.). Examples of synthetic fibers include semi-synthetic fibers (acetate, triacetate, oxide acetate, promix, chlorinated rubber, hydrochloric acid rubber, etc.), metal fibers , Carbon fiber, inorganic fiber (eg glass fiber, ceramic fiber, etc.) . Also, polyolefins such as high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, etc., polyester, polyvinylidene chloride, starch, polyvinyl alcohol or polyvinyl acetate, single fibers such as copolymers or modified products thereof, or these A core-sheath composite fiber having a resin component in the sheath can be used. Among these, polyolefins and modified polyesters are preferably used because they have high adhesive strength between fibers, are easy to form a three-dimensional network structure by fusion of fibers, and have a melting point lower than the ignition point of pulp fibers. Synthetic fibers such as polyolefin having branches are also preferably used because of their good fixability with oxidizable metals and water retention agents. These fibers can be used alone or in combination of two or more. In addition, these fibers can be used in the form of collected and reused. Among these, wood pulp and cotton are preferably used in terms of the oxidizable metal, the fixability of the water retaining agent, the flexibility of the resulting papermaking, the oxygen permeability resulting from the presence of voids, the production cost, and the like. It is done.

The fibrous material preferably has a Canadian Standard Freeness (CSF) of 600 ml or less, more preferably 450 ml or less. When the CSF is 600 ml or less, the fixing property between the fibrous material and the components such as the oxidizable metal and the water retention agent is good, and the oxygen scavenger obtained by maintaining a predetermined blending amount is excellent in the oxygen scavenging performance. It will be a thing. In addition, the moldability is good, such as obtaining an oxygen scavenger intermediate with a uniform thickness. In addition, since the fixing between the fibrous material and the component is good, it is possible to obtain a bond strength derived from the dropping of the component, the entanglement between the component and the fibrous material, and hydrogen bonding. For this reason, mechanical strength such as bending strength and tensile strength is maintained, and workability is also improved.
The lower the CSF of the fibrous material, the better. However, in the normal papermaking only of pulp fiber, when the component ratio other than the fibrous material is low, the drainage is very poor and the dehydration is difficult when the CSF is less than 100 ml. As a result, a paper product having a uniform thickness cannot be obtained, or molding failure such as blister breakage occurs during drying. On the other hand, in the present invention, since the ratio of components other than the fibrous material is high, an oxygen scavenger intermediate with good drainage and uniform thickness can be obtained even if the CSF is less than 100 ml. In addition, since the CSF is lower as the CSF is lower, the fixability between the fibrous material and components other than the fibrous material is improved, and a high-strength oxygen scavenger intermediate can be obtained.
Adjustment of the CSF of the fibrous material can be performed by a beating process or the like. CSF may be adjusted by mixing low and high CSF fibers. In addition, CSF can be obtained by measuring by the method shown in JIS P8121 (pulp freeness test method), and is an index representing the degree of water breakage of a fibrous material having a value of 0 or more.

The fibrous material preferably has a negative (negative) surface charge. As the surface charge is strongly negatively charged, the fixability of powder components such as oxidizable metals and water retention agents to the fibrous material is good, the powder retention is improved, and the obtained oxygen scavenger Deoxygenation performance is further improved. Further, it is possible to prevent a large amount of powder components such as an oxidizable metal and a water retaining agent from being mixed in the waste water in the wet papermaking process, and this does not adversely affect productivity and environmental conservation. In particular, from the viewpoint of further increasing the yield of the obtained oxygen scavenger intermediate, the fibrous material preferably has a charge amount of −2.5 × 10 ⁻⁶ eq / g or less, and the charge amount is − 4.0 × 10 ⁻⁶ eq / g or less is more preferable. Here, the charge amount of the fibrous material is measured by colloid titration. The same applies to the zeta potential, which is the apparent potential at the shear plane between the charged particle interface and the solution, and this is measured by the streaming potential method, the electrophoresis method, or the like.

  The fibrous material preferably has an average fiber length of 0.1 to 50 mm, and more preferably 0.2 to 20 mm. When the average fiber length is within such a range, sufficient mechanical strength such as bending strength and tensile strength of the obtained oxygen scavenger intermediate can be obtained. Further, since the paper layer is not formed too densely and the air permeability of the oxygen scavenger intermediate is not impaired, the oxygen supply is good and the oxygen scavenging property is excellent. Further, the fibrous material is uniformly dispersed in the oxygen scavenger intermediate, and uniform mechanical strength can be obtained. In addition, an oxygen scavenger intermediate with a uniform thickness is obtained, the fiber spacing is not too wide, and the ability to retain components such as the oxidizable metal and water retention agent by the fibers is obtained, so that the components can be removed. It can be suppressed.

  The blending amount of the fibrous material in the oxygen scavenger intermediate is preferably 2 to 50% by mass, and more preferably 5 to 40% by mass. When the blending amount is within such a range, an effect of preventing the oxidizable metal and the water retention agent from falling off can be obtained. Also, the oxygen scavenger intermediate is flexible. Further, the ratio of the components such as the oxidizable metal and the water retention agent in the obtained oxygen scavenger intermediate is not lowered, and a desired oxygen scavenging performance can be obtained.

  Here, the composition ratio of each component is obtained by, for example, obtaining the content of the fibrous material and the content of the oxidizable substance by thermogravimetry, and subtracting these from the total amount to obtain the content of the water retention agent. Can do.

  The oxygen scavenger intermediate preferably contains 50% by mass or more of components other than the fibrous material, more preferably 70% by mass or more, and even more preferably 80% by mass or more. . When the components other than the fibrous material are 50% by mass or more, the oxygen scavenging performance is good. The more components other than the fibrous material, the better. However, the upper limit is preferably about 98% by mass from the viewpoint of obtaining the strength necessary to maintain the processability of the oxygen scavenger intermediate.

As described later, a flocculant may be added to the oxygen scavenger intermediate.
In addition, the oxygen scavenger intermediate is usually used for paper making such as a sizing agent, a colorant, a paper strength enhancer, a yield improver, a filler, a thickener, a pH control agent, and a bulking agent. The additive used can be added without any particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.

  In order to make it possible to use the oxygen scavenger in a microwave heating apparatus such as a microwave oven, it is preferable to add a fibrous material or powder such as silicon, alumina or the like having high magnetic resistance to the oxygen scavenger intermediate. . Further, when coloring is necessary for the appearance of the product, colored powders such as titanium oxide, calcium carbonate, and alumina white may be added. Furthermore, powders such as fluorite, isolite and talc, ceramic fibers and synthetic fibers can be added to promote the oxidation reaction and improve flexibility.

  When the oxygen scavenger intermediate is formed in a sheet form, the thickness of one sheet is preferably 0.08 to 1.2 mm, more preferably 0.1 to 0.6 mm. . When the thickness is 0.08 mm or more, the deoxidation performance, mechanical strength, fixability of components such as the oxidizable metal and water retention agent are good, and a stable and uniform thickness and composition distribution can be obtained. . Further, it is difficult for the sheet to be broken due to the occurrence of pinholes and the like, and there is no problem in productivity and workability. When the thickness is within 1.2 mm, a decrease in bending strength of the oxygen scavenger intermediate is also suppressed. Moreover, it is difficult to cause brittle fracture and a soft sheet can be obtained. In terms of productivity, the paper layer formation time and drying time can be shortened, and the operability is excellent. Moreover, the deoxidation performance is also good. Moreover, since it is hard to be cracked or broken, it is excellent in workability.

When said oxygen scavenger intermediate was formed into a sheet form, the basis weight of one thereof is preferably from 10 to 1000 g / m ^2, and more preferably 50~600g / m ^2. When the basis weight is 10 g / m ² or more, a particularly stable sheet can be formed when an oxidizable metal having a large specific gravity is used. When the basis weight is within 1000 g / m ^2, it is light and has a good feeling of use. In addition, productivity and operability are also improved.

When the oxygen scavenger intermediate is formed into a sheet-like form, the breaking length of one sheet is preferably 100 to 4000 m, and more preferably 200 to 3000 m. When the breaking length is 100 m or more, the sheet can be stably formed without breaking or cutting the sheet during operation. In addition, the product can be processed well for the same reason during processing. Further, even during use, it is reasonably comfortable and has a good feeling of use. When the breaking length is 4000 m or less, the fibrous material and adhesive component forming the sheet do not increase excessively, and the material is flexible and excellent in deoxidation performance. Here, the tearing length is determined by cutting a test piece of length 150 mm × width 15 mm from the sheet, then mounting the test piece on a tensile tester with a chuck interval of 100 mm according to JIS P8113, and a pulling speed of 20 mm / min. It is a value calculated by the following calculation formula after conducting a tensile test.
Breaking length (m) = (1 / 9.8) × (tensile strength [N / m]) × 10 ⁶ / (specimen basis weight [g / m ^2])

The oxygen scavenger intermediate has a basis weight in consideration of the point that the oxygen scavenging reaction proceeds favorably, the improvement of the ability, and the ability to contain the electrolyte more uniformly when the electrolyte is added. The air permeability per 100 g / m ² is preferably 0.1 to 1000 seconds / (6.4 cm ² · 300 ml), and preferably 0.1 to 500 seconds / (6.4 cm ² · 300 ml). More preferred.

  The thickness of the oxygen scavenger is appropriately set according to the use and form (for example, when the oxygen scavenger intermediate is in the form of a sheet, a plurality of sheets are used in a stacked manner). Considering processability and packaging specifications, 0.08 to 20 mm is preferable, and 0.1 to 10 mm is more preferable.

Next, a preferred embodiment of the oxygen scavenger complex of the present invention will be described.
In the oxygen scavenger complex of the present invention, a functional layer is provided on the oxygen scavenger of the present invention.

  The functional layer has a function of preventing a solid component of the oxygen scavenger from falling off, concealing, deodorizing, anti-magnetic, moisture barrier or oil barrier, or a combination of these functions.

  The functional layer having a function to prevent the solid component of the oxygen scavenger from falling out has air permeability for expressing the oxygen scavenging performance of the oxygen scavenger, but does not contaminate the solid component contained in the oxygen scavenger by dropping. It is something to prevent. The functional layer having such a function can be provided by applying a resin composition to paper, a nonwoven fabric, a porous resin film, a functional layer base material combined with these, or the oxygen scavenger, and drying. As the paper, paper pulp, synthetic pulp, or a mixture thereof is preferably produced by a wet or dry manufacturing method. As said nonwoven fabric, what was manufactured by manufacturing methods, such as wet, dry type, and a spun bond, can be used. The material of the nonwoven fabric is preferably made of fibers of thermoplastic resin such as polyolefin such as polyethylene or polypropylene, polyamide such as nylon, polyester such as polyethylene terephthalate, polyfluorinated olefin such as polytetrafluoroethylene. As the porous resin film, a thermoplastic resin such as a polyolefin such as polyethylene and polypropylene, a polyamide such as nylon, a polyester such as polyethylene terephthalate, and a polyfluorinated olefin such as polytetrafluoroethylene is preferable, as is the case with the material of the nonwoven fabric. As the perforated resin film, a film in which an inorganic or organic filler insoluble or hardly soluble in water is contained in the thermoplastic resin in order to form a large number of holes is used. As the filler, silica, calcium carbonate, alumina, titanium white barium sulfate, zeolite, diatomaceous earth, activated clay, acid clay, talc, bentonite, iron oxide and the like are preferably used. The particle size of the filler is preferably as fine as possible, but is preferably 0.01 to 100 μm, particularly preferably 0.1 to 50 μm. Examples of the resin composition include natural resin compositions such as starch, carboxymethyl cellulose, guar gum, polyvinyl alcohol, modified cellulose, vinyl chloride, acrylic, silicone, silicone acrylic, polyamide, polyester, and polyolefin. And a resin composition comprising a single or copolymer of a synthetic resin such as phenol, ethylene / vinyl acetate copolymer or polybutadiene, or a mixture thereof.

  The functional layer having a function of concealing the oxygen scavenger has air permeability for expressing the oxygen scavenging performance of the oxygen scavenger, but conceals the color of the oxygen scavenger so that it cannot be seen from the outside. The functional layer having such a function is a paper, a nonwoven fabric, a porous resin film, or a functional layer base material that is a combination thereof, containing a white or colored pigment, or a layer coated with a resin emulsion containing the pigment and dried. Can be provided. Examples of the white pigment include titanium oxide, zinc oxide, calcium carbonate, talc, kaolin, alumina silicate, clay, gypsum, and alumina white. Examples of the colored pigment include inorganic pigments such as carbon black, bengara, molybdate orange, and ultramarine blue, and azo, isoindolinone, phthalocyanonine, and quinacridone organic pigments. It is also possible to provide a non-pigmented non-pigmented layer on the outer surface side of the pigment-containing layer to improve impact resistance, strength, heat sealability and tackiness. For these paper, nonwoven fabric, perforated resin film and resin emulsion used for the functional layer having a shielding function, the same material as that of the functional layer having a function of preventing the solid component from dropping off can be appropriately selected.

The functional layer having a deodorizing function of the oxygen scavenger has air permeability for expressing the oxygen scavenging performance, but deodorizes the adsorbent by adsorbing or decomposing odor components emitted from the oxygen scavenger. The functional layer having such a function can be provided by paper, a nonwoven fabric, a perforated resin film or a combination thereof, or a resin emulsion coating layer containing a deodorant. For these paper, non-woven fabric, perforated resin film and resin emulsion used for the functional layer having a deodorizing function, the same material as that of the functional layer having a function of preventing the solid component from falling off can be appropriately selected. Examples of the deodorant include various activated carbons, diatomaceous earth, various aluminosilicates, activated alumina, titanium oxide and the like. As the activated carbon, a material used for the water retention agent can be used. The activated carbon is preferably dry charcoal having a moisture content of 10% or less (JIS K1470). Those subjected to treatment such as acid addition or alkali attachment can also be used. As the aluminosilicates, various tectosilicates such as natural or synthetic zeolites and natural or synthetic phyllosilicates can be used. Examples of the phyllosilicate include magnesium phyllosilicate, zinc phyllosilicate, bentonite, activated clay, and acid clay. A deodorant having a particle size of 0.01 to 100 μm, particularly 0.1 to 50 μm is preferable in consideration of dispersibility in a substrate and the like. Moreover, deodorant which exhibits deodorant by adsorption, specific surface area of 50~5000m ² / g, particularly preferably those of 100~4000m ² / g.

  The functional layer having a magnetic resistance function of the oxygen scavenger is preferably a magnetically resistant fibrous material such as silicon or alumina or a material in which powder is dispersed in a resin or a material in which the powder is supported on the fibrous material. Used.

  The functional layer having the moisture barrier function and the oil barrier function of the oxygen scavenger is, for example, the prevention of food contamination by the oxygen scavenger and the food that can occur when the oxygen scavenger is used for the preservation of food with a high water content such as retort It prevents contamination of the oxygen scavenger due to moisture from the water. As the functional layer having the moisture barrier function, a layer made of a thermoplastic resin film can be used. As the thermoplastic resin, for example, polyolefins such as polyethylene, polypropylene, and polymethylpentene, polyamides such as nylon, polyesters such as polyethylene terephthalate, polyfluorinated olefins such as polytetrafluoroethylene, and the like are preferably used. The thermoplastic resin may contain a poorly water-soluble filler. The poorly water-soluble filler is an inorganic or organic substance that is insoluble or hardly soluble in water. As the poorly water-soluble filler, for example, silica, calcium carbonate, alumina, titanium white barium sulfate, zeolite, diatomaceous earth, activated clay, acidic clay, talc, bentonite, iron oxide and the like are preferably used. In addition, the functional layer having the moisture barrier function and the like may be a paper pulp, synthetic pulp, synthetic fiber, or a mixture thereof having water resistance and oil resistance manufactured by a wet or dry manufacturing method.

  The thickness of the functional layer is appropriately set according to the function of the functional layer and the form of the oxygen scavenger complex. Considering processability, packaging specifications, etc., 1 to 10000 μm is preferable, and 10 to 1000 μm is more preferable.

  The functional layer may be partially provided on the surface of the oxygen scavenger or may be provided on the entire surface. As described later, the functional layer can be provided on the surface of the oxygen scavenger by lamination, coating, or impregnation. When the functional layer is provided by lamination, it is preferably laminated on the oxygen scavenger via an adhesive layer, as will be described later.

  The adhesive layer is not particularly limited in material and form as long as it can adhere the oxygen scavenger and the functional layer without adversely affecting the oxygen scavenging performance of the oxygen scavenger, but has air permeability. It is preferable. Such an air-permeable adhesive layer is a method in which a pressure-sensitive adhesive or an adhesive is applied to one or both of an oxygen scavenger or a functional layer in a streak-like or mesh-like pattern, and laminated, resin fibers , A method in which a heat-meltable resin material of a perforated resin film is placed on one or both of an oxygen scavenger or a functional layer and heat-laminated, or one or both of a heat-meltable resin and an oxygen scavenger or a functional layer The resin can be provided by a method in which the resin is extruded in a streak shape and laminated. As the pressure-sensitive adhesive, a urethane-based or acrylic-based pressure-sensitive adhesive is preferable. As the adhesive, a hot melt adhesive or an adhesive for dry lamination is preferable. Examples of the resin constituting the heat-meltable resin material include polyolefin resins and polyethylene resins.

  The thickness of the oxygen scavenger complex is appropriately set according to the form. Considering processability and packaging specifications, 0.08 to 30 mm is preferable, and 0.5 to 20 mm is more preferable.

Next, the method for producing the oxygen scavenger and oxygen scavenger complex of the present invention will be described based on its preferred embodiment.
First, a raw material composition (slurry) containing the oxidizable metal, the water retention agent, the fibrous material, and water is prepared.

The flocculant is preferably added to the raw material composition.
Examples of the flocculant include inorganic flocculants composed of metal salts such as sulfate band, polyaluminum chloride, ferric chloride, polyferric sulfate, and ferrous sulfate; polyacrylamide, sodium polyacrylate, polyacrylamide Mannich modified products, poly (meth) acrylic acid aminoalkyl ester-based, carboxymethylcellulose sodium-based, chitosan-based, starch-based, polyamide epichlorohydrin-based polymer flocculants; dimethyldiallylammonium chloride-based or ethyleneimine-based Organic coagulants such as condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide / formalin condensates; clay minerals such as montmorillonite and bentonite; silicon dioxide such as colloidal silica or hydrates thereof; hydrous magnesium silicate such as talc And the like. And among these flocculants, anionic colloidal silica, bentonite, etc. from the viewpoint of sheet surface properties, formation of texture, improvement of moldability, fixing rate of components such as the oxidizable metal and water retention agent, and improvement of paper strength The combined use of cationic starch, polyacrylamide or the like, or the combined use of anionic carboxymethylcellulose sodium salt and cationic polyamide epichlorohydrin cationic and anionic drugs is particularly preferred. Besides these combinations, these flocculants can be used alone or in combination of two or more.

  The addition amount of the flocculant is preferably 0.01 to 5% by mass and more preferably 0.05 to 3% by mass with respect to the solid content of the raw material composition. When the added amount is within such a range, an aggregating effect can be obtained, and dropping of components such as the oxidizable metal and water retention agent during papermaking can be suppressed. Moreover, a raw material composition becomes uniform and a papermaking body having a uniform thickness and composition can be obtained. Further, it does not cause sticking, tearing, burning, or scorching on the drying means during drying, and the productivity is not adversely affected. Further, the potential balance of the raw material composition is maintained, and the amount of the component dropped into the white water during papermaking can be suppressed. In addition, the oxidation reaction of the papermaking progresses, and the storage stability such as deoxygenation characteristics and strength decreases.

  The concentration of the raw material composition is preferably 0.05 to 15% by mass, and more preferably 0.1 to 2% by mass. With such a concentration, a large amount of water is not required, and time is not required for forming the papermaking product. Further, since the raw material composition is uniformly dispersed, the surface property of the obtained paper product is good, and a paper product having a uniform thickness can be obtained.

Next, the raw material composition is made into a paper.
The papermaking method when the papermaking is made into a sheet-like form is, for example, a papermaking method using a continuous papermaking type circular paper machine, long net paper machine, short net paper machine, twin wire paper machine, etc. In addition, there is a manual method which is a batch type papermaking method. Furthermore, a papermaking body can also be shape | molded by the multilayer papermaking using the said raw material composition and the composition of a composition different from this raw material composition. Further, by laminating sheets obtained by papermaking the raw material composition in multiple layers, or by laminating a sheet-like material obtained from a composition having a composition different from the raw material composition on the sheet, This sheet can also be formed. When making a papermaking body other than a sheet-like form, a three-dimensional shape can be shaped by the wet papermaking method conventionally used in the pulp mold method.

  The papermaking body can be dehydrated until the moisture content (mass moisture content, hereinafter the same) is 70% or less from the viewpoint of maintaining the shape after papermaking (shape retention) and maintaining the mechanical strength. Preferably, it is more preferable to dehydrate to 60% or less. Examples of the dewatering method of the papermaking after papermaking include dewatering by suction, a method of dehydrating by blowing pressurized air, a method of dehydrating by pressing with a pressure roll or a pressure plate, and the like.

  In the present embodiment, the paper-making body containing the oxidizable metal is actively dried to separate the moisture, thereby being excellent in suppressing oxidation of the oxidizable metal during the manufacturing process and long-term storage stability. It is possible to obtain an oxygen scavenger intermediate. Furthermore, in addition to the point of increasing the supporting force of the oxidizable metal to the fibrous material after drying and suppressing its falling off, from the point of expectation of improvement in mechanical strength due to the addition of a hot melt component and a thermal crosslinking component, It is preferable that the papermaking body is dried after the papermaking body and before the electrolyte is contained. Here, as drying means, heat drying, vacuum drying, freeze drying, or the like can be used as appropriate.

  The papermaking body is preferably dried by heat drying from the viewpoint of production speed, equipment cost, and the like. In this case, the heat drying temperature is preferably 60 to 300 ° C, more preferably 80 to 250 ° C. When the drying temperature is within such a temperature range, the drying time does not become too long, and the oxidation reaction of the oxidizable metal is not promoted along with the drying of moisture. For this reason, the deoxidation performance of the oxygen scavenger is not reduced. Further, the oxidation reaction of the oxidizable metal is not promoted only in the front and back layers of the oxygen scavenger intermediate, and discoloration to light brown is suppressed. In addition, it is possible to suppress a decrease in the deoxygenation effect of the oxygen scavenger without causing performance deterioration of the water retention agent or the like. In addition, water is not suddenly vaporized inside the oxygen scavenger intermediate, and the structure of the oxygen scavenger intermediate is not destroyed.

  The moisture content of the oxygen scavenger intermediate after drying is preferably 20% or less, and more preferably 10% or less. When the water content is 20% or less, excellent long-term storage stability, for example, when formed into a sheet and temporarily stored in a wound roll state, moisture movement hardly occurs in the thickness direction of the roll, and deoxidation performance. And changes in mechanical strength can be suppressed.

  The drying method of the papermaking body can be appropriately selected according to the form of the papermaking body, the processing method of the papermaking body before drying, the moisture content before drying, the moisture content after drying, and the like. Examples of the drying method include drying methods such as contact with a heating structure (heating element), spraying of heated air or steam (superheated steam), vacuum drying, electromagnetic wave heating, and electric heating. Moreover, it can also implement simultaneously with the above-mentioned dehydration method.

  In the present embodiment, the papermaking body and the oxygen scavenger intermediate are molded in the normal air atmosphere because the papermaking body and the oxygen scavenger intermediate do not contain an electrolyte as an oxidation reaction aid as described above. Can be molded. For this reason, manufacturing equipment can be simplified. Further, if necessary, it is possible to perform creping, slitting, trimming, and processing such as changing the form by processing. Since the obtained oxygen scavenger intermediate has high strength, when formed into a sheet form, it can be wound into a roll as necessary. In addition, when the oxygen scavenger intermediate is formed into a sheet-like form, it may be used alone or in layers, or overlaid with other sheets such as paper, cloth (woven fabric or nonwoven fabric), resin film, etc. Can be embossed or needle punched to laminate and integrate a plurality of sheets, or to perform uneven forming or punching. Moreover, by including a thermoplastic resin component or a hot water-dissolving component in the raw material composition, heat sealing can be performed to facilitate bonding and the like.

  The functional layer is provided on the oxygen scavenger intermediate. In the manufacturing process of the oxygen scavenger alone without providing the functional layer, the process of providing the following functional layer is not performed, but a process of adding an electrolyte to the oxygen scavenger intermediate is performed as described later.

  The functional layer can be selected according to the form of the oxygen scavenger intermediate. When the oxygen scavenger intermediate is formed into a sheet, it is preferable to provide a functional layer by a lamination method, particularly wet lamination, dry lamination, or extrusion lamination. By adopting the lamination processing method, wet lamination, dry lamination, and extrusion lamination are selected and incorporated in-line in accordance with the papermaking process of the sheet-shaped oxygen scavenger intermediate that becomes the base material of the oxygen scavenger. A functional layer can be provided on the surface of the oxygen agent through an adhesive as necessary. The functional layer can also be provided by applying and drying the resin composition for providing each functional layer as described above on the surface of the oxygen scavenger. Moreover, a functional layer can be provided on the surface and inside of the oxygen scavenger by impregnating the above-described resin composition. This method is effective when the oxygen scavenger intermediate is formed in a form other than the sheet form. For example, a wet paper product or a dry oxygen scavenger intermediate is processed by extrusion, pressure molding, tableting, etc., and processed into a spherical, noodle or fibrous shape, and then impregnated with the resin composition. You can also As described above, it is preferable to heat-dry the oxygen scavenger intermediate before providing the functional layer. However, heat-drying can also be performed after the functional layer is provided by laminating or coating.

  Next, the electrolyte is contained in the oxygen scavenger intermediate. The step of containing the electrolyte is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. However, when the electrolyte is added by impregnation of the electrolyte as described later, the oxidation reaction immediately after the addition is slow. Therefore, the electrolyte can be contained in a normal air atmosphere.

  The method of incorporating the electrolyte into the oxygen scavenger intermediate can be appropriately set according to the processing method, water content, form, etc. of the oxygen scavenger intermediate after papermaking. Examples of the method of containing the electrolyte include a method of impregnating the oxygen scavenger intermediate with an electrolyte solution having a predetermined concentration of the electrolyte, and adding an electrolyte having a predetermined particle size in a solid state as a oxygen scavenger. Examples of the method include the intermediate, and among them, the oxygen scavenger intermediate can be made to contain the electrolyte uniformly, and the water content can be adjusted at the same time. The method is preferred.

  The electrolytic solution is preferably water or a mixture of water and alcohol obtained by electrolyzing an electrolyte. From the viewpoint of handleability, an electrolytic solution containing only water is preferable, and a mixed solution of water and alcohol is preferable for further improving the self-reactive deoxygenation performance. The mixing ratio of water and alcohol is water / alcohol (mass ratio), preferably 80 to 10% / 20 to 90%, and more preferably 70 to 20% / 30 to 80%.

  As described above, when the oxygen absorber intermediate is impregnated with the electrolyte, the impregnation method can be appropriately selected according to the form of the oxygen absorber intermediate and the water content. In the impregnation method, the electrolytic solution is spray-coated on the oxygen scavenger intermediate, the electrolyte is injected into a part of the oxygen scavenger intermediate with a syringe or the like, and the capillary action of the fibrous material is reduced. Examples include the method of infiltrating the oxygen scavenger intermediate using the method, the method of coating with a brush, the method of immersing in the electrolyte, the gravure coating method, the reverse coating method, the doctor blade method, etc. A spray coating method is preferred because it can distribute the electrolyte uniformly, is simple, and requires relatively little equipment cost. In addition, in the case of products with complicated shapes and layer configurations, from the point that productivity is improved, the flexibility of production is improved by making the final finishing as a separate process, and the facility is simplified, electrolytic A method of injecting the liquid with a syringe or the like is preferable. The method of injecting the electrolytic solution can be performed after the oxygen scavenger intermediate is accommodated in, for example, an oxygen permeable container.

  As described above, after the oxygen scavenger intermediate contains the electrolyte, the moisture content can be adjusted and stabilized as necessary to obtain a scavenger. If necessary, in the case of a trimming or sheet-like form, two or more sheets can be laminated and processed into a predetermined size.

  The surface of the oxygen scavenger and oxygen scavenger complex obtained as described above is preferably coated with a coating layer having oxygen permeability. The coating layer may have oxygen permeability over the entire surface, or may partially have oxygen permeability. The material of the coating layer is not particularly limited as long as it has oxygen permeability. The coating layer can be provided by, for example, laminating a paper, a nonwoven fabric, a multi-porous film, a resin film provided with fine pores, etc. on the surface of the oxygen scavenger. Further, a synthetic resin paint, an emulsion paint, or the like can be provided by impregnating or applying an oxygen scavenger.

  In addition, the oxygen removal property can be arbitrarily controlled by the oxygen permeability and water vapor permeability of the coating layer. An oxygen permeability coefficient or the like is used as one index of oxygen permeability. Further, as one index of water vapor permeability, a water vapor transmission coefficient or the like is used. For example, by selecting a coating layer with a high oxygen transmission coefficient or water vapor transmission coefficient, a deoxygenating agent having high deoxygenation characteristics can be obtained in a short time, and a coating layer with a low oxygen transmission coefficient or water vapor transmission coefficient is selected. By doing so, it is possible to obtain an oxygen scavenger having a mild oxygen scavenging characteristic over a long period of time.

  The obtained oxygen scavenger and oxygen scavenger complex are provided in a non-oxygen permeable, non-water permeable packaging bag or the like in order to avoid contact with oxygen before use.

  As described above, the oxygen scavenger and oxygen scavenger complex of this embodiment can provide high oxygen scavenging performance in a quick time. In addition, it has high strength, is not easily torn when it is thinned, and has flexibility, so it is excellent in workability and productivity. Further, since the amount of water that can be held can be set widely, it can be applied to articles having a wide range of water activity. In addition, the oxygen absorption rate can be increased by increasing the content of oxidizable metals and adjusting the amount and concentration of the electrolyte solution, so that the oil-impregnating properties include oil-containing foods such as french fries and fried chicken. It is possible to prevent deterioration of the quality of the article due to oxidative degradation of the oil of the article.

Further, as described above, since the raw material composition does not contain an electrolyte serving as an oxidation aid, the oxidizable metal in the raw material composition is reduced by reducing the ion concentration in the suspension. The dispersibility of is improved. Then, by substantially bringing the oxidizable metal and the fibrous material into contact with each other during the preparation of the raw material composition, the oxidizable metal is uniformly fixed on the surface of the fibrous material, and the resulting oxygen scavenger is removed. Oxygen characteristics are improved.
For example, in a suspension in which an electrolyte serving as an oxidation aid is blended, the salt concentration in the system increases, so that the components such as the oxidizable metal and the water retention agent and the electrical interface at the interface of the fibrous material can be obtained. Since the double layer is compressed, the contact between the component and the fibrous material is significantly inhibited, and it becomes difficult to fix the component on the surface of the fibrous material, the wall thickness is thin, and a large amount of the component is filled. It becomes difficult to form the sheet. Further, in a system having a high salt concentration as described above, fixing with a flocculant becomes very difficult for the same reason, and the oxygen scavenging property of the oxygen scavenger obtained is extremely inferior. In addition, it may react with oxygen in water to cause oxidation, which may cause a reduction in deoxygenation performance. Furthermore, the papermaking body tends to react with oxygen in the air, has poor long-term storage stability, and may easily rust a molding machine such as a papermaking machine or a processing machine.

  Furthermore, in order to dry-mold the oxygen scavenger intermediate that does not contain the electrolyte in advance, the strength of the oxygen scavenger intermediate can be maintained, secondary processing is facilitated, and rusting of the cutting blade is generated. Wear can be suppressed. In addition, in the impregnation of the electrolyte, the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger can be easily controlled, and the reaction can be performed on the same surface by pattern impregnation in a certain arbitrary shape. It is possible to divide it into a portion that does not and a portion that does not, and it is possible to suppress oxidation of the oxidizable metal during the manufacturing process as much as possible, and to obtain a deoxygenated molded article having good deoxidation characteristics.

  In addition, according to the oxygen scavenger complex of the present embodiment, various functions of the functional layer can be imparted to the oxygen scavenger exhibiting the above effects.

  The present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit of the present invention.

  In the method for producing the oxygen scavenger complex described above, the electrolyte is included after providing the functional layer on the surface of the oxygen scavenger intermediate. However, the production order is not limited to this, and the oxygen scavenger intermediate The functional layer may be provided after producing an oxygen scavenger by adding an electrolyte to the body. Further, as described above, a functional layer can be provided on the surface and inside of the oxygen scavenger by impregnating the resin composition. For example, after impregnating an oxygen scavenger with an aqueous solution of polyvinyl alcohol, it is dried by heating to a moisture content that requires the oxygen scavenger and crosslinking polyvinyl alcohol, thereby preventing the iron powder contained in the oxygen scavenger from falling off. It can also be given.

  It is preferable that the oxygen scavenger and oxygen scavenger complex of the present invention is formed into a predetermined shape by cutting or the like, and is housed in a container together with a stored material. A container such as a bag or a pouch can be formed from the agent or the oxygen scavenger complex, or a container having a deoxidation function can be formed by press molding to form a desired three-dimensional shape. Also, it can be used by being bonded to a base sheet of a container and formed into a paperboard container or pouch, or in a form other than a sheet shape such as a hollow shape such as a cylindrical shape or a bottle shape or a container shape such as a carton or a tray shape. By making the oxygen scavenger intermediate, it is possible to manufacture a container having a deoxygenating function having a form adapted to these containers.

  In addition, the oxygen scavenger or oxygen scavenger complex of the present invention can be processed into a spherical shape, a noodle shape, a fiber shape or the like by using extrusion molding, pressure molding, tableting molding or the like after production.

  The oxygen scavenger and oxygen scavenger complex of the present invention are applied to food freshness maintenance, anti-oxidation of medical equipment, anti-corrosion of metal, bedding, clothes, anti-fungus for art, etc. be able to.

Hereinafter, the present invention will be described more specifically with reference to examples.
Oxygen scavengers were prepared as in Examples 1 and 2 and Comparative Examples 1 and 2 below, and their deoxygenation performance was examined. Table 1 shows the composition ratio and basis weight of the oxygen scavenger, Table 2 shows the blending ratio of the solid content in the raw material composition and the papermaking yield, and Table 3 shows the effective reaction rate of iron powder in the oxygen scavenger and VSM. The amount of effective iron powder contributing to oxygen absorption and the composition ratio of solid content determined from TG are shown.

[Example 1]
<Combination of raw material composition>
Fibrous material: Pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, trade name “Mackenzie”, CSF 150 ml) 15% by mass
Oxidizable metal: Iron powder (made by Dowa Iron Mining Co., Ltd., trade name “RKH”) 75% by mass
Water retention agent: Activated carbon (manufactured by Nippon Enviro Chemical Co., Ltd., trade name “Carborafyn”) 10% by mass
Flocculant: 1.0 part by mass of the following cationic flocculant and 0.2 part by mass of the following anionic flocculant with respect to 100 parts by mass of the raw material composition Cationic flocculant: polyamide epichlorohydrin resin (Starlight PMC (stock) ), Product name "WS4020")
Anionic flocculant: Sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, degree of etherification 1.45, viscosity 2500 to 3500 mPa · s)
Water: Industrial water, added until the solid content is 1.25% by mass

<Raw material preparation conditions>
Assuming a papermaking process using an actual machine, the slurry was stirred according to JIS P8209 using a JIS pulper and stopped at a support scale of 1000.

<Making conditions>
Using the raw material composition of the above blend, dilute to 0.11% by mass, and make paper using a square sheet machine (manufactured by Kumagaya Riki Kogyo Co., Ltd.) having a width of 250 × 250 mm in accordance with JIS P8209. A wet sheet-like papermaking product was prepared.

<Drying conditions>
Using a KRK rotary dryer (manufactured by Kumagaya Riki Kogyo Co., Ltd.), drying was performed so that the water content was 1% by mass or less, to obtain a sheet-shaped oxygen scavenger intermediate.

<Electrolytic solution addition conditions>
55 parts by mass of the following electrolyte was added to 100 parts by mass of the oxygen scavenger intermediate to obtain a desired oxygen scavenger. As shown in Table 1, the moisture content of the obtained oxygen scavenger was 35.1% by mass.

<Electrolyte>
Electrolyte: Purified salt (NaCl)
Water: Industrial water Electrolyte concentration: 1% by mass

[Example 2]
An oxygen scavenger was prepared in the same manner as in Example 1 except that the raw material preparation conditions were adjusted by hand stirring for about 15 seconds without using JIS pulper.

[Comparative Example 1]
<Combination of raw material composition>
Fibrous material: Pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, trade name “Mackenzie”, CSF 150 ml) 17% by mass
Oxidizable metal: Iron powder (manufactured by Dowa Iron Mining Co., Ltd., trade name “RKH”) 83 mass%
Flocculant: 1.0 part by mass of the following cationic flocculant and 0.2 part by mass of the following anionic flocculant with respect to 100 parts by mass of the raw material composition Cationic flocculant: polyamide epichlorohydrin resin (Starlight PMC (stock) ), Product name "WS4020")
Anionic flocculant: Sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, degree of etherification 1.45, viscosity 2500 to 3500 mPa · s)
Water: Industrial water, added until the solid concentration is 1.25% by mass. Salt: 1.0 part by mass of sodium chloride with respect to 100 parts by mass of the slurry.

<Raw material preparation conditions>
Assuming a papermaking process using an actual machine, the slurry was stirred according to JIS P8209 using a JIS pulper and stopped at a support scale of 1000.

<Making conditions>
Using the raw material composition of the above blend, diluted to 0.11% by mass, and after paper making using a square sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.) having a width of 250 × 250 mm according to JIS P8209, A wet sheet-like papermaking product was produced by pressing. Moreover, 1 mass% NaCl aqueous solution was used for the dilution water. As shown in Table 1, the moisture content of the obtained oxygen scavenger was 34.7% by mass.

[Comparative Example 2]
Mitsubishi Gas Chemical Co., Ltd. product name Ageless SA (self-reactive type, fast-acting type) was used.

<Form of oxygen scavenger>
As shown in Table 1, the obtained oxygen scavenger had a thickness of 0.2 to 0.4 mm and a basis weight of 194 to 302 g / m ² . In addition, thickness measured 5 points | pieces or more of oxygen absorber according to JISP8118, the average value was computed as thickness, and basic weight measured the oxygen absorber weight of the area of at least 100 cm < ² > or more, Calculated by dividing by area.

[Measurement of oxygen scavenging performance of oxygen scavenger]
10 g of the oxygen scavenger of Example 1 and Comparative Examples 1 and 2 was placed in a desiccator having an air volume of 5.5 liters without being covered with an oxygen-permeable coating layer, and the oxygen concentration in the desiccator was measured. The deoxygenation performance was investigated. The oxygen concentration was measured using an oxygen monitor OM-25MS01 manufactured by Taiho Electric Co., Ltd. The results are shown in FIG.

[Measurement of amount of iron powder effective for deoxygenation in oxygen absorber by VSM]
Using VSM-P7-15 manufactured by Toei Kogyo Co., Ltd. as the VSM, the amount of iron powder effective for deoxygenation in the oxygen scavenger was measured. The results are shown in Table 3.

[Measurement of composition ratio of oxygen scavenger by TG]
The composition ratio of the oxygen scavenger was measured using a high-temperature differential thermal thermogravimetric simultaneous measurement device TG / DTA-6300 and an autosampler unit AST-2 manufactured by Seiko Instruments Inc. as TG. Moreover, the sample container used the product made from Pt (phi) 5mm and height 5mm so that it might endure the high temperature of 1000 degreeC. The results are shown in Table 3.

  As shown in FIG. 1 and Tables 2 and 3, the oxygen scavenger obtained in Example 1 does not contain an electrolyte as a reaction aid at the paper making stage, so that the oxidation reaction does not proceed and iron powder It was revealed that the effective reaction rate of was high. Therefore, the critical oxygen concentration was 0% in Example 1, whereas it was saturated at 6% in Comparative Example 1. Furthermore, since Example 1 has a water retention agent, it was found that it had the ability to absorb oxygen in a quicker time than Comparative Example 1. Also, in the papermaking yield, Example 1 does not contain an electrolyte as a reaction aid at the papermaking stage, so the papermaking yield is high, and it is industrially stable, high quality, and low cost. is there. Furthermore, in comparison with a commercially available powder type oxygen scavenger containing the water retention agent of Comparative Example 2, it was found that high oxygen scavenging performance was obtained in a quick time.

It is a figure which shows the deoxidation performance of the deoxidizer of Example 1 and Comparative Examples 1 and 2 of this invention.

Claims (10)

An oxygen scavenger comprising an oxygen scavenger intermediate formed by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material, and an electrolyte as an oxidation reaction aid,
An oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass.   The oxygen scavenger according to claim 1, wherein the fibrous material has a CSF of 600 ml or less.   The oxygen scavenger according to claim 1 or 2, wherein an effective reaction rate of the oxidizable metal is 75% or more.   The oxygen absorber intermediate used in the oxygen absorber according to any one of claims 1 to 3, wherein the oxygen absorber is formed by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. Intermediates.   The oxygen absorber complex in which the functional layer is provided in the oxygen absorber in any one of Claims 1-3.   The oxygen scavenger complex according to claim 5, wherein the functional layer is laminated via an adhesive layer.   The oxygen scavenger according to claim 5 or 6, wherein the functional layer has a function of preventing solid components from falling off, concealing, deodorizing, anti-magnetic, moisture barrier or oil barrier, or a combination of these functions. Complex.   2. The method for producing an oxygen scavenger according to claim 1, wherein the oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material serves as an oxidation reaction aid. A method for producing an oxygen scavenger that contains water.   The method for producing an oxygen scavenger complex according to claim 5, wherein the functional layer is applied to an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. A method for producing an oxygen scavenger complex containing an electrolyte that becomes an oxidation reaction aid after being provided.   6. The method for producing an oxygen scavenger complex according to claim 5, wherein an oxidation reaction aid is added to an oxygen scavenger intermediate formed by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material. A method for producing an oxygen scavenger complex in which an oxygen scavenger is produced by including an electrolyte to be used, and then the functional layer is provided on the oxygen scavenger.

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