WO2007049677A1

WO2007049677A1 - Oxygen scavenger, oxygen scavenger intermediate, oxygen scavenger composite, and process for producing the same

Info

Publication number: WO2007049677A1
Application number: PCT/JP2006/321340
Authority: WO
Inventors: Yoshiaki Kumamoto; Masataka Ishikawa; Taijun Yoshida
Original assignee: Kao Corporation
Priority date: 2005-10-27
Filing date: 2006-10-26
Publication date: 2007-05-03

Abstract

An oxygen scavenger which comprises: an oxygen scavenger intermediate obtained by drying a sheet comprising an oxidizable metal and a fibrous material and formed by a papermaking method; and an electrolyte, as an oxidation aid, incorporated in the intermediate. The oxygen scavenger contains 0.1-10 mass% the electrolyte and has a water content of 0.1-5 mass%, excluding 5 mass%. The fibrous material preferably has a CSF of 600 mL or less. The oxidizable metal preferably is one at least 75% of which effectively undergoes a reaction.

Description

Specification

Oxygen absorber, oxygen absorber intermediate, oxygen absorber complex and method for producing the same

TECHNICAL FIELD [0001] 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.

Background art

[0002] As a conventional technique related to an oxygen scavenger using an oxidation reaction between oxygen in the air and an oxidizable metal powder, for example, a technique described in Patent Document 1 below is known.

[0003] In this technique, a mixture of a fibrous substance, iron powder, water and an electrolyte is formed into a sheet by papermaking, and its Gurley air permeability is set to 50000 seconds or less ZlOOml.

[0004] By the way, the oxygen scavenger produced by this technique is made by making a sheet of paper made from 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 iron powder occurs during the preparation of the slurry, during supply, and during sheet forming, and the performance of the resulting oxygen scavenger decreases. In addition, particularly during the supply of the slurry, the oxidation reaction of the iron powder proceeds with the passage of time, and the deoxidation performance of the resulting oxygen scavenger decreases with the passage of time. there were. Therefore, a large amount of oxygen scavenger was necessary to guarantee the minimum oxygen scavenging performance required for the quality assurance of the oxygen scavenger. Furthermore, there was a problem that wrinkles were likely to occur in the manufacturing machine. Further, the obtained sheet also has a problem in storage stability because of 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.

Patent Document 1: Japanese Patent Application Laid-Open No. 62-234544

Disclosure of the invention

[0006] Therefore, the first object of the present invention is to provide an oxygen scavenger, a scavenger intermediate, and a scavenger capable of efficiently oxidizing an oxidizable metal and obtaining high oxygen scavenging performance in a smaller amount. It is to provide a composite and a method for producing the same. [0007] In addition, a second 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.

[0008] The present invention is an oxygen scavenger comprising an oxygen scavenger intermediate obtained by drying a paper product containing an oxidizable metal 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 an electrolyte and having a water content of 0.1 to less than 5% by mass. Hereinafter, this invention is also referred to as a first invention.

[0009] Further, the present invention provides an oxygen scavenger intermediate used for the oxygen scavenger of the first invention, wherein the oxygen scavenger intermediate is formed by drying a paper product containing an oxidizable metal and a fibrous material. It provides the body.

[0010] The present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the first invention.

[0011] Further, the present invention is the method for producing an oxygen scavenger according to the first invention, wherein an oxygen scavenger intermediate obtained by drying a paper product containing an oxidizable metal 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.

[0012] Further, the present invention provides a method for producing the oxygen scavenger complex of the present invention, wherein the oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal and a fibrous material is used as the oxygen scavenger intermediate. After the functional layer is provided, a method for producing an oxygen scavenger complex containing an electrolyte as an oxidation reaction aid is provided.

[0013] Further, the present invention provides a method for producing the oxygen scavenger complex of the present invention, wherein an oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal and a fibrous material is oxidized. The present invention provides a method for producing an oxygen scavenger complex in which an oxygen scavenger is produced by including an electrolyte as a reaction aid, and then the functional layer is provided on the oxygen scavenger.

[0014] The present invention relates to an oxygen scavenger comprising an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material, and an electrolyte serving 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 0.1 to less than 5% by mass. Hereinafter, this invention is also referred to as a second invention.

[0015] Further, the present invention is an oxygen scavenger intermediate used for the oxygen scavenger of the second invention, The present invention provides an oxygen scavenger intermediate obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material.

[0016] The present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the second invention.

[0017] The present invention is also the method for producing an oxygen scavenger according to the second invention, wherein the oxygen scavenger intermediate is obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. In addition, the present invention provides a method for producing an oxygen scavenger containing an electrolyte as an oxidation reaction aid.

[0018] The present invention also provides a method for producing the oxygen scavenger complex of the present invention, wherein the oxygen scavenger intermediate formed by drying a papermaking 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 electrolyte as an oxidation reaction aid is contained after the functional layer is provided on the body.

[0019] Further, the present invention is a method for producing the oxygen scavenger complex of the present invention, wherein the 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 adding an electrolyte as an oxidation reaction aid to the body, and then the functional layer is provided on the oxygen scavenger.

Brief Description of Drawings

[0020] FIG. 1 is a diagram showing the oxygen scavenging performance of oxygen scavengers of Example 11 of the present invention and Comparative Example 11.

[0021] FIG. 2 is a diagram showing the oxygen scavenging performance of oxygen scavengers of Example 2-1 and Comparative Examples 2-1 and 2-2 of the present invention.

Detailed Description of the Invention

Hereinafter, the present invention will be described based on its preferred embodiments with reference to the drawings. In the following, first, the oxygen scavenger of the first invention, the oxygen scavenger complex using the oxygen scavenger, and the production method thereof will be described, and then the oxygen scavenger of the second invention and the use thereof. The oxygen scavenger complex and the manufacturing method thereof will be described.

[0023] The oxygen scavenger of the first invention is an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal and a fibrous material, and an electrolyte as an oxidation reaction aid. is there. The oxygen scavenger in this embodiment exhibits oxygen scavenging performance with moisture in the external environment of the oxygen scavenger! It is a minute-dependent oxygen scavenger.

[0024] In the oxygen scavenger of this embodiment, the electrolyte is 0.1 to 10% by mass, preferably 0.2 to 8% by mass, more preferably 0.3 to 8% by mass, and more preferably 0.3. Up to 6% by weight, even more preferably 0.5 to 5% by weight, and a moisture content of 0.1 to less than 5% by weight (0.1 to 5% by weight), preferably 0.3 -4% by mass, more preferably 0.5-3% by mass.

When the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger are within such ranges, the external force can be taken in enough to maintain the oxidation reaction, and the oxidation reaction proceeds sufficiently. . Further, since the air permeability of the oxygen scavenger is not impaired, high oxygen scavenging performance can be obtained in a quick time. In addition, sufficient shape retention and mechanical strength can be obtained.

[0025] As the electrolyte, an electrolyte usually used for this type of oxygen scavenger can be used without any particular limitation. Examples of the electrolyte include alkali metal, alkaline earth metal, or heavy metal sulfates, carbonates, chlorides, hydroxides, and the like. Among these, the points of excellent conductivity, chemical stability, and production cost are salty sodium, salty potassium, salty calcium, magnesium chloride, ferrous chloride, ferric chloride, etc. Of these, various salts are preferably used. These electrolytes can be used alone or in combination of two or more.

[0026] For the oxidizable metal, any conventional oxidizable metal that is usually used for this type of oxygen scavenger can be used without any particular limitation. As the form of the oxidizable metal, it is preferable to use a powder or fibrous form from the viewpoints of handleability, moldability, and the like.

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, handleability, safety, and manufacturing cost are included. The point power of 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 a powder, or dynamic light scattering because the fixability to the fibrous material and the reaction control described later are good. The average particle size measured by the laser diffraction method, etc.) is preferably 0.1 to 300 / ζ πι, and the preferred particle size is 0.1 to 150 m and 50% by mass or more. It is more preferable to use what is contained.

Moreover, as an oxidizable metal having a fibrous form, steel fiber, aluminum fiber, A magnesium fiber etc. are mentioned. Among these, steel fibers, aluminum fibers, and the like are preferably used from the viewpoints of handleability, safety, and manufacturing cost. An oxidizable metal having a fibrous form has a fiber length of 0.1 to 50 mm and a thickness of 1 to 1000 in terms of formability, mechanical strength of the oxygen scavenger obtained, surface smoothness, and deoxidation performance. It is preferable to use m.

[0027] The oxidizable metal in the oxygen scavenger preferably has an effective reaction rate of 75% or more, more preferably 85% or more. If the effective reaction rate is within such a range, the oxidation reaction of the oxidizable metal is suppressed during the slurry preparation and papermaking during the production of the oxygen scavenger, so that the oxygen scavenging ability required for packaging specifications can be obtained. The oxygen scavenger can be made smaller and lighter, and 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. This is the value obtained by Equation 3 below divided by the ratio. The upper limit of the effective reaction rate is 100%.

[0028] Mass of oxidizable metal effective for deoxidation Mass of Z deoxidizer = Α ·· 'Equation 1

Mass of oxidizable metal at raw material stage 質量 Mass of oxygen scavenger = Β · 'Equation 2 Effective reaction rate of oxygen scavenger (%) = (Α / Β) X 100 · · · Equation 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 and evaporating the water, but the mass in a state containing water may be used as it is. Yes. However, the oxygen content of the oxygen scavenger in Equation 1 and Equation 2 must be matched.

In addition, the above packaging specification means that the thickness and weight of a product manufactured by filling a bag such as a bouch 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.

[0029] The following is an example of an oxygen scavenger using iron powder as an oxidizable metal and wood pulp as a fibrous material. Thermogravimetry (abbreviated as TG) and Vibrating Sample Magnetometer (Vibrating Sample Magnetometer, The method for obtaining the effective reaction rate using the abbreviated name VSM) is explained.

[0030] The mass ratio of the iron powder at the raw material stage can be determined by thermogravimetry. When a sample was prepared from the oxygen scavenger, and this sample was placed in a sample container and gradually raised from room temperature in a nitrogen atmosphere, the water contained in the oxygen scavenger evaporated near 100 ° C, Mass rapidly decreases around 350 ° C. This mass loss is the amount of cellulose degradation contained in the wood pulp. When the temperature is further raised and air is introduced at a temperature of 550 ° C and heated to 1000 ° C, the wood pulp burns, 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 amount of cellulose degradation and the ash content derived from wood pulp can be determined. Therefore, the mass of iron oxide is obtained by subtracting the ash derived from wood pulp calculated from the amount of cellulose degradation from the sample container residue.

[0031] Based on the mass of the iron oxide, the mass of the iron powder contained in the sample can be determined. Mass strength of acid iron iron The correction coefficient for obtaining the mass of iron powder of raw materials is generally obtained from the iron oxidation reaction equation, but the iron powder supplied from raw material manufacturers is usually pure. Since it is not 100% iron, the correction factor is obtained experimentally. Put a sample of iron powder in a sample container, dry it completely in a nitrogen atmosphere up to 600 ° C, heat it up to 1000 ° C with air and generate iron oxide. The relationship force correction coefficient between the generated mass of iron oxide and the mass of raw iron powder can be obtained. Using the correction factor obtained in this experiment, the mass force of iron oxide can also determine the mass of iron powder, and the mass ratio of iron powder at the raw material stage (Formula 5) is obtained from the ratio to the mass of the sample. be able to.

[0032] Next, a method for obtaining the mass of iron powder effective for deoxygenation in a deoxidant using a vibrating sample magnetometer will be described. When an external magnetic field is applied using a vibrating sample magnetometer with iron powder as a sample, the iron powder is magnetized. The amount of magnetism of iron powder saturates as the external magnetic field increases, and this saturation magnetization 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 the iron powder is changed to iron oxide and deoxidation ability is lost, the saturation magnetic flux is almost zero. Therefore, by measuring the saturation magnetic flux of the oxygen scavenger sample, the mass of iron powder effective for oxygen scavenging contained in the oxygen scavenger sample can be determined. Dividing the mass of iron powder effective for deoxygenation by the mass of the sample yields the ratio of iron powder effective for oxygen absorption in the oxygen scavenger (Equation 4). The effective reaction rate of the oxygen scavenger sample is the ratio of iron powder effective for oxygen scavenging in the oxygen scavenger represented by the following formula 4. This is the value obtained by the following formula 6 divided by the ratio of iron powder at the raw material stage represented by the following formula 5.

[0033] Mass of iron powder effective for deoxygenation Sample mass of Z oxygen scavenger = C '·' Equation 4

Mass of iron powder at raw material stage Sample mass of Z oxygen scavenger = D '·' Equation 5

Effective reaction rate of oxygen scavenger (%) = (C / D) X 100 ··· Equation 6

[0034] The amount of the oxidizable metal in the oxygen scavenger intermediate is preferably 10 to 98% by mass, more preferably 30 to 90% by mass. If the amount of the oxidizable metal is within such a range, a desired deoxygenation performance can be obtained. In addition, it is possible to suppress an increase in the fibrous materials and adhesive components (coagulant, etc.), which will be described later, constituting the oxygen scavenger intermediate. In addition, 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, the air permeability is not impaired. A high deoxygenation performance can be obtained because the reaction easily occurs. Further, the acid-oxidized metal does not expand and condense due to the acid-acid reaction, and does not become too hard. In addition, it is possible to suppress the dropping of the acid-bearing metal. Further, since the fibrous material and the adhesive component described later 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. In addition, for example, in the case of iron, it can be quantified by a sample type magnetic field measurement test using the vibrating sample type magnetometer by utilizing the property that magnetic field is generated when an external magnetic field is applied.

[0035] Examples of the fibrous material include plant fibers (cotton, cabbage, wood pulp, non-wood pulp, peanut protein fiber, corn protein fiber, soybean protein fiber, mannan fiber, rubber, Fiber, hemp, Manila hemp, sisal hemp, New Zealand hemp, Rafu hemp, eggplant, rush, straw, etc.), animal fiber (wool, goat hair, mohair, cashmere, alkanoku, angora, 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, Salted rubber, hydrochloric acid rubber, etc.), metal fiber, carbon fiber, inorganic fiber (for example, glass fiber) Fiber, ceramic fiber, etc.). Polyolefins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and polypropylene, polyester, polyvinylidene chloride, starch, polybulal alcohol or polyacetic acid bule, or a single fiber such as a copolymer or modified body thereof, Alternatively, a core-sheath composite fiber having these rosin components in the sheath can be used. Of these, polyolefins and modified polyesters are preferably used because they can easily form a three-dimensional network structure by fusing fibers with high fiber-to-fiber bonding strength and have a melting point lower than the ignition point of pulp fibers. Further, a synthetic fiber such as a polyolefin having a branch is also preferably used because of its good fixability with an oxidizable metal. 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. Of these, wood pulp and cotton are preferred from the standpoints of fixability of the oxidizable metal, the flexibility of the resulting paper product, the presence of voids, oxygen permeability, and manufacturing costs. Used.

The fibrous material preferably has a Canadian Standard Freeness (CSF) force 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 component such as the oxidizable metal is good, and the oxygen scavenger obtained by maintaining a predetermined blending amount has excellent oxygen scavenging performance. . Also, 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, the component can be removed, the component and the fibrous material can be entangled, and the bond strength derived from hydrogen bonding can be obtained. 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 case of ordinary pulp fiber-only paper, when the component ratio other than the fibrous material is low, if the CSF is less than 100 ml, the drainage is very poor and difficult to dewater. As a result, it becomes difficult to obtain a paper product having a uniform thickness, and a molding failure such as a tearing of the prestar during drying occurs. 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 CSF is less than 100 ml. In addition, the lower the CSF, the more fibrils, the better the fixability between the fibrous material and the components other than the fibrous material, and the higher the CSF. V, a strong 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. It is an index that represents the degree of drainage of a fibrous material that can be obtained by measuring by the method shown in CSFi and IS P8 121 (pulp freeness test method) and shows a value of 0 or more.

[0037] Preferably, the fibrous material has a negative (negative) surface charge. As the surface charge becomes strongly negative, the adherence of powder components such as oxidizable metals to the fibrous material becomes better, the powder retainability becomes higher, and the resulting oxygen scavenger is deoxygenated. Performance is further enhanced. In addition, a large amount of powder components such as oxidizable metals are prevented from being mixed in the wastewater in the wet papermaking process, and there is no adverse effect on productivity and environmental conservation. In particular, the further increase point the yield of oxygen scavenger intermediates obtained, the fibrous material, the amount of charge 2. 5 X 10- ⁶ is preferably instrument charge amount that eqZg or less is 4. OX 10 " ⁶ eq Zg or less is more preferred. Here, the amount of charge of the fibrous material is measured by colloid titration. Also, at the zeta potential, which is the apparent potential at the shear surface between the charged particle interface and the solution. This is also the same, and this is measured by streaming potential method, electrophoresis method or the like.

[0038] It is preferable to use the fibrous material having an average fiber length of 0.1 to 50 mm.

It is more preferable to use a 2-20 mm one. 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 hold the components such as the oxidizable metal by the fibers is obtained, so that dropping of the components can be suppressed. .

[0039] The amount of the fibrous material in the oxygen scavenger intermediate is preferably 2 to 50% by mass, more preferably 5 to 40% by mass. When the blending amount is within such a range, an effect of preventing the oxidizable metal from falling off can be obtained. Also, the oxygen scavenger intermediate is flexible. Further, the ratio of components such as the oxidizable metal in the obtained oxygen scavenger intermediate is not lowered, and a desired oxygen scavenging performance can be obtained. [0040] Here, the composition ratio of each component can determine the content of the fibrous material or the content of the oxidizable substance by, for example, thermogravimetry.

[0041] The oxygen scavenger intermediate contains 50 mass% or more of components other than the fibrous material, preferably 70 mass% or more, more preferably 80 mass% or more. More preferably, it is. When the component other than the fibrous material is 50% by mass or more, the deoxidation 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 additivity of the oxygen scavenger intermediate.

[0042] 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 of sizing agent, colorant, paper strength enhancer, yield improver, filler, thickener, pH control agent, bulking agent, etc. Additives to be used can be added without particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.

[0043] If coloring is necessary for the appearance of the product, colored powders such as titanium oxide, calcium carbonate, and alumina white may be added. Furthermore, in order to promote oxidation reaction and improve flexibility, powder such as florite, isolite, talc, etc., and ceramic fibers and synthetic fibers can be added.

[0044] When the oxygen scavenger intermediate is formed in a sheet form, the thickness of one sheet is 0.

08-1. 2 mm is preferred 0.1 to 0.6 mm is more preferred. When the thickness is 0.08 mm or more, the oxygen removal performance, mechanical strength, and fixability of components such as the oxidizable metal are good, and a stable and uniform thickness and composition distribution can be obtained. In addition, there is no hindrance to productivity and workability, which is unlikely to cause sheet breakage due to pinholes. When the thickness is within 1.2 mm, a decrease in the bending strength of the oxygen scavenger intermediate can be suppressed. Further, a soft sheet that hardly causes brittle fracture can be obtained. In terms of productivity, the paper layer formation time and drying time can be shortened, resulting in excellent operability. In addition, deoxidation performance is also good. Moreover, since it is hard to be cracked or broken, it is excellent in workability.

[0045] wherein when the oxygen scavenger intermediate was formed into a sheet form, the basis weight of one that is more preferably 1 0～1000GZm is preferred instrument 50～600GZm ² from ² . The When the basis weight is lOgZm ² or more, a particularly stable sheet can be formed, for example, in the case where a material having a large specific gravity is used among the oxidizable metals. When the basis weight is within lOOOgZm 2, it is light and feels good. In addition, productivity and operability are also improved.

[0046] When the oxygen scavenger intermediate is formed into a sheet-like form, the breaking length of one sheet is preferably 100 to 4000 m, 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 400 Om or less, the fibrous material and adhesive component forming the sheet do not increase excessively, and the material is flexible and excellent in oxygen removal performance. Here, the tear length is determined by cutting a test piece of length 150mm x width 15mm from the sheet, then mounting the test piece on a tensile tester with a chuck interval of 100mm according to JIS P8113, and a tensile test at a pulling speed of 20mmZmin. The value is calculated by the following formula.

Breaking length [m] = (l / 9.8) X (Tensile strength [N / m]) X 10 ⁶ / (Test piece basis weight [g / m ² ])

[0047] The oxygen scavenger intermediate takes into account the fact that the oxygen scavenging reaction proceeds favorably, the ability is improved, and the electrolyte can be more uniformly contained when the electrolyte is added. Then, the air permeability per basis weight lOOgZm ² is 0.1 to: L000 seconds Z (6.4 cm ² '300ml) S force, preferably 0.1 to 500 seconds Z (6.4 cm ² ' 300ml) ) Is more preferable.

[0048] The thickness of the oxygen scavenger is appropriately set according to the application 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). In consideration of processability and packaging specifications, 0.0 to 20mm is preferred. 0.1 to: LOmm is more preferred.

[0049] 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, the oxygen scavenger of the present invention is provided with a functional layer.

[0050] The functional layer has a function of preventing solid components of the oxygen scavenger from falling off, concealing, deodorizing, resistance to magnetism, moisture noria or oil barrier, or a combination of these functions. [0051] The functional layer having a function of preventing the solid component of the oxygen scavenger from falling out has air permeability for expressing the oxygen scavenging performance of the oxygen scavenger, but the solid component contained in the oxygen scavenger is Prevents contamination from falling off. The functional layer having such a function is provided by applying a resin composition to paper, a nonwoven fabric, a porous resin film, or a functional layer substrate in combination of these, or the oxygen scavenger and drying. Can do. The paper is preferably a paper pulp, synthetic pulp or a mixture thereof produced by a wet or dry manufacturing method. As the non-woven fabric, those manufactured by a manufacturing method such as wet, dry, and spunbond can be used. The material of the non-woven fabric is preferably a fiber of thermoplastic resin such as polyolefin such as polyethylene and polypropylene, polyamide such as nylon, polyester such as polyethylene terephthalate, and polyfluorinated polyolefin such as polytetrafluoroethylene. As the porous resin film, as in the case of the non-woven fabric, heat such as polyolefin such as polyethylene and polypropylene, polyamide such as nylon, polyester such as polyethylene terephthalate, and polyfluorinated polyolefin such as polytetrafluoroethylene, etc. Plastic resin is preferred. For the porous resin film, a film containing an inorganic or organic filler that is insoluble or hardly soluble in water in the thermoplastic resin to form a large number of holes is used. As the filler, silica, calcium carbonate, alumina, titanium white sulfate barium, 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: LOO m, particularly preferably 0.1 to 50 m. Examples of the resin composition include natural resin compositions such as starch, carboxymethyl cellulose and guar gum, polybulal alcohol, modified cellulose, chlorinated, acrylic, silicone, silicone acrylic, Examples thereof include a single resin or a copolymer of a synthetic resin such as a polyamide-based, a polyester-based, a polyolefin-based, a phenol-based, an ethylene butyl acetate copolymer, or a polybutagen-based resin, or a mixture thereof.

[0052] 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 the external force cannot be seen. Is. 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, or a face containing a white or colored pigment. It can be provided by a layer coated with a resin-containing emulsion and dried. 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. A non-pigmented non-pigmented layer can be provided on the outer surface side of the pigment-containing layer to improve impact resistance, strength, heat sealability and tackiness. For these paper, non-woven 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 the function of preventing the solid component from falling off can be appropriately selected.

[0053] The functional layer having a deodorizing function of the oxygen scavenger has air permeability for expressing the oxygen scavenging performance, but deodorizes by adsorbing or decomposing odor components emitted from the oxygen scavenger. . The functional layer having such a function can be provided by a paper, a nonwoven fabric, a porous resin film or a combination of these containing a deodorant, or a coating layer of a resin emulsion. 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 the 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, and titanium oxide. The activated carbon is preferably dry charcoal with a moisture content of 10% or less (CFIS K1470). Those subjected to treatment such as acid addition or alkali attachment can also be used. As the aluminosilicate, various natural or synthetic silicates such as synthetic zeolite and natural or synthetic phyllosilicates can be used. Examples of the phyllosilicate include magnesium phyllosilicate, zinc phyllosilicate, bentonite, activated clay, and acid clay. In consideration of dispersibility in the base material, the deodorizer preferably has a particle diameter of 0.01 to: LOO / zm, particularly 0.1 to 50 m. Also, a deodorant that exhibits deodorization by adsorption preferably has a specific surface area of 50 to 5000 m ² / g, particularly 100 to 4000 m ² Zg.

[0054] The functional layer having a magnetic resistance function of the oxygen scavenger is a magnetic material such as silicon or alumina, or a powder in which powder is dispersed in a resin, and the powder is supported on the fiber. Etc. are preferably used. [0055] The functional layer having a moisture barrier function and an oil content barrier function of the oxygen scavenger is a food contamination caused by the oxygen scavenger that can occur when the oxygen scavenger is used to store foods with a high water content such as retort food. This is to prevent contamination of oxygen scavengers by water from food. 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, and polyfluorinated polyolefins such as polytetrafluoroethylene are preferably used. Also, the thermoplastic resin contains 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 sulfate, zeolite, diatomaceous earth, activated clay, acid clay, talc, bentonite, iron oxide and the like are preferably used. 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 produced by a wet or dry manufacturing method.

[0056] 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-: LOOOO / zm is preferable, and 10-: L00 is more preferable.

[0057] The functional layer may be provided on the entire surface of the oxygen scavenger or on the entire surface. As will be 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 described later.

[0058] The material and form of the adhesive layer are not particularly limited as long as they can adhere the oxygen scavenger and the functional layer without adversely affecting the oxygen scavenging performance of the oxygen scavenger. It is preferable. Such an air-permeable adhesive layer is a method in which a pressure-sensitive adhesive or 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. A method of thermally laminating a fiber or porous resin film with a heat-meltable resin material on one or both of the oxygen absorber or functional layer, or a heat-meltable resin with oxygen absorber or function Place them on one or both of the layers to push the fat into a streak Can be provided by a laminating method. As the pressure-sensitive adhesive, a urethane-based or acrylic-based pressure-sensitive adhesive is preferable. The adhesive is preferably a hot melt adhesive or an adhesive for dry lamination. Examples of the resin constituting the heat-meltable resin material include polyolefin resin, polyethylene resin and the like.

[0059] The thickness of the oxygen scavenger complex is appropriately set according to its form. In consideration of processability and packaging specifications, 0.0 to 30 mm is preferable, and 0.5 to 20 mm is more preferable.

[0060] Next, the oxygen scavenger of the first invention and the method for producing the oxygen scavenger complex using the oxygen scavenger will be described based on the preferred embodiment.

First, a raw material composition (slurry) containing the oxidizable metal, the fibrous material, and water is prepared.

[0061] The flocculant is preferably added to the raw material composition.

Examples of the flocculant include inorganic flocculants having metal salt strength, such as sulfate band, polyaluminum chloride aluminum, ferric chloride, polyferric sulfate, ferrous sulfate, etc .; polyacrylamide type, sodium polyacrylate type, Polymer flocculating agent such as polyacrylamide Mannich modified product, poly (meth) acrylic acid aminoalkyl ester type, sodium carboxymethyl cellulose, chitosan type, starch type, polyamide epoxy hydrin type; dimethyldiarylammo -Organic coagulants such as condensates of umchloride or ethyleneimine alkylene dichloride and polyalkylene polyamine, dicyandiamide 'formalin condensate; clay minerals such as montmorillonite and bentonite; silicon dioxide such as colloidal silica or its Hydrate: Magnesium hydrated silicate such as talc Um etc. are mentioned. Among these flocculants, sheet surface properties, texture formation, improved formability, fixability of components such as the oxidizable metal, and on-ion colloidal silica and bentonite from the viewpoint of improving paper strength. And cationic starch, polyacrylamide, and the like are particularly preferably used in combination with a cationic carboxymethylcellulose sodium salt and a cationic polyamide-epoxychlorohydrin cationic and cationic drug. In addition to the above combinations, these flocculants can be used alone or in combination of two or more.

[0062] The amount of the flocculant added is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on the solid content of the raw material composition. In the range where the amount of the additive is such When present, an aggregating effect is obtained, and dropping off of components such as the oxidizable metal during papermaking is suppressed. Further, the raw material composition becomes uniform, and a papermaking product having a uniform thickness and composition can be obtained. In addition, it does not cause sticking, tearing, burning or scorching on the drying means during drying, and it does not adversely affect productivity. In addition, 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 storage stability such as deoxidation characteristics and strength decreases.

[0063] The concentration of the raw material composition is preferably 0.05 to 15% by mass, 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.

[0064] Next, the raw material composition is made into a paper.

The papermaking method for making the papermaking sheet into a sheet-like form is, for example, paper making using a continuous paper-making type circular paper machine, long net paper machine, short net paper machine, twin wire paper machine, etc. And a manual method which is a batch type papermaking method. Furthermore, a papermaking body can also be formed by multi-layer papermaking using the raw material composition and a composition having a composition different from that of the raw material composition. Further, by laminating sheets obtained by papermaking the raw material composition in multiple layers, or by laminating a sheet-like material having a composition force having a composition different from the raw material composition to the sheet, Multi-layer sheets can also be formed. When papermaking is made in a form other than a sheet form, it has been used in the pulp mold method and can be shaped by a wet papermaking method.

[0065] From the viewpoint of maintaining the form after paper making (shape retention) and maintaining mechanical strength, the papermaking product is dehydrated until the moisture content (mass moisture content, the same shall apply hereinafter) becomes 70% or less. It is more preferable to dehydrate until 60% or less. Examples of the dewatering method of the papermaking after papermaking include dehydration by suction, dehydration by blowing pressurized air, and dehydration by pressurization with a pressure roll or pressure plate.

[0066] In the present embodiment, the papermaking containing the oxidizable metal is actively dried to separate moisture, thereby suppressing oxidation of the oxidizable metal during the manufacturing process. An oxygen scavenger intermediate excellent in long-term storage stability can be obtained. Furthermore, in addition to increasing the supporting ability of the oxidizable metal to the fibrous material after drying and suppressing its falling off, it can be expected to improve mechanical strength by adding a hot-melt component and a thermal cross-linking component. Therefore, it is preferable to dry the papermaking body after the papermaking body and before containing the electrolyte. Here, as drying means, heat drying, vacuum drying, freeze drying and the like can be used as appropriate.

[0067] It is preferable that the papermaking product is dried by heat drying in terms 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 as the moisture is dried. For this reason, it does not cause a decrease in the oxygen removal performance of the oxygen absorber. In addition, only the front and back layers of the oxygen scavenger intermediate promotes the oxidation reaction of the oxidizable metal, and the color change to light brown can be suppressed. Moreover, the fall of the deoxidation effect of a deoxidizer can be suppressed. In addition, the structure of the oxygen scavenger intermediate is not destroyed due to the rapid evaporation of moisture inside the oxygen scavenger intermediate.

[0068] The moisture content of the oxygen scavenger intermediate after drying is preferably 20% or less, more preferably 10% or less. When the moisture content is 20% or less, it is excellent in long-term storage stability.For example, when it is formed into a sheet and temporarily stored in a wound roll, it is difficult for moisture to move in the thickness direction of the roll. It is possible to suppress changes in performance and mechanical strength.

[0069] The drying method of the papermaking can be appropriately selected according to the form of the papermaking, the processing method of the papermaking 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. It can also be carried out simultaneously with the above-described dehydration method.

[0070] In the present embodiment, the papermaking body and the oxygen scavenger intermediate are molded, as described above, containing an electrolyte that serves as an oxidation reaction aid in the papermaking body and the oxygen scavenger intermediate. ! / Since it is easy to mold, it can be molded under normal air atmosphere. For this reason, simplify production equipment. Can do. If necessary, creping, slitting, trimming, and processing such as changing the form by processing can be performed. Since the obtained oxygen scavenger intermediate has a high strength, it can be wound into a tool as needed when formed into a sheet form. Further, when the oxygen scavenger intermediate is formed into a sheet-like form, it may be used alone or in layers, or may be stacked with other sheets such as paper, cloth (woven fabric or non-woven fabric), resin film, etc., and pressurized. Furthermore, by pressurizing and embossing force needle punching, a plurality of sheets can be laminated and integrated, or uneven shaped punching can be performed. In addition, by adding a thermoplastic resin component or a hot water-dissolving component to the raw material composition, it is possible to make it easy to perform bonding or the like by applying a heat sealing force.

[0071] The functional layer is provided on the oxygen scavenger intermediate. In the manufacturing process of the oxygen scavenger unit without providing the functional layer, the process of providing the following functional layer is not performed, and the process of incorporating an electrolyte into the oxygen scavenger intermediate is performed as described later.

[0072] The functional layer can be selected according to the form of the oxygen scavenger intermediate. In the case where the oxygen scavenger intermediate is formed into a sheet, it is preferable to provide a functional layer by a lamination process, particularly wet lamination, dry lamination, or extrusion lamination. By adopting the laminating method, we select in-line wet lamination, dry lamination, and extrusion lamination according to the papermaking process of the sheet-shaped oxygen scavenger intermediate that becomes the base material of the oxygen scavenger. In this case, a functional layer can be provided on the surface of the oxygen scavenger via an adhesive if 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 rosin 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 into a spherical, noodle-like, fiber-like, etc. composition by extrusion, pressure molding, tableting, etc. Can also be impregnated. 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 laminated or coated.

Next, the electrolyte is contained in the oxygen scavenger intermediate. Containing this electrolyte The process is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. However, when the electrolyte is added by impregnation with the electrolyte solution as described later, the acid / acid reaction immediately after the addition is moderately strong. Therefore, the electrolyte can be contained in a normal air atmosphere.

[0074] 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 to remove oxygen. And the like. Among these, the deoxidizing agent intermediate can contain the electrolyte uniformly, and the water content can be adjusted at the same time. The method of impregnating is preferred.

[0075] The electrolytic solution is preferably water or a mixture of water and alcohol obtained by electrolyzing an electrolyte. From the viewpoint of handling, a mixed solution of water and alcohol is preferable in order to further improve the deoxygenation performance, which is preferable for an electrolytic solution containing only water. The mixing ratio of water and alcohol is water Z alcohol (mass ratio), preferably 80 to 10% Z20 to 90%, more preferably 70 to 20% Z30 to 80%.

[0076] As described above, when the oxygen scavenger intermediate is impregnated with the electrolyte, the impregnation method can be appropriately selected according to the form of the oxygen scavenger 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 of the fibrous material is expressed. A method of penetrating the oxygen scavenger intermediate using an elephant, a method of coating with a brush, a method of immersing in the electrolyte, a gravure coating method, a reverse coating method, a doctor blade method, etc. Among these, the spray coating method is preferable because the electrolyte can be uniformly distributed, is simple, and requires relatively little equipment cost. In addition, in the case of products with complex shapes and layer configurations, the product has a predetermined concentration because it improves productivity, improves the flexibility of production by making the final finishing a separate process, and simplifies the equipment. A method of injecting the electrolytic solution with a syringe or the like is preferable. This method of injecting the electrolytic solution can also be performed after the oxygen scavenger intermediate is accommodated in, for example, an oxygen permeable container.

[0077] As described above, the oxygen scavenger intermediate contains an electrolyte and then dried to reduce the water content to 0.1. It can be adjusted to less than ˜5% by mass and stabilized to form an oxygen scavenger. Then, if necessary, in the case of a sheet-like form, two or more sheets can be laminated and processed into a predetermined size. 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. This step is preferably performed under an atmosphere of an inert gas such as nitrogen or argon.

[0078] The oxygen scavenger and oxygen scavenger complex obtained as described above is preferably coated on the surface with a coating layer having oxygen permeability. The coating layer may have oxygen permeability on the entire surface, or may partially have oxygen permeability. There is no particular limitation on the material of the coating layer as long as it has oxygen permeability. The coating layer can be provided by, for example, stacking paper, a nonwoven fabric, a multi-porous film, a resin film having fine pores, etc. on the surface of the oxygen scavenger. In addition, a synthetic resin paint, an emulsion paint, or the like can be provided by impregnating or applying an oxygen scavenger.

[0079] Further, the deoxidation characteristic 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 permeability coefficient and water vapor permeability coefficient, it is possible to obtain an oxygen scavenger with high V-deoxygenation characteristics in a short time, and a low oxygen permeability coefficient and water vapor permeability coefficient. By selecting the coating layer, it is possible to obtain a deoxygenating agent having a slow and deoxidizing characteristic over a long period of time.

[0080] 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.

[0081] As described above, the oxygen scavenger and oxygen scavenger complex of the present embodiment efficiently oxidizes an oxidizable metal, and high oxygen scavenging performance can be obtained with a smaller amount. In addition, it has high strength and is flexible enough to be torn when thinned, so it is excellent in workability and productivity. In addition, the oxygen absorption rate can be increased by increasing the content of oxidizable metals or adjusting the content of the electrolyte, so that the oil-impregnated content includes oil-containing foods such as French fries and chicken. Articles due to oxidative degradation of oil Can prevent quality degradation. In addition, since it does not ignite even when used in a microwave heating device such as a microwave oven, it can be used to maintain the freshness of retort foods.

[0082] Further, as described above, the raw material composition does not contain an electrolyte that serves as an oxidation aid, so that the ion concentration in the suspension decreases, so that the raw material composition contains The dispersibility of the oxidizable metal in the resin is improved. Then, by substantially contacting the oxidizable metal and the fibrous material during the preparation of the raw material composition, the oxidizable metal is uniformly fixed on the surface of the fibrous material, and the deoxidation obtained The deoxygenation properties of the agent are improved.

For example, in a suspension in which an electrolyte that serves as an oxidation assistant is blended, the salt concentration in the system increases, so that the electric double metal at the interface between the component such as the acid-resistant metal and the fibrous material can be obtained. Since the layer is compressed, the contact between the component and the fibrous material is remarkably hindered, making it 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 a 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 acidification, resulting in a decrease in deoxygenation performance. Furthermore, the papermaking body may easily react with oxygen in the air and may have poor long-term storage stability, or may easily form a molding machine such as a papermaking machine or a processing machine.

[0083] Further, since the oxygen scavenger intermediate containing no electrolyte is preliminarily dried and molded, the strength of the oxygen scavenger intermediate can be maintained, and secondary processing is facilitated. Generation and 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 pattern impregnation can be carried out in a certain arbitrary shape on the same surface. It is possible to obtain a deoxygenated molded article that can be divided into a part that does not react and a part that does not react with acid in the production process as much as possible and has good deoxygenation characteristics. Can do.

[0084] Further, according to the oxygen scavenger complex of this embodiment, various functions of the functional layer can be imparted to the oxygen scavenger exhibiting the above effects.

[0085] Next, the oxygen scavenger of the second invention will be described based on its preferred embodiment with reference to the drawings. In the following description, the characteristic part of the oxygen scavenger of the second invention will be described, and the description of the parts common to the oxygen scavenger of the first invention will be omitted. . Therefore, the description in the first invention is applied as appropriate to portions not specifically described.

[0086] The oxygen scavenger of the second invention is an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material, and an electrolyte that serves as an acid-oxidation reaction aid. It is included. The oxygen scavenger of this embodiment is a so-called moisture-dependent oxygen scavenger that exhibits oxygen scavenging performance with moisture in the external environment of the oxygen scavenger.

[0087] The oxygen scavenger of this embodiment contains 0.1 to 10% by mass of the electrolyte, preferably 0.2 to 8% by mass, more preferably 0.3 to 6% by mass and has a water content of 0. 1 to less than 5% by mass (0.1 to 5% by mass), preferably 0.3 to 4% by mass, more preferably 0.5 to 3% by mass.

[0088] For the electrolyte, an electrolyte that is 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, hydroxides, and the like. Among these, the points of excellent conductivity, chemical stability, and production cost are salty sodium, salty potassium, salty calcium, magnesium chloride, ferrous chloride, ferric chloride, etc. Of these, various salts are preferably used. These electrolytes can be used alone or in combination of two or more.

[0089] The description of the oxidizable metal in the embodiment of the oxygen scavenger of the first invention is applied to the oxidizable metal contained in the oxygen scavenger of the present embodiment.

[0090] As the water retention agent, a water retention agent that is conventionally used for conventional oxygen scavengers can be used without particular limitation. In addition to functioning as a water retention agent, the water retention agent also has a function as an oxygen retention Z supply agent for an oxidizable metal. Examples of the water-retaining agent include activated carbon (coconut shell charcoal, charcoal powder, calendar bituminous coal, peat, lignite), carbon black, acetylene black, black lead, zeolite, perlite, vermiculite, silica, cantalinite, fluorite, and the like. But 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 powder having an effective particle size of 0.1 to 500 111 capable of forming an effective contact state with an oxidizable metal. It is more preferable to use those containing 50 mass% or more of / ζ πι. As the water retention agent, those having a form other than the powder form as described above can be used. For example, a form having a fibrous form such as activated carbon fiber can also be used.

[0091] The content of the water retention agent in the oxygen scavenger intermediate is preferably 0.5 to 60% by mass, 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 deoxidizing agent intermediate are not reduced, and mechanical strength such as bending strength and tensile strength is maintained.

[0092] The description of the fibrous material in the embodiment of the oxygen absorber of the first invention is applied to the fibrous material contained in the oxygen absorber of the present embodiment.

[0093] A flocculant may be added to the oxygen scavenger intermediate, as will be described later. If necessary, a sizing agent, a colorant, a paper strength enhancer, a yield improver, a filler, Additives usually used in paper making such as thickeners, ρΗ control agents, bulking agents, etc. can be added without particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.

[0094] In order to make it possible to use the oxygen scavenger in a microwave heating apparatus such as a microwave oven, for example, a highly magnetically resistant fibrous material or powder such as silicon or alumina is added to the oxygen scavenger intermediate. Caro is preferred. If coloring is necessary for the appearance of the product, colored powders such as titanium oxide, calcium carbonate, and alumina white may be added. Furthermore, in order to promote the oxidation reaction and improve flexibility, powders such as florite, isolite, and talc, and ceramic fibers and synthetic fibers may be added.

[0095] When the oxygen scavenger intermediate is formed in a sheet form, the thickness per sheet, the basis weight per sheet, the tear length per sheet, and the air permeability per lOOgZm ² 1 In the embodiment of the invention The following explanation applies.

[0096] The description of the thickness of the oxygen scavenger in the embodiment of the first invention is applied to the thickness of the oxygen scavenger of the present embodiment.

Next, a preferred embodiment of the oxygen scavenger complex using the oxygen scavenger of the second invention will be described.

The oxygen scavenger complex of the present embodiment is one in which a functional layer is provided on the oxygen scavenger of the second invention.

[0098] The functional layer and the adhesive layer of the oxygen scavenger complex using the oxygen scavenger of the second invention, the thickness of the oxygen scavenger complex is the oxygen scavenger using the oxygen scavenger of the first invention The description of the thickness of the functional layer, the adhesive layer, and the oxygen scavenger complex in the embodiment of the agent complex applies.

Next, the oxygen scavenger of the second invention and the method for producing the oxygen scavenger complex using the oxygen scavenger will be described based on the preferred embodiment.

First, a raw material composition (slurry) containing the oxidizable metal, the water retention agent, the fibrous material, and water is prepared.

[0100] Regarding the addition of the flocculant to the raw material composition, the explanation of the addition of the flocculant described in the embodiment of the oxygen scavenger of the first invention is applied.

[0101] The concentration of the raw material composition is preferably 0.05 to 15% by mass, 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 body.

. In addition, since the raw material composition is uniformly dispersed, the surface properties of the resulting papermaking product are good.

A paper product having a uniform thickness can be obtained.

[0102] Next, the raw material composition is made into a paper.

The description of the oxygen scavenger of the first invention is applied to the papermaking method when the papermaking body is made into a sheet form.

[0103] The description of the first invention is applied to the moisture content of the papermaking product, the dehydration method, the drying method, and the moisture content of the oxygen scavenger intermediate after drying.

[0104] In the present embodiment, the papermaking product and the oxygen scavenger intermediate are formed by containing an electrolyte as an oxidation reaction aid in the papermaking product and the oxygen scavenger intermediate as described above.通 Molding can be performed in an ordinary air atmosphere. For this reason, the manufacturing equipment can be simplified. If necessary, creping, slitting, trimming, and processing such as changing the form by processing can be performed. Since the obtained oxygen scavenger intermediate has a high strength, it can be wound into a tool as needed when formed into a sheet form. Further, when the oxygen scavenger intermediate is formed into a sheet-like form, it may be used alone or in layers, or may be stacked with other sheets such as paper, cloth (woven fabric or non-woven fabric), resin film, etc., and pressurized. Furthermore, by pressurizing and embossing force needle punching, a plurality of sheets can be laminated and integrated, or uneven shaped punching can be performed. In addition, by adding a thermoplastic resin component or a hot water-dissolving component to the raw material composition, it is possible to make it easy to perform bonding or the like by applying a heat sealing force.

[0105] The functional layer is provided on the oxygen scavenger intermediate. In the manufacturing process of the oxygen scavenger unit without providing the functional layer, the process of providing the following functional layer is not performed, and the process of incorporating an electrolyte into the oxygen scavenger intermediate is performed as described later.

[0106] The description of the oxygen scavenger embodiment of the first invention is applied to the functional layer provided in the oxygen scavenger intermediate.

[0107] Next, the electrolyte is contained in the oxygen scavenger intermediate. The description in the embodiment of the oxygen scavenger of the first invention is applied to the step of containing the electrolyte.

[0108] 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 description of the coating layer in the oxygen scavenger of the first invention and the oxygen scavenger complex using the same is applied to the coating layer.

[0109] 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.

[0110] 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, since it has high strength and is flexible enough to be torn when thinned, it is excellent in workability and productivity. In addition, the oxygen absorption rate can be increased by increasing the content of oxidizable metals or adjusting the electrolyte content, so that oil-containing foods including oil-containing foods such as French fries and fried chicken can be used. It is possible to prevent deterioration of the quality of the product due to deterioration of the acidity of the oil of the product.

[0111] Further, as described above, the raw material composition does not contain an electrolyte that serves as an oxidation aid, so that the ion concentration in the suspension is reduced, so that the raw material composition contains The dispersibility of the oxidizable metal in the resin is improved. Then, by substantially contacting the oxidizable metal and the fibrous material during the preparation of the raw material composition, the oxidizable metal is uniformly fixed on the surface of the fibrous material, and the deoxidation obtained The deoxygenation properties of the agent 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 of the oxidizable metal, the water retention agent, and the like and the interface of the fibrous material can be reduced. Since the electric double layer is compressed, the contact between the component and the fibrous material is remarkably hindered, making it difficult to fix the component on the surface of the fibrous material, and the thickness is thin and the component is filled with a large amount. It becomes difficult to form the formed sheet. Further, in a system having a high salt concentration as described above, fixing with a flocculant is 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 acidification, resulting in a decrease in deoxygenation performance. In addition, the papermaking body may easily react with oxygen in the air and may have poor long-term storage stability, or may easily form a paper machine or other molding machine or processing machine.

[0112] Furthermore, since the oxygen scavenger intermediate containing no electrolyte is previously dry-molded, the strength of the oxygen scavenger intermediate can be maintained, secondary processing is facilitated, and the cutting tool blades are cut. Generation and 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 pattern impregnation can be carried out in a certain arbitrary shape on the same surface. It is possible to obtain a deoxygenated molded article that can be divided into a part that does not react and a part that does not react with acid in the production process as much as possible and has good deoxygenation characteristics. Can do.

[0113] Further, 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.

[0114] 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.

[0115] In the above-described method for producing an oxygen scavenger complex, both of the above are provided on the surface of the oxygen scavenger intermediate. Although the electrolyte was included after the functional layer was provided, the production order is not limited to this, and the functional layer is provided after the oxygen scavenger intermediate includes the electrolyte and the oxygen scavenger is manufactured. May be. In addition, 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 heated and dried to a moisture content that requires the oxygen scavenger, and the polyvinyl alcohol is cross-linked to prevent the iron powder contained in the oxygen scavenger from falling off. It can also be given.

[0116] The oxygen scavenger and oxygen scavenger complex of the present invention is preferably molded into a predetermined form by cutting or the like, and housed in a container together with the contents, but has flexibility. Therefore, a container such as a bag or a bouch can be formed with an oxygen scavenger or oxygen scavenger complex, or a container having a oxygen scavenging function can be formed by press molding to form a desired three-dimensional shape. it can . It can also be used by bonding it to the base material sheet of the container and forming it into a paperboard container or a voucher. By making the oxygen scavenger intermediate in a form, it is possible to produce a container having a deoxidation function having a form matched to these containers.

[0117] Further, 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. .

[0118] The oxygen scavenger and oxygen scavenger complex of the present invention are used for maintaining the freshness of foods, preventing oxidation of medical equipment, antifungal of metal, bedding, clothes, antifungal of art, etc. It can be applied to.

Example

[0119] Hereinafter, the present invention will be described more specifically with reference to Examples.

The following examples 1-1, 1-2, 2-1 and 2-2 and comparative examples 1-1, 2-1 and 2-2 were prepared as oxygen scavengers, and their oxygen scavenging performance was examined. . Tables 11 and 2-1 show the composition ratio and basis weight of the oxygen scavenger, Tables 1 and 2 and 2 show the mixing ratio of the solids in the raw material composition and the papermaking yield, and Tables 1 and 3 show the composition. The effective reaction rate of iron powder in the oxygen agent, the amount of effective iron powder that contributes to oxygen absorption determined from VSM, and the solid thread yield determined from TG are shown. [Example 1 1]

The fibrous material: pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, the trade name of "Mackenzie", CSF150ml,) 17 mass ^_0/0

Oxidizable metal: Iron powder (made by Dowa Iron Mining Co., Ltd., trade name “RKH”) 83% by mass Flocculant: 100 parts by mass of the above raw material composition, 1.0% by mass of the following cationic flocculant and The following ion flocculant 0.2 parts by mass

Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hoshimitsu PMC Co., Ltd., trade name “WS4020”)

Char-on flocculant: Sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)

Water: Industrial water, solid content 1.25% by mass until added

[0121] <Raw material preparation conditions>

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

[0122] <Conditioning conditions>

Using the raw material composition of the above formulation, dilute to 0.11% by mass and make paper using a square sheet machine (Kumagaya Riki Kogyo Co., Ltd.) with a width of 250 x 250 mm according to JIS P8209. A wet sheet-like papermaking product was prepared.

[0123] <Drying conditions>

Using a KRK rotary dryer (manufactured by Kumagai Riki Kogyo Co., Ltd.), drying was carried out so that the water content was 1% by mass or less to obtain a sheet-shaped oxygen scavenger intermediate.

[0124] <Electrolytic solution addition conditions>

55 parts by mass of the following electrolytic solution was added to 100 parts by mass of the oxygen scavenger intermediate, followed by drying in a nitrogen atmosphere at 110 ° C. to obtain a desired oxygen scavenger. The water content of the obtained oxygen scavenger was 2% by mass as shown in Table 11.

[0125] <Electrolyte>

Electrolyte: Purified salt (NaCl) Water: Industrial water

Electrolyte concentration: 1

[0126] [Table 1-1]

[Example 1 2]

An oxygen scavenger was prepared in the same manner as in Example 11 except that the raw material preparation conditions were prepared by hand stirring for about 15 seconds without using JIS pulper.

[Comparative Example 1 1]

Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hokko PMC Co., Ltd., trade name “W S4020”;>

Water: Industrial water, solid content 1.25% by mass until added

Salt: 1.0 part by weight of salt per 100 parts by weight of the slurry

[0129] <Raw material preparation conditions>

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

[0130] <Conditioning conditions> Using the raw material composition of the above formulation, dilute to 0.11% by weight, and after paper making using a square sheet machine (made by Kumagaya Riki Kogyo Co., Ltd.) with a width of 250 x 250mm according to JIS P8209 A wet sheet-like papermaking product was produced by pressing. The dilution water was a 1% by weight aqueous NaCl solution. The moisture content of the obtained oxygen scavenger was 34.7% by mass as shown in Table 1-1. And it dried under 110 degreeC nitrogen atmosphere, and obtained the desired oxygen scavenger. The water content of the oxygen scavenger obtained was 2% by mass as shown in Table 11.

[0131] <Form of oxygen scavenger>

The obtained oxygen scavenger had a thickness of 0.2 to 0.4 mm and a basis weight of 125 to 170 gZm ² . The thickness was measured in accordance with JIS P8118 at 5 or more points of the oxygen scavenger, the average value was calculated as the thickness, and the basis weight was measured on the weight of the oxygen scavenger at an area of at least 100 cm ^2. Calculated by dividing by area.

[0132] [Measurement of oxygen scavenger performance of oxygen scavenger]

Example 1 1 and Comparative Example 1 The oxygen scavenger 6g of 1 was placed in a desiccator with an air volume of 5.5 liters without being covered with a coating layer having oxygen permeability, and the oxygen concentration in the desiccator was determined. Measurements were made to determine the deoxygenation performance. The oxygen concentration was measured using an oxygen monitor OM-25MS01 manufactured by Taiho Electric Co., Ltd. The results are shown in Fig. 1.

[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 deoxidation in the oxygen scavenger was measured. The results are shown in Table 13.

[Measurement of composition ratio of oxygen scavenger by TG]

The composition ratio of the oxygen scavenger was measured using TGZDTA-6300 and autosampler unit AST-2, a high-temperature differential thermal thermogravimetric simultaneous measurement device manufactured by Seiko Instruments Inc. as TG. The sample container used was a Pt φ5 mm and a height of 5 mm so as to withstand a high temperature of 1000 ° C. The results are shown in Table 13.

[0135] [Table 1-2] Composition! : Percentage (mass%)

Paper making yield (%) Iron powder Panolep

Example 1 1 1 83 17 94

Example 1 1 2 83 17 92

Comparative Example 1 1 1 83 17 71

[0136] [Table 1-3]

[0137] As shown in Fig. 1 and Tables 12 and 13, the effective reaction rate of the iron powder of Example 11 is similar to that of the sample stirred by hand in Example 1 2. However, it was clear that the oxidation reaction hardly progressed. On the other hand, Comparative Example 1-1 contains an electrolyte as a reaction aid at the papermaking stage, so that the oxidation reaction proceeds and the effective reaction rate of iron powder is low. It was. Also, in terms of the papermaking yield, Examples 1-1 and 1-2 do not contain an electrolyte as a reaction aid at the papermaking stage, so that the papermaking yield is high and the industry is stable, high quality, and low cost. It was possible to manufacture with.

[Example 2-1]

The fibrous material: pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, the trade name of "Mackenzie", CSF150ml,) 15 mass ^_0/0

Oxidizable metal: Iron powder (made by Dowa Iron Mining Co., Ltd., trade name “RKH”) 75% by mass Water retention agent: Activated carbon (made by Nippon Enbiguchi Chemical Co., Ltd., trade name “Carborafine”) Agent: 1.0 parts by mass of the following cationic flocculant and 0.2 parts by mass of the following ionic flocculant with respect to 100 parts by mass of the above raw material composition Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hoshimitsu PMC Co., Ltd., trade name “WS4020”)

Water: Industrial water, solid content 1.25% by mass until added

[0139] <Raw material preparation conditions>

[0140] <Making conditions>

[0141] <Drying conditions>

[0142] <Electrolytic solution addition conditions>

55 parts by mass of the following electrolytic solution was added to 100 parts by mass of the oxygen scavenger intermediate, followed by drying in a nitrogen atmosphere at 110 ° C. to obtain a desired oxygen scavenger. The moisture content of the obtained oxygen scavenger was 2% by mass as shown in Table 2-1.

[0143] Electrolyte>

Electrolyte: Purified salt (NaCl)

Water: Industrial water

Electrolyte concentration: 1% by mass

[0144] [Table 2-1] Composition ratio of oxygen scavenger (mass%)

Iron powder Activated carbon Panorep NaCl water (g / m ') Male example 2 _ 1 70.7 12.6 14.3 0.4 2 195 Example 2— 2 70.7 12.6 14.3 0.4 2 187 Comparative example 2— 1 74.6 23.0 0.3 2 125 Comparative example 2—2 "Less FX—LD40

[Example 2-2]

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

[Comparative Example 2-1]

Water: Industrial water, solid content 1.25% by mass until added

Salt: 1.0 part by weight of salt per 100 parts by weight of the slurry

[0147] <Raw material preparation conditions>

[0148] <Conditioning conditions>

Using the raw material composition of the above formulation, dilute to 0.11% by weight, and after paper making using a square sheet machine (made by Kumagaya Riki Kogyo Co., Ltd.) with a width of 250 x 250mm according to JIS P8209 A wet sheet-like papermaking product was produced by pressing. The dilution water is 1% N aCl aqueous solution was used. The moisture content of the obtained oxygen scavenger was 34.7% by mass as shown in Table 2-1. And it dried under 110 degreeC nitrogen atmosphere, and obtained the desired oxygen scavenger. The water content of the obtained oxygen scavenger was 2% by mass as shown in Table 2-1.

[Comparative Example 2-2]

The product name Ageless FX-LD40 (moisture dependent type) manufactured by Mitsubishi Gas Chemical Co., Ltd. was used.

[0150] <Form of oxygen scavenger>

Deoxidizer obtained, as shown in Table 2 1, one thickness thereof 0. 2 to 0. 4 mm, was basis weight 125~195gZm ^2. The thickness was measured in accordance with JIS P8118 at 5 points or more of the oxygen scavenger, the average value was calculated as the thickness, and the basis weight was measured on the weight of the oxygen scavenger in an area of at least 100 cm ^2. Calculated by dividing by area.

[0151] [Measurement of oxygen scavenger performance of oxygen scavenger]

In the desiccator, 6 g of the oxygen scavenger of Example 2-1 and Comparative Examples 2-1 and 2-2 was placed in a desiccator having an air volume of 5.5 liters without being covered with a coating layer having oxygen permeability. The oxygen concentration was measured to determine the deoxygenation performance. The oxygen concentration was measured using an oxygen monitor OM-25MS01 manufactured by Taiho Electric Co., Ltd. The results are shown in Fig. 2.

[0152] [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 deoxidation in the oxygen scavenger was measured. The results are shown in Table 2-3.

[Measurement of composition ratio of oxygen scavenger by TG]

The composition ratio of the oxygen scavenger was measured using TGZDTA-6300 and autosampler unit AST-2 as a high-temperature differential thermal thermogravimetric measuring device manufactured by Seiko Instruments Inc. as TG. The sample container used was a Pt φ5 mm and a height of 5 mm so as to withstand a high temperature of 1000 ° C. The results are shown in Table 2-3.

[0154] [Table 2-2] Composition ratio (% by mass)

Paper making yield (%) Iron powder Activated carbon Panolep

Example 2— 1 75 10 15 97

Example 2-2 75 10 15 94

Comparative Example 2— 1 83 17 71

Comparative Example 2— 2 Ageless FX— LD40

[0155] [Table 2-3]

[0156] As shown in Fig. 2 and Table 2-2 2 2-3, the oxygen scavenger obtained in Example 2-1 does not contain an electrolyte as a reaction aid in the papermaking stage. It became clear that the oxidation reaction did not proceed and the effective reaction rate of iron powder was high. Furthermore, since Example 2-1 has a water retention agent V, it has the ability to absorb oxygen quickly and quickly compared to Comparative Example 2-1! / I was able to help. Also, in terms of papermaking yield, Example 2-1 does not contain an electrolyte as a reaction aid at the papermaking stage, and therefore, it must be manufactured stably, with high quality and at low cost even in industrial terms where the papermaking yield is high. Is possible. Furthermore, in comparison with a commercially available moisture-dependent oxygen scavenger in which iron powder is kneaded into the thermoplastic resin of Comparative Example 2-2 and formed into a sheet mold, it is quick, high in time, and provides oxygen scavenging performance. I was strong.

Industrial applicability

[0157] According to the oxygen scavenger of the first invention, an oxidizable metal is efficiently oxidized and high oxygen scavenging performance can be obtained with a smaller amount. 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 method for producing the oxygen scavenger and oxygen scavenger complex according to the present invention comprises an electrolyte serving as an oxidation reaction aid. By preparing and manufacturing a slurry made of oxidizable metal and fibrous material, the degradation of deoxidation performance due to oxidation of the oxidizable metal during slurry preparation, supply and / or molding is minimized. The oxygen absorber and oxygen absorber complex can be suitably produced.

According to the oxygen scavenger of the second invention, high oxygen scavenging performance can be obtained in a quick time. Furthermore, 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 method for producing an oxygen scavenger and oxygen scavenger complex according to the present invention does not include an electrolyte as an oxidation reaction aid, and prepares and manufactures a slurry made of an oxidizable metal, a water retention agent, and a fibrous material. Therefore, it is possible to minimize the deterioration of the oxygen removal performance due to the oxidation of the oxidizable metal during the slurry preparation, supply and / or molding, and the above oxygen absorber and oxygen absorber composite are suitable. Can be manufactured.

Claims

The scope of the claims

[1] An oxygen scavenger comprising an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal and a fibrous material, and an electrolyte as an oxidation reaction aid,

A deoxidizing agent comprising 0.1 to 10% by mass of the electrolyte and having a water content of 0.1 to less than 5% by mass.

[2] The oxygen absorber according to claim 1, wherein the fibrous material has a CSF of 600 ml or less.

[3] The oxygen scavenger according to claim 1 or 2, wherein an effective reaction rate of the oxidizable metal is 75% or more.

[4] An oxygen scavenger intermediate for use in the oxygen scavenger according to any one of claims 1 to 3, wherein the papermaking body containing an oxidizable metal and a fibrous material is dried. An oxygen scavenger intermediate.

[5] An oxygen scavenger complex, wherein the oxygen scavenger according to any one of claims 1 to 3 is provided with a functional layer.

[6] The oxygen scavenger complex according to claim 5, wherein the functional layer is laminated via an adhesive layer.

[7] The function layer according to claim 5 or 5, wherein the functional layer has a function of preventing solid components from falling off, concealing, deodorizing, anti-magnetic, moisture barrier or oil noria, or a combination of these functions. The oxygen scavenger complex according to item 6.

[8] The method for producing an oxygen scavenger according to claim 1, wherein the oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal and a fiber is added to an oxygen scavenger intermediate. A method for producing an oxygen scavenger that contains an electrolyte that serves as an agent.

[9] The method for producing an oxygen scavenger complex according to claim 5, wherein the function is added to the oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal and a fibrous material. A method for producing an oxygen scavenger complex that includes an electrolyte as an oxidation reaction aid after providing a layer.

[10] The method for producing an oxygen scavenger complex according to claim 5, wherein the oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal and a fibrous material is subjected to an oxidation reaction. A method for producing an oxygen scavenger complex in which an oxygen scavenger is produced by including an electrolyte as an auxiliary agent, and then the functional layer is provided on the oxygen scavenger.

[11] 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 serving as an oxidation reaction aid.

[12] The oxygen absorber according to claim 11, wherein the fibrous material has a CSF of 600 ml or less.

[13] The oxygen scavenger according to [11] or [12], wherein an effective reaction rate of the oxidizable metal is 75% or more.

[14] An oxygen scavenger intermediate used in the oxygen scavenger according to any one of claims 11 to 13, wherein the papermaking includes an oxidizable metal, a water retention agent, and a fibrous material. An oxygen scavenger intermediate made by drying the body.

[15] An oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger according to any one of claims 11 to 13.

16. The oxygen scavenger complex according to claim 15, wherein the functional layer is laminated via an adhesive layer.

[17] The scope of claim 15 or 15, wherein the functional layer has a function of preventing solid components from falling off, concealing, deodorizing, resistance to magnetism, moisture barrier or oil noria, or a combination of these functions. Item 17. The oxygen scavenger complex according to item 16.

[18] A method for producing an oxygen scavenger according to claim 11, wherein 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 containing an electrolyte that serves as an oxidation reaction aid.

[19] The method for producing the oxygen scavenger complex according to claim 15, wherein the oxidizable metal

, A water retention agent, and an oxygen scavenger intermediate formed by drying a paper product containing a fibrous material, and after providing the functional layer, manufacturing an oxygen scavenger complex containing an electrolyte as an oxidation reaction aid Method.

[20] The method for producing the oxygen scavenger complex according to claim 15, wherein the oxygen scavenger intermediate is obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. In addition, an oxygen scavenger is added to the electrolyte to produce an oxygen scavenger, and then the functional layer is added to the oxygen scavenger. And a method for producing an oxygen scavenger complex.