WO2007049676A1 - Oxygen scavenger, oxygen scavenger intermediate, oxygen scavenger composite, and process for producing the same - Google Patents

Oxygen scavenger, oxygen scavenger intermediate, oxygen scavenger composite, and process for producing the same Download PDF

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Publication number
WO2007049676A1
WO2007049676A1 PCT/JP2006/321339 JP2006321339W WO2007049676A1 WO 2007049676 A1 WO2007049676 A1 WO 2007049676A1 JP 2006321339 W JP2006321339 W JP 2006321339W WO 2007049676 A1 WO2007049676 A1 WO 2007049676A1
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Prior art keywords
oxygen scavenger
oxygen
electrolyte
oxidizable metal
fibrous material
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PCT/JP2006/321339
Other languages
French (fr)
Japanese (ja)
Inventor
Yoshiaki Kumamoto
Masataka Ishikawa
Taijun Yoshida
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Kao Corporation
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Publication of WO2007049676A1 publication Critical patent/WO2007049676A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23L3/3436—Oxygen absorbent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds

Definitions

  • Oxygen absorber oxygen absorber intermediate, oxygen absorber complex and method for producing the same
  • 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.
  • the oxygen scavenger produced by this technique is obtained by making a paper from a mixture of a fibrous substance, iron powder, water and an electrolyte and forming it into a sheet. Since an electrolyte that serves as an oxidation reaction aid is added to the slurry, the iron powder oxidation reaction occurs during the preparation of the slurry, during the supply, and / or during the sheet forming, and the performance of the resulting oxygen scavenger is reduced. In addition, particularly during the supply of the slurry, the oxidation reaction of iron powder progresses over time, and the deoxidation performance of the resulting oxygen scavenger decreases over time, and there is a problem that certain performance cannot be obtained. I got it.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 62-234544
  • the first object of the present invention is to provide an oxygen scavenger, oxygen scavenger intermediate, oxygen 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 its manufacturing method.
  • the second object of the present invention is to provide an oxygen scavenger capable of obtaining high oxygen scavenging performance in a quick time.
  • the present invention is an oxygen scavenger comprising an oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal and a fibrous material and an electrolyte serving as an oxidation reaction aid.
  • the first object is achieved by providing an oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass.
  • this invention is also referred to as a first invention.
  • the present invention provides an oxygen scavenger intermediate used in the oxygen scavenger of the first invention, wherein the oxygen scavenger intermediate is formed by drying a papermaking product containing an oxidizable metal and a fibrous material. It provides the body.
  • the present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the first invention.
  • the present invention provides a 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 oxidized.
  • the present invention provides a method for producing an oxygen scavenger containing an electrolyte as a reaction aid.
  • the present invention provides a method for producing the oxygen scavenger complex according to the first invention, wherein an oxygen scavenger intermediate formed by drying a paper product containing an oxidizable metal and a fibrous material is provided. After the functional layer is provided, a method for producing an oxygen scavenger complex containing an electrolyte as an oxidation reaction aid is provided.
  • the present invention provides a method for producing the oxygen scavenger complex according to the first invention, wherein an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal and a fibrous material is provided.
  • the present invention provides a method for producing an oxygen scavenger complex, in which an oxygen scavenger is produced by including an electrolyte as an oxidation reaction aid, and then the functional layer is provided on the oxygen scavenger.
  • 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. Then, the second object is achieved by providing an oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass.
  • this invention is also referred to as the second invention.
  • the present invention is an oxygen scavenger intermediate used in the oxygen scavenger of the second invention, and is obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material.
  • Middle oxygen scavenger Provide the body.
  • the present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the second invention.
  • 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.
  • the present invention provides a method for producing an oxygen scavenger containing an electrolyte as an oxidation reaction aid.
  • the present invention is a method for producing the oxygen scavenger complex according to the second invention, wherein the oxygen scavenger is obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material.
  • An object of the present invention is to provide a method for producing an oxygen scavenger complex in which an intermediate layer is provided with the functional layer and then contains an electrolyte that serves as an oxidation reaction aid.
  • the present invention is a method for producing the oxygen scavenger complex according to the second invention, wherein the oxygen scavenger is obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material.
  • the oxygen scavenger is obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material.
  • a method for producing an oxygen scavenger complex in which an oxygen scavenger is produced by adding an electrolyte as an oxidation reaction aid to an intermediate, and then the functional layer is provided on the oxygen scavenger. .
  • FIG. 1 is a diagram showing the oxygen scavenging performance of oxygen scavengers of Example 11 and Comparative Example 11 of the present invention.
  • 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.
  • the present invention will be described based on preferred embodiments with reference to the drawings.
  • 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.
  • 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 that serves as an oxidation reaction aid. .
  • the oxygen scavenger of this embodiment is a so-called self-reactive oxygen scavenger in which the oxidation reaction of the oxidizable metal occurs with the moisture of the oxygen scavenger itself.
  • 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. 5 to 70% by mass, preferably 7 to 60% by mass, more preferably 10 to 50% by mass.
  • the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger are within such ranges, sufficient water can be secured to sustain the oxidation reaction, and the oxidation reaction proceeds sufficiently.
  • water can be uniformly supplied to the oxygen scavenger, uniform oxygen scavenging performance can be obtained and air permeability of the oxygen scavenger is not impaired. Oxidation reaction is good, and the amount of deoxygenation can be increased with less amount and high amount.
  • an electrolyte that is conventionally used for this type of oxygen scavenger can be used without particular limitation.
  • the electrolyte include sulfates, carbonates, salts, hydroxides, and the like of alkali metals, alkaline earth metals, or heavy metals.
  • various kinds such as sodium chloride sodium, sodium chloride potassium, sodium chloride calcium, magnesium chloride, ferrous chloride, ferric chloride are provided because of their excellent conductivity, chemical stability, and production cost. Salty salt is preferably used.
  • These electrolytes can be used alone or in combination of two or more.
  • an oxidizable metal that is conventionally used for this type of oxygen scavenger can be used without particular limitation.
  • As the form of the oxidizable metal it is preferable to use a form having a powdery or fibrous form from the viewpoints of handleability and moldability.
  • Examples of the oxidizable metal having a powder form include iron powder, aluminum powder, zinc powder, manganese powder, magnesium powder, and calcium powder. Among these, 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 / ⁇ ⁇ , 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.
  • Examples of the oxidizable metal having a fibrous form include steel fibers, aluminum fibers, and magnesium fibers. Among these, handling, safety, manufacturing cost From this point, steel fibers, aluminum fibers and the like are preferably used.
  • 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.
  • the oxidizable metal in the oxygen scavenger has an effective reaction rate of preferably 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 deoxidizing agent, so that the deoxygenation ability required for the packaging specification is obtained.
  • the oxygen scavenger can be made small and light, and the raw material cost of the oxygen scavenger can be reduced.
  • 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 oxidizability at the raw material stage represented by the following formula 2. This is the value obtained by the following formula 3 divided by the metal ratio.
  • the upper limit of the effective reaction rate is 100%.
  • Effective reaction rate of oxygen scavenger (%) ( ⁇ / ⁇ ) X 100 ⁇ ⁇ ⁇ Equation 3
  • the mass of the oxygen scavenger is the dry mass obtained by heating the oxygen scavenger to near 100 ° C in a nitrogen atmosphere to evaporate the water, but the mass in a state containing water may be used as it is. .
  • the oxygen content of the oxygen scavenger in Equation 1 and Equation 2 must be matched.
  • the above packaging specification means that, for example, 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.
  • the mass ratio of the iron powder at the raw material stage can be determined by thermogravimetry.
  • thermogravimetry When a sample was prepared from the deoxidizer, and the sample was placed in a sample container and gradually raised from room temperature in a nitrogen atmosphere, the water contained in the deoxidizer evaporated near 100 ° C. , Mass rapidly decreases around 350 ° C. This mass loss is the cell contained in the wood pulp. It is the amount of roast degradation.
  • the temperature is further raised and air is introduced from 550 ° C and heated to 1000 ° C, the wood pulp burns and eventually 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.
  • the mass of iron oxide is obtained by subtracting the ash content derived from wood pulp calculated from the residual amount of cellulose in the sample container.
  • the mass of iron powder contained in the sample can be determined.
  • the mass coefficient of acid iron iron The correction coefficient for obtaining the mass of iron powder of the raw material is generally obtained from the iron oxidation reaction equation, but the iron powder supplied from the raw material manufacturer 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 mass of the iron oxide produced and the mass of the iron powder of the raw material can be obtained. The correction factor obtained from this experiment was used.
  • the mass force of ferrous iron can also determine the mass of the iron powder, and the ratio force with the mass of the sample can also determine the mass ratio of the iron powder at the raw material stage (Equation 5).
  • the mass of iron powder effective for oxygen scavenging contained in the oxygen scavenger sample can be determined.
  • the ratio of iron powder effective for oxygen absorption in the oxygen scavenger can be obtained (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 expressed by the following formula 4, and the ratio of iron powder in the raw material stage expressed by formula 5 below. The value obtained by the following formula 6 divided by It is.
  • 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.
  • 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.
  • 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.
  • fibrous material examples include plant fibers (cotton, caboch, 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, vicu ⁇ a, silk, feathers , Down, feather, algin fiber, chitin fiber, casein fiber, etc.) and mineral fiber (asbestos, etc.).
  • plant fibers cotton, caboch, 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, vicu ⁇ a, silk, feather
  • synthetic fibers include semi-synthetic fibers (acetate, triacetate, oxide acetate, promix, Salt fiber rubber, hydrochloric acid rubber, etc.), metal fibers, carbon fibers, inorganic fibers (e.g. glass fibers, ceramic fibers, etc.) Can be mentioned.
  • the composite fiber having a core-sheath structure can be used.
  • 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.
  • 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.
  • these fibers can be used in the form of collected and reused.
  • wood pulp and cotton are preferably used from the viewpoints of fixability of the oxidizable metal, flexibility of the resulting papermaking, oxygen permeability due to the presence of voids, production cost, and the like.
  • the fibrous material preferably has a Canadian Standard Freeness (CSF) force of 600 ml or less, more preferably 450 ml or less.
  • CSF Canadian Standard Freeness
  • 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. .
  • moldability is improved, such as obtaining an oxygen scavenger intermediate with a uniform thickness.
  • the fixing between the fibrous material and the component is good, it is possible to obtain a bond strength derived from the removal of the component, the entanglement between the component and the fibrous material, and hydrogen bonding. For this reason, mechanical strength such as bending strength and tensile strength is maintained, and workability is also improved.
  • the component ratio other than the fibrous material if the component ratio other than the fibrous material is low, if the CSF is less than 100 ml, the drainage will be very poor and difficult to dewater. As a result, it becomes difficult to obtain a paper product having a uniform thickness, or a molding failure such as blister breakage occurs during drying.
  • the ratio of components other than the fibrous material is high, an oxygen scavenger intermediate with good drainage and uniform thickness can be obtained even if the CSF is less than 100 ml.
  • 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 water breakage of a fibrous material that can be obtained by measuring by the method shown in CSFi and IS P81 21 (pulp freeness test method).
  • the fibrous material has a negative (negative) surface charge.
  • the fixability of powder components such as oxidizable metals to the fibrous material is good, the powder retention is high, and the oxygen scavenger performance of the resulting oxygen scavenger Is increased.
  • a large amount of powder components such as oxidizable metals are prevented from being mixed in the wastewater in the wet papermaking process, and it does not adversely affect productivity and environmental conservation.
  • the terms further increase the yield of the oxygen scavenger intermediates obtained, the fibrous material, the electric load amount 2.
  • OX 10 " 6 eq / g or less is more preferred.
  • the amount of charge of the fibrous material is measured by colloid titration. It is the apparent potential at the shear surface between the charged particle interface and the solution. The same applies to the zeta potential, which is measured by the streaming potential method, the electrophoresis method or the like.
  • the fibrous material preferably has an average fiber length of 0.1 to 50 mm, more preferably 0.2 to 20 mm.
  • 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.
  • 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.
  • the fibrous material is uniformly dispersed in the oxygen scavenger intermediate, and uniform mechanical strength can be obtained.
  • an oxygen scavenger intermediate having a uniform thickness is obtained, the fiber spacing is not excessively wide, and the ability of the component such as the oxidizable metal to be retained by the fiber is obtained, so that dropping of the component is suppressed.
  • the blending 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.
  • composition ratio of each component is determined by, for example, thermogravimetry, the content of the fibrous material or the acid content.
  • the content of chemical substances can be determined.
  • the oxygen scavenger intermediate contains 50% by mass or more of components other than the fibrous material, more preferably 70% by mass or more, and more preferably 80% by mass. More preferably, it is contained.
  • 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.
  • 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.
  • a flocculant may be added to the oxygen scavenger intermediate.
  • the oxygen scavenger intermediate is usually used for paper making such as sizing agent, coloring agent, paper strength enhancer, yield improver, filler, thickener, pH control agent, bulking agent, etc.
  • the additive used can be added without any particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.
  • 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, it can be done by adding powder of florite, isolite, talc, etc., or ceramic fibers and synthetic fibers.
  • the thickness of one sheet is 0.
  • 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.
  • 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.
  • the basis weight of one that is more preferably from 10 ⁇ 1000gZm 2 is preferably tool 50 ⁇ 600gZm 2.
  • the basis weight is lOgZm 2 or more, a metal having a high specific gravity is used among acid-oxidizing metals.
  • a particularly stable sheet can be formed.
  • the basis weight is within lOOOgZm 2, it is light and feels good. In addition, productivity and operability are also improved.
  • the breaking length of one sheet is preferably 100 to 4000 m, more preferably 200 to 3000 m.
  • the breaking length is 100 m or more, the sheet can be stably formed without breaking or cutting the sheet during operation. Also, 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.
  • the breaking length is 4000 m or less, the fibrous material and adhesive component forming the sheet do not increase excessively, and the material is flexible and excellent in deoxygenation performance.
  • 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 ])
  • the oxygen scavenger intermediate allows the oxygen scavenging reaction to proceed satisfactorily, improving the ability, and taking into account the fact that the electrolyte can be more uniformly contained when the electrolyte is added.
  • the air permeability per basis weight lOOgZm 2 is 0.1 to: LOOO sec Z (6.4 cm 2 '300ml) S force, 0.1 to 500 sec Z (6.4 cm 2 ' 300ml) ) Is more preferable.
  • the thickness of the oxygen scavenger is appropriately set according to the use and form (for example, when the oxygen scavenger intermediate is in the form of a sheet, a plurality of sheets are used in a stacked manner). Considering processability and packaging specifications, 0.0 to 20mm is preferred. 0.1 to: LOmm is more preferred.
  • the oxygen scavenger of the first invention is provided with a functional layer.
  • the functional layer has a function of preventing solid components of the oxygen scavenger from falling off, concealing, deodorizing, anti-magnetic, moisture barrier or oil barrier, or a combination of these functions.
  • the functional layer having a function of preventing the solid component of the oxygen scavenger from falling off has a gas permeability for expressing the oxygen scavenging performance of the oxygen scavenger. The solid component contained in the oxygen scavenger is removed. Prevents contamination.
  • 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 substrate for a functional layer in combination thereof, or the oxygen scavenger and drying. Can do.
  • the paper is preferably a paper pulp, a synthetic norp or a mixture thereof produced by a wet or dry manufacturing method.
  • 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 made of 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.
  • thermoplastics such as polyolefin such as polyethylene and polypropylene, polyamide such as nylon, polyester such as polyethylene terephthalate, polyfluorinated polyolefin such as polytetrafluoroethylene, etc. Fat is preferred.
  • 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.
  • the filler silica, calcium carbonate, alumina, titanium white barium sulfate, zeolite, diatomaceous earth, activated clay, acid clay, talc, bentonite, iron oxide and the like are preferably used.
  • the particle size of the filler is preferably an Itoda force, more preferably 0. Ol-lOO ⁇ m, particularly preferably 0.1 to 50 m.
  • the resin composition include natural resin compositions such as starch, carboxymethyl cellulose and guar gum, polybulal alcohols, modified celluloses, salted bulls, acrylics, silicones, silicone acrylics, polyamides, polyesters.
  • examples thereof include a resin composition comprising a single resin or a copolymer of a synthetic resin such as a rubber, polyolefin, phenol, ethylene butyl acetate copolymer, polybutadiene, or a mixture thereof.
  • the functional layer having a function of concealing the oxygen scavenger has air permeability for expressing the oxygen scavenging performance of the oxygen scavenger, but conceals the color of the oxygen scavenger so that the external force cannot be seen.
  • 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.
  • the white pigment include titanium oxide, zinc oxide, calcium carbonate, talc, kaolin, alumina silicate, clay, gypsum, and alumina white.
  • the colored pigment examples 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.
  • the same material as that of the functional layer having the function of preventing the solid component from falling off can be appropriately selected.
  • the functional layer having a deodorizing function of the oxygen scavenger has air permeability for expressing the oxygen scavenging performance, but deodorizes it 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.
  • the same material as that of the functional layer having the function of preventing the solid component from falling off can be appropriately selected. .
  • the deodorant examples 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).
  • CFIS K1470 dry charcoal with a moisture content of 10% or less
  • 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.
  • the phyllosilicate include magnesium phyllosilicate, zinc phyllosilicate, bentonite, activated clay, and acid clay.
  • the deodorizer preferably has a particle diameter of 0.01 to: LOO / zm, particularly 0.1 to 50 m.
  • 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.
  • the functional layer of the oxygen scavenger having a magnetic resistance function is obtained by dispersing a magnetically resistant fibrous material or powder such as silicon or alumina in a resin, and the powder is supported on the fibrous material. A thing etc. are used suitably.
  • the functional layer having a moisture barrier function and an oil content barrier function of the oxygen scavenger is used for the food product by the oxygen scavenger that may occur when the oxygen scavenger is used for the preservation of foods with a high water content such as retort foods. It prevents pollution and contamination of oxygen scavenger by moisture from food.
  • a layer made of a thermoplastic resin film can be used as the functional layer having the moisture barrier function.
  • 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.
  • the thermoplastic resin may contain a poorly water-soluble filler.
  • the poorly water-soluble filler is an inorganic or organic substance that is insoluble or hardly soluble in water.
  • the poorly water-soluble filler for example, silica, calcium carbonate, alumina, titanium white barium sulfate, zeolite, diatomaceous earth, activated clay, acid clay, talc, bentonite, iron oxide and the like are preferably used.
  • the functional layer having the moisture barrier function or the like may be a paper pulp, synthetic pulp, synthetic fiber, or a mixture thereof having water resistance and oil resistance manufactured by a manufacturing method such as a wet type or a dry type. it can.
  • 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.
  • the functional layer may be provided on the entire surface of the oxygen scavenger or may be provided on the entire surface. As described later, the functional layer can be provided on the surface of the oxygen scavenger by lamination, coating, or impregnation. When the functional layer is provided by lamination, it is preferably laminated on the oxygen scavenger via an adhesive layer, as will be described later.
  • the adhesive layer is not particularly limited in material and form as long as it can adhere the oxygen scavenger and the functional layer without adversely affecting the oxygen scavenging performance of the oxygen scavenger. It is preferable to have it.
  • Such an air-permeable adhesive layer is a method in which a pressure-sensitive adhesive or an adhesive is applied to one or both of an oxygen scavenger or a functional layer in a streak-like or mesh-like pattern, and laminated.
  • the pressure-sensitive adhesive is preferably a urethane-based pressure-sensitive adhesive.
  • a hot melt adhesive or an adhesive for dry lamination is preferable.
  • the resin constituting the heat-meltable resin material include polyolefin resin and polyethylene resin.
  • the thickness of the oxygen scavenger complex is appropriately set according to the form. In consideration of processability and packaging specifications, 0.0 to 30 mm is preferable, and 0.5 to 20 mm is more preferable.
  • a raw material composition (slurry) containing the oxidizable metal, the fibrous material, and water is prepared.
  • the flocculant examples include inorganic flocculants having metal salt strength, such as sulfate band, polyaluminum chloride aluminum, ferric chloride, polyferric sulfate, and ferrous sulfate; polyacrylamide-based, sodium polyacrylate-based, Polymer flocculating agents such as polyacrylamide Mannheim modified products, poly (meth) acrylic acid aminoalkyl ester series, sodium carboxymethyl cellulose, chitosan series, starch series, polyamide epichlorohydrin series; dimethyl diallyl Organic coagulants such as ammonium chloride or ethyleneimine alkylene dichloride and polyalkylene polyamine condensates, dicyandiamide and formalin condensates; clay minerals such as montmorillonite and bentonite; silicon dioxide such as colloidal silica or hydrates thereof; Hydrous silicate, such as talc Or the like.
  • metal salt strength such as sulfate band, polyaluminum chloride aluminum, ferr
  • flocculants ionic colloidal silica, bentonite, and the like are used in order to improve sheet surface properties, texture formation, formability, fixing rate of components such as the oxidizable metal, and paper strength. It is particularly preferable to use a combination of a cationic starch-polyhydramide-based cationic carboxymethyl cellulose sodium salt and a thione polyamide-epoxychlorohydrin-based cationic and a cationic drug. In addition to the above combinations, these flocculants can be used alone or in combination of two or more.
  • the addition amount of the flocculant is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, based on the solid content of the raw material composition.
  • 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.
  • the raw material composition becomes uniform, and a papermaking product having a uniform thickness and composition can be obtained.
  • it does not cause sticking, tearing, burning, or scorching on drying means during drying, and it does not adversely affect productivity.
  • 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.
  • the oxidation reaction of the papermaking progresses and storage stability such as deoxidation characteristics and strength decreases.
  • 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.
  • the raw material composition is made into a paper.
  • Examples of the papermaking method when the papermaking is made into a sheet form include, for example, a continuous papermaking type circular paper machine, long paper machine, short net paper machine, twin wire paper machine and the like.
  • a manual method which is a batch type papermaking method.
  • a papermaking body can also be formed by multi-layer papermaking using the raw material composition and a composition having a composition different from the raw material composition.
  • the sheets obtained by papermaking the raw material composition are laminated in multiple layers, or a sheet-like material obtained from a composition having a composition different from the raw material composition is laminated on the sheet.
  • a multilayer sheet can also be formed.
  • the three-dimensional shape can be formed by the wet papermaking method that is conventionally used in the pulp molding method.
  • the papermaking body has a moisture content (mass moisture content, the same shall apply hereinafter) until 70% or less. It is preferable to dehydrate it. It is more preferable to dehydrate until it is 60% or less.
  • Examples of the dewatering method of the papermaking after papermaking include dehydration by suction, spraying with pressurized air, dehydration by pressing with a caloric pressure roll or pressure plate, and the like.
  • the paper-making body containing the oxidizable metal is actively dried to separate moisture, thereby suppressing oxidation of the oxidizable metal during the manufacturing process and long-term storage stability. It is possible to obtain an oxygen scavenger intermediate having excellent properties. Furthermore, dry In addition to increasing the supporting ability of the oxidizable metal to the fibrous material later and suppressing its falling off, it is possible to expect improvement in mechanical strength by adding a hot melt component and a thermal crosslinking component. It is preferable to dry the papermaking after the papermaking and before containing the electrolyte.
  • drying means heat drying, vacuum drying, freeze drying and the like can be used as appropriate.
  • the papermaking product is dried by heat drying in terms of production speed, equipment cost, and the like.
  • the heat drying temperature is preferably 60 to 300 ° C, more preferably 80 to 250 ° C.
  • 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.
  • 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.
  • the fall of the deoxidation effect of a deoxidizer can be suppressed.
  • the structure of the oxygen scavenger intermediate is not destroyed due to the rapid evaporation of moisture inside the oxygen scavenger intermediate.
  • the moisture content of the oxygen scavenger intermediate after drying is preferably 20% or less, more preferably 10% or less.
  • 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.
  • the drying method of the papermaking body can be appropriately selected according to the form of the papermaking body, the processing method of the papermaking body before drying, the moisture content before drying, the moisture content after drying, and the like.
  • Examples of the drying method include drying methods such as contact with a heating structure (heating element), spraying of heated air or steam (superheated steam), vacuum drying, electromagnetic wave heating, and electric heating. It can also be carried out simultaneously with the above-mentioned dewatering method.
  • the papermaking body and the oxygen scavenger intermediate are molded, as described above, containing the 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, the manufacturing equipment can be simplified. Also, if necessary, creping, slitting, trimming, processing Processing such as changing the form by processing can also 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.
  • the oxygen scavenger intermediate 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.
  • the functional layer is provided on the oxygen scavenger intermediate.
  • the following functional layer is not provided, but the process of incorporating an electrolyte into the oxygen scavenger intermediate is performed as described later.
  • the functional layer can be selected according to the form of the oxygen scavenger intermediate.
  • the oxygen scavenger intermediate is formed into a sheet
  • a lamination process particularly wet lamination, dry lamination, or extrusion lamination.
  • 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.
  • 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.
  • 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.
  • the electrolyte is contained in the oxygen scavenger intermediate.
  • the step of containing the electrolyte is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • an electrolyte is added by impregnation of the electrolyte, the acid-oxidation reaction immediately after the addition is weak, so the electrolyte can be contained in a normal air atmosphere.
  • the method of incorporating the electrolyte into the oxygen scavenger intermediate can be appropriately set according to the processing method, water content, form, etc. of the oxygen scavenger intermediate after papermaking.
  • Examples of the method of containing the electrolyte include a method of impregnating the oxygen scavenger intermediate with an electrolyte solution having a predetermined concentration of the electrolyte, and adding an electrolyte having a predetermined particle size as a solid to the oxygen scavenger.
  • Examples of the method include the method of inclusion in an intermediate, and among these, the oxygen scavenger intermediate can contain an electrolyte uniformly, and the water content can be adjusted at the same time. I prefer the way to let go.
  • the electrolytic solution is preferably water or a mixture of water and alcohol obtained by electrolyzing an electrolyte. From the standpoint of ease of handling, a water-alcohol mixture is preferred in order to further enhance the self-reactive deoxygenation performance, in which a water-only electrolyte is preferred.
  • 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%.
  • the impregnation method can be appropriately selected according to the form of the oxygen absorber intermediate and the water content.
  • the electrolytic solution is spray-coated on the oxygen scavenger intermediate, and the electrolyte is injected into a part of the oxygen scavenger intermediate with a syringe or the like to reduce the capillary action of the fibrous material.
  • Examples thereof include a method of making use of the oxygen scavenger intermediate, 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.
  • a spray coating method is preferred because it can distribute the electrolyte uniformly, is simple, and requires relatively low equipment costs.
  • 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.
  • the moisture content can be adjusted and stabilized as necessary to obtain an oxygen absorber. And trimming, sheet if necessary In the case of a shape, it can be processed into a predetermined size by performing a process such as stacking two or more sheets.
  • the surface of the oxygen scavenger and oxygen scavenger complex obtained as described above is preferably coated with a coating layer having oxygen permeability.
  • the coating layer may have oxygen permeability on the entire surface, or may partially have oxygen permeability.
  • the material of the coating layer is not particularly limited as long as it has oxygen permeability.
  • the coating layer can be provided, for example, by laminating paper, a nonwoven fabric, a multi-porous film, a resin film provided with fine pores, etc. on the surface of the oxygen scavenger. Further, a synthetic resin paint, an emulsion paint, or the like can be provided by impregnating or applying in an oxygen scavenger.
  • the oxygen removal property can be arbitrarily controlled by the oxygen permeability and water vapor permeability of the coating layer.
  • An oxygen permeability coefficient or the like is used as one index of oxygen permeability.
  • a water vapor transmission coefficient or the like is used as one index of water vapor permeability.
  • 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. .
  • the oxygen scavenger and oxygen scavenger complex of the present embodiment efficiently oxidizes the oxidizable metal, and high oxygen scavenging performance can be obtained with a smaller amount.
  • it has high strength and is flexible enough to be torn when thinned, so it is excellent in workability and productivity.
  • the amount of water that can be held can be set widely, it can also be applied to articles having a wide range of water activity.
  • the oxygen absorption rate can be increased, so oil-containing foods including oil-containing foods such as French fries and fried chicken can be used.
  • 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 coating in the raw material composition is reduced. Dispersibility of the acid metal is improved.
  • 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.
  • the concentration of the salt in the system increases, so that the components such as the oxidizable metal and the electrical interface at the interface of the fibrous material are increased. Since the multilayer is compressed, contact between the component and the fibrous material is remarkably inhibited, and it becomes difficult to fix the component on the surface of the fibrous material, and the sheet is thin and filled with a large amount of the component. It becomes difficult to mold the mold. 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 properties of the oxygen scavenger obtained are significantly inferior.
  • the papermaking body may react with oxygen in water to cause acidification, resulting in a decrease in deoxygenation performance.
  • the papermaking body may easily react with oxygen in the air and may have poor long-term storage stability, and may easily form a molding machine or a processing machine such as a papermaking machine.
  • 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 edge of the cutting blade Generation and wear can be suppressed.
  • the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger can be easily controlled, and pattern impregnation in a certain arbitrary shape can be performed on the same surface. It is possible to obtain a deoxygenated molded article that can be divided into non-reacting parts and non-reactive parts, and can suppress as much as possible the acidity of the oxidizable metal during the production process. Can do.
  • the oxygen scavenger of the second invention is an electrolyte that serves as an acid-oxidation reaction aid to an oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. Is included.
  • the oxygen scavenger of the present embodiment is a so-called self-reactive oxygen scavenger that causes an oxidation reaction of the oxidizable metal with the water content of the oxygen scavenger itself!
  • the water retention agent a water retention agent that is conventionally used for conventional oxygen scavengers can be used without particular limitation.
  • the water retention agent also has a function as an oxygen retention Z supply agent for an oxidizable metal.
  • the water retention agent include activated carbon (rice husk charcoal, charcoal powder, calendar bituminous coal, peat, lignite), carbon black, acetylene black, graphite, zeolite, perlite, vermiculite, silica, cantalinite, fluorite, and the like.
  • activated carbon is preferably used because it has water retention ability, oxygen supply ability, and catalytic ability.
  • the water retention agent it is preferable to use a powdery powder having a particle size of 0.1 to 500 111 from the viewpoint that an effective contact state with an oxidizable metal can be formed. It is more preferable to use a material containing 50% by mass or more of 200 / ⁇ ⁇ .
  • a form other than the powder form as described above for example, a form of a fibrous form such as activated carbon fiber.
  • 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.
  • moisture necessary for the oxidation reaction of the oxidizable metal for obtaining a desired deoxygenation effect can be accumulated in the deoxygenation agent.
  • the air permeability of the oxygen scavenger intermediate is not impaired, the oxygen supply is good, and the oxygen scavenging efficiency is excellent.
  • the occurrence of the water retention agent falling off can be suppressed.
  • the fibrous materials and adhesive components described later constituting the oxygen scavenger intermediate are not reduced, and mechanical strength such as bending strength and tensile strength is also maintained.
  • 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.
  • the oxygen scavenger intermediate may be added with a flocculant, and if necessary, a sizing agent, a colorant, a paper strength enhancer, a step.
  • Additives usually used in paper making such as a retention improver, filler, thickener, pH control agent, bulking agent and the like can be added without particular limitation.
  • the addition amount of the additive can be appropriately set according to the additive to be added.
  • 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.
  • powders such as florite, isolite, and talc, and ceramic fibers and synthetic fibers may be added.
  • the oxygen scavenger intermediate of the present embodiment is formed into a sheet-like form
  • the thickness, basis weight, tear length of one sheet, and air permeability per basis weight lOOgZm 2 are the same as those of the first invention. The description in the embodiment is applied.
  • the description of the thickness of the oxygen scavenger in the embodiment of the first invention is applied.
  • the oxygen scavenger complex of the present embodiment is obtained by providing a functional layer on the oxygen scavenger of the second invention.
  • the functional layer and the adhesive layer of the oxygen scavenger complex using the oxygen scavenger of the second invention, and the thickness of the oxygen scavenger complex are desorbed 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 oxygen agent complex applies.
  • a raw material composition (slurry) containing the oxidizable metal, the water retention agent, the fibrous material, and water is prepared.
  • the addition of the flocculant to the raw material composition the addition of the flocculant described in the embodiment of the oxygen scavenger production method of the first invention is applied.
  • 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.
  • 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.
  • the description in 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.
  • the papermaking body and the oxygen scavenger intermediate are formed by containing an electrolyte as an oxidation reaction aid in the papermaking body and the oxygen scavenger intermediate as described above.
  • an electrolyte as an oxidation reaction aid in the papermaking body and the oxygen scavenger intermediate as described above.
  • the oxygen scavenger intermediate when the oxygen scavenger intermediate is formed into a sheet-like form, it can be used alone or in layers, or on 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.
  • the functional layer is provided on the oxygen scavenger intermediate.
  • the following functional layer is not provided, but the process of incorporating an electrolyte into the oxygen scavenger intermediate is performed as described later.
  • 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 oxygen scavenger according to the first invention is appropriately applied to the coating layer.
  • 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. .
  • the oxygen scavenger and oxygen scavenger complex of the present embodiment can provide high oxygen scavenging performance quickly and in time.
  • it since it has high strength and is flexible enough to resist tearing when thinned, it has excellent workability and productivity.
  • the amount of water that can be retained can be set widely, it can be applied to articles having a wide range of water activity.
  • the oxygen absorption rate can be increased, so that oil-containing foods including oil-containing foods such as French fries and fried chicken are included. The deterioration of the quality of the product due to the deterioration of the acidity of the oil of the product can be prevented.
  • 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 coating in the raw material composition is reduced. Dispersibility of the acid metal 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.
  • the salt concentration in the system increases, so that the components such as the oxidizable metal and the water retention agent and the interface of the fibrous material are increased. Since the electric double layer is compressed, contact between the component and the fibrous material is remarkably hindered, and it becomes 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 becomes very difficult for the same reason, and the oxygen scavenging property of the resulting oxygen scavenger is extremely inferior.
  • the papermaking body may easily react with oxygen in the air and may have poor long-term storage stability, and a molding machine or a processing machine such as a papermaking machine may be easily crushed.
  • 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 cutting blades are used for cutting. Generation and wear can be suppressed.
  • the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger can be easily controlled, and pattern impregnation in a certain arbitrary shape can be performed on the same surface. It is possible to obtain a deoxygenated molded article that can be divided into non-reacting parts and non-reactive parts, and can suppress as much as possible the acidity of the oxidizable metal during the production process. Can do.
  • the electrolyte is included after providing the functional layer on the surface of the oxygen scavenger intermediate, but the production order is not limited to this.
  • the functional layer may be provided after producing an oxygen scavenger by adding an electrolyte to the oxygen scavenger intermediate.
  • a functional layer can be provided on the surface and inside of the oxygen scavenger by impregnating the resin composition.
  • a dehydrating agent After impregnating a dehydrating agent with an aqueous polyvinyl alcohol solution, it is dried by heating to a moisture content that requires the deoxidizing agent, and crosslinking of polybutyl alcohol prevents iron powder contained in the deoxidizing agent from falling off. You can also have a chance.
  • the oxygen scavenger of the present invention and the oxygen scavenger complex of them are molded into a predetermined form by cutting or the like, and housed in a container together with the contents, but have flexibility. Therefore, it is possible to form a container such as a bag or a vouch with an oxygen scavenger or oxygen scavenger complex, or to form a desired three-dimensional shape by press molding into a container having a oxygen scavenging function. You can also. In addition, it can be used by bonding it to the base sheet of the container and forming it into a paperboard container, a hollow shape such as a cylindrical shape or a bottle shape, or a container shape such as a carton or tray shape. By making the oxygen scavenger intermediate in a form other than the sheet form, a container having a deoxygenating function having a form adapted to these containers can be produced.
  • the oxygen scavenger or oxygen scavenger complex of the present invention can be processed into a spherical shape, a noodle shape, a fiber shape, or the like by using extrusion molding, pressure molding, tableting molding or the like after production. .
  • the oxygen scavenger and oxygen scavenger complex of the present invention are used for maintaining the freshness of food, preventing oxidation of medical equipment, anti-mold of metal, bedding, clothes, anti-fungals for art, etc. It can be applied to applications.
  • Tables 1 and 2-1 show the composition ratio and basis weight of the deoxidizing agent
  • Tables 1 and 2 and 2 show the blending ratio of the solid content in the raw material composition and the papermaking yield
  • Tables 1 and 3 show the removal ratio.
  • the effective reaction rate of iron powder in the oxygen agent, the amount of effective iron powder contributing to oxygen absorption determined by VSM force, and the composition ratio of solid content determined by TG force are shown.
  • 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 Hokko PMC Co., Ltd., trade name “W S4020”;>
  • Char-on flocculant sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
  • Electrolyte concentration 1% by mass
  • 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.
  • Fibrous material Pulp fiber (NBKP, Manufacturer: Fletcher Challenge Canada, commodity The name “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 Hokko PMC Co., Ltd., trade name “W
  • Char-on flocculant sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
  • Salt 1.0 part by weight of salt per 100 parts by weight of the slurry
  • the slurry was stirred using JIS pulper according to JIS P8209 and stopped at a support scale of 1000.
  • the obtained oxygen scavenger had a thickness of 0.2 to 0.4 mm and a basis weight of 194 to 263 gZm 2 .
  • the thickness is measured in accordance with JIS P8118 at 5 points or more of the oxygen scavenger, the average value is calculated as the thickness, and the basis weight is measured at the weight of the oxygen scavenger at an area of at least 100 cm 2 . It was calculated by dividing by the area.
  • Example 1-1 An oxygen scavenger of Example 1-1 and Comparative Example 1-1 was installed in a desiccator having an air volume of 5.5 liters without being covered with an oxygen-permeable coating layer, and the oxygen concentration in the desiccator was determined. Measurements were made to determine the deoxygenation performance. Oxygen concentration is made by Taiho Electric Co., Ltd. It was measured using Utah OM-25MS01. The results are shown in Fig. 1.
  • 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.
  • 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 ⁇ 5 mm and a height of 5 mm so as to withstand a high temperature of 1000 ° C. The results are shown in Table 13.
  • Example 1 1 shows an effective reaction rate close to that of the sample stirred by hand of Example 1 2. It was clear that the oxidation reaction was hardly progressing.
  • 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. Therefore, the limiting oxygen concentration of Example 1-1 was 0%, whereas Comparative Example 1-1 was saturated at 6%. Also in paper making yield, Since Examples 1 1 and 1 2 do not contain an electrolyte as a reaction aid at the stage of papermaking, they can be manufactured at a stable, high quality, and low cost industrially with a high papermaking yield. I understood it.
  • 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 weight
  • Water retention agent Activated carbon (produced by Nippon Enviguchi Chemical Co., Ltd., trade name “Carborafyn”)
  • Flocculant The following cationic flocculant 1.0 parts by mass and the following ion flocculant 0.2 parts by mass with respect to 100 parts by mass of the above raw material composition
  • Cationic flocculant Polyamide epoxy hydrin rosin (manufactured by Hokko PMC Co., Ltd., trade name “W S4020”;>
  • Char-on flocculant sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
  • the slurry was stirred using JIS pulper according to JIS P8209 and stopped at a support scale of 1000.
  • ⁇ Electrolytic solution addition conditions 55 parts by mass of the following electrolyte was added to 100 parts by mass of the oxygen scavenger intermediate to obtain a desired oxygen scavenger.
  • the moisture content of the obtained oxygen scavenger was 35.1% by mass as shown in Table 2-1.
  • Electrolyte concentration 1% by mass
  • 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.
  • 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 Hokko PMC Co., Ltd., trade name “W S4020”;>
  • Char-on flocculant sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
  • the slurry was stirred using JIS pulper according to JIS P8209 and stopped at a support scale of 1000.
  • Ageless SA self-reactive type, fast-acting type manufactured by Mitsubishi Gas Chemical Co., Ltd. was used.
  • the obtained oxygen scavenger had a thickness of 0.2 to 0.4 mm and a basis weight of 194 to 302 g / m 2 .
  • 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.
  • 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.
  • 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. Therefore, the critical oxygen concentration was 0% in Example 2-1 while it was saturated at 6% in Comparative Example 2-1. Furthermore, since Example 21 has a water retention agent, it was found that it had the ability to absorb oxygen in a quicker time than Comparative Example 2-1. Also, in terms of papermaking yield, Example 2-1 does not contain an electrolyte as a reaction aid at the papermaking stage, so the papermaking yield is high and it can be manufactured at an industrially stable, high quality and low cost. Is possible. Furthermore, in comparison with a commercially available powder-type oxygen scavenger containing the water retention agent of Comparative Example 22 or 2, it was found that high oxygen scavenging performance was obtained in a quick time.
  • the oxygen scavenger of the first invention the oxidizable metal is efficiently oxidized to reduce the amount. High deoxygenation performance is obtained in quantity.
  • various functions of the functional layer can be imparted to the oxygen scavenging performance of the oxygen scavenger.
  • the production method of the oxygen scavenger and oxygen scavenger complex of the present invention does not include an electrolyte that serves as an oxidation reaction aid, and prepares and manufactures a slurry made of an oxidizable metal and a fibrous material. It is possible to minimize the deterioration of the oxygen removal performance due to the oxidation of the oxidizable metal during preparation, supply and / or molding, and the oxygen absorber and oxygen absorber complex can be preferably produced.
  • 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.

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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 5-70 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

明 細 書  Specification
脱酸素剤、脱酸素剤中間体、脱酸素剤複合体及びその製造方法 技術分野  Oxygen absorber, oxygen absorber intermediate, oxygen absorber complex and method for producing the same
[0001] 本発明は、空気中の酸素と被酸化性金属との酸化反応を利用した脱酸素剤、脱酸 素剤中間体、脱酸素剤複合体及びその製造方法に関する。  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.
背景技術  Background art
[0002] 空気中の酸素と被酸化性金属粉体との酸化反応を利用した脱酸素剤に関する従 来技術としては、例えば、下記特許文献 1に記載の技術が知られている。  [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] この技術は、繊維状物質、鉄粉、水及び電解質からなる混合物を抄紙によりシート 状に成形し、そのガーレ式透気度を 50000秒 ZlOOml以下としたものである。  [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] ところで、この技術で製造された脱酸素剤は、繊維状物質、鉄粉、水及び電解質か らなる混合物を抄紙してシート状に成形して ヽる。酸化反応助剤となる電解質がスラ リー中に添加されているために、スラリーの調製中、供給中及び或いはシート成形中 から鉄粉の酸化反応が起こり、得られる脱酸素剤の性能が低下するほか、特に前記 スラリーを供給中、時間の経過とともに鉄粉の酸化反応が進み、得られる脱酸素剤の 脱酸素性能が時間の経過とともに低下し、一定の性能が得られないなどの問題があ つた。従って、脱酸素剤の品質保証上、最低限必要とされる脱酸素性能を保証する ために、多量の脱酸素剤が必要であった。さらに製造機械に鲭を生じ易くなる問題が あった。また、得られたシートも酸ィ匕が進行するために保存安定性に課題があった。 さらに、脱酸素剤の適用分野によっては、素早い時間で高い脱酸素性能が得られる 脱酸素性能が望まれている分野もあり、それに対応できる脱酸素剤も望まれていた。  [0004] By the way, the oxygen scavenger produced by this technique is obtained by making a paper from a mixture of a fibrous substance, iron powder, water and an electrolyte and forming it into a sheet. Since an electrolyte that serves as an oxidation reaction aid is added to the slurry, the iron powder oxidation reaction occurs during the preparation of the slurry, during the supply, and / or during the sheet forming, and the performance of the resulting oxygen scavenger is reduced. In addition, particularly during the supply of the slurry, the oxidation reaction of iron powder progresses over time, and the deoxidation performance of the resulting oxygen scavenger decreases over time, and there is a problem that certain performance cannot be obtained. I got it. Therefore, a large amount of oxygen scavenger was required to guarantee the minimum required oxygen scavenging performance for the quality assurance of the oxygen scavenger. In addition, there was a problem that wrinkles were likely to occur on the manufacturing machine. Further, the obtained sheet also has a problem in storage stability due to the progress of oxidation. Furthermore, depending on the field of application of the oxygen scavenger, there is a field in which high oxygen scavenging performance can be obtained in a quick time.
[0005] 特許文献 1：特開昭 62— 234544号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 62-234544
発明の開示  Disclosure of the invention
[0006] 従って、本発明の第 1の目的は、被酸化性金属を効率良く酸化反応させ、より少な い量で高い脱酸素性能が得られる脱酸素剤、脱酸素剤中間体、脱酸素剤複合体及 びその製造方法を提供することにある。  Accordingly, the first object of the present invention is to provide an oxygen scavenger, oxygen scavenger intermediate, oxygen 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 its manufacturing method.
また、本発明の第 2の目的は、素早い時間で高い脱酸素性能が得られる脱酸素剤 、脱酸素剤中間体、脱酸素剤複合体及びその製造方法を提供することにある。 The second object of the present invention is to provide an oxygen scavenger capable of obtaining high oxygen scavenging performance in a quick time. An oxygen absorber intermediate, an oxygen absorber complex, and a method for producing the same.
[0007] 本発明は、被酸化性金属及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中 間体に、酸化反応助剤となる電解質を含ませた脱酸素剤であって、前記電解質を 0 . 1〜10質量％含み且つ含水率が 5〜70質量％である脱酸素剤を提供することによ り、前記第 1の目的を達成したものである。以下、この発明を第 1発明ともいう。  [0007] The present invention is an oxygen scavenger comprising an oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal and a fibrous material and an electrolyte serving as an oxidation reaction aid. The first object is achieved by providing an oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass. Hereinafter, this invention is also referred to as a first invention.
[0008] また、本発明は、前記第 1発明の脱酸素剤に使用する脱酸素剤中間体であって、 被酸化性金属及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体を提供す るものである。  [0008] Further, the present invention provides an oxygen scavenger intermediate used in the oxygen scavenger of the first invention, wherein the oxygen scavenger intermediate is formed by drying a papermaking product containing an oxidizable metal and a fibrous material. It provides the body.
[0009] また、本発明は、前記第 1発明の脱酸素剤に機能層が設けられている脱酸素剤複 合体を提供するものである。  [0009] The present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the first invention.
[0010] また、本発明は、前記第 1発明の脱酸素剤の製造方法であって、被酸化性金属及 び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反応助剤となる 電解質を含ませる脱酸素剤の製造方法を提供するものである。 [0010] Further, the present invention provides a 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 oxidized. The present invention provides a method for producing an oxygen scavenger containing an electrolyte as a reaction aid.
[0011] また、本発明は、前記第 1発明の脱酸素剤複合体の製造方法であって、被酸化性 金属及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、前記機能層を 設けた後、酸化反応助剤となる電解質を含ませる脱酸素剤複合体の製造方法を提 供するものである。  [0011] Further, the present invention provides a method for producing the oxygen scavenger complex according to the first invention, wherein an oxygen scavenger intermediate formed by drying a paper product containing an oxidizable metal and a fibrous material is provided. After the functional layer is provided, a method for producing an oxygen scavenger complex containing an electrolyte as an oxidation reaction aid is provided.
[0012] また、本発明は、前記第 1発明の脱酸素剤複合体の製造方法であって、被酸化性 金属及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反応助剤 となる電解質を含ませて脱酸素剤を製造した後、該脱酸素剤に前記機能層を設けた 脱酸素剤複合体の製造方法を提供するものである。  [0012] Further, the present invention provides a method for producing the oxygen scavenger complex according to the first invention, wherein an oxygen scavenger intermediate obtained by drying a papermaking product containing an oxidizable metal and a fibrous material is provided. The present invention provides a method for producing an oxygen scavenger complex, in which an oxygen scavenger is produced by including an electrolyte as an oxidation reaction aid, and then the functional layer is provided on the oxygen scavenger.
[0013] 本発明は、被酸化性金属、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱 酸素剤中間体に、酸化反応助剤となる電解質を含ませた脱酸素剤であって、前記電 解質を 0. 1〜10質量％含み且つ含水率が 5〜70質量％である脱酸素剤を提供す ることにより、前記第 2の目的を達成したものである。以下、この発明を第 2発明ともい  [0013] 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. Then, the second object is achieved by providing an oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass. Hereinafter, this invention is also referred to as the second invention.
[0014] また、本発明は、前記第 2発明の脱酸素剤に使用する脱酸素剤中間体であって、 被酸化性金属、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間 体を提供するものである。 [0014] Further, the present invention is an oxygen scavenger intermediate used in the oxygen scavenger of the second invention, and is obtained by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. Middle oxygen scavenger Provide the body.
[0015] また、本発明は、前記第 2発明の脱酸素剤に機能層が設けられている脱酸素剤複 合体を提供するものである。  [0015] The present invention also provides an oxygen scavenger complex in which a functional layer is provided on the oxygen scavenger of the second invention.
[0016] また、本発明は、前記第 2発明の脱酸素剤の製造方法であって、被酸化性金属、 保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反応 助剤となる電解質を含ませる脱酸素剤の製造方法を提供するものである。  [0016] 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.
[0017] また、本発明は、前記第 2発明の脱酸素剤複合体の製造方法であって、被酸化性 金属、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、前 記機能層を設けた後、酸化反応助剤となる電解質を含ませる脱酸素剤複合体の製 造方法を提供するものである。  [0017] Further, the present invention is a method for producing the oxygen scavenger complex according to the second invention, wherein the oxygen scavenger is obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material. An object of the present invention is to provide a method for producing an oxygen scavenger complex in which an intermediate layer is provided with the functional layer and then contains an electrolyte that serves as an oxidation reaction aid.
[0018] また、本発明は、前記第 2発明の脱酸素剤複合体の製造方法であって、被酸化性 金属、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸 化反応助剤となる電解質を含ませて脱酸素剤を製造した後、該脱酸素剤に前記機 能層を設けた脱酸素剤複合体の製造方法を提供するものである。  [0018] Further, the present invention is a method for producing the oxygen scavenger complex according to the second invention, wherein the oxygen scavenger is obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material. Provided is 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 an intermediate, and then the functional layer is provided on the oxygen scavenger. .
図面の簡単な説明  Brief Description of Drawings
[0019] [図 1]本発明の実施例 1 1及び比較例 1 1の脱酸素剤の脱酸素性能を示す図で ある。  FIG. 1 is a diagram showing the oxygen scavenging performance of oxygen scavengers of Example 11 and Comparative Example 11 of the present invention.
[0020] [図 2]本発明の実施例 2— 1及び比較例 2— 1、 2— 2の脱酸素剤の脱酸素性能を示 す図である。  [0020] 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.
発明の詳細な説明  Detailed Description of the Invention
[0021] 以下本発明を、その好ましい実施形態に基づき図面を参照しながら説明する。以 下においては、先ず、前記第 1発明の脱酸素剤及びそれを使用した脱酸素剤複合 体並びにそれらの製造方法について説明し、次に、前記第 2発明の脱酸素剤及びそ れを使用した脱酸素剤複合体並びにそれらの製造方法について説明する。  Hereinafter, the present invention will be described based on 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.
[0022] 第 1発明の脱酸素剤は、被酸化性金属及び繊維状物を含む抄造体を乾燥してなる 脱酸素剤中間体に、酸化反応助剤となる電解質を含ませたものである。本実施形態 の脱酸素剤は、脱酸素剤自身の有する水分で被酸化性金属の酸化反応が生じる ヽ わゆる自力反応型の脱酸素剤である。 [0023] 本実施形態の脱酸素剤は、前記電解質を 0. 1〜10質量％、好ましくは 0. 2〜8質 量％、より好ましくは 0. 3〜6質量％含み、且つ含水率が 5〜70質量％、好ましくは 7 〜60質量％、より好ましくは 10〜50質量％である。 [0022] 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 that serves as an oxidation reaction aid. . The oxygen scavenger of this embodiment is a so-called self-reactive oxygen scavenger in which the oxidation reaction of the oxidizable metal occurs with the moisture of the oxygen scavenger itself. [0023] 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. 5 to 70% by mass, preferably 7 to 60% by mass, more preferably 10 to 50% by mass.
脱酸素剤に含まれる電解質量及び脱酸素剤の含水率が斯かる範囲であると、酸化 反応を持続するために必要な水分を十分確保でき、酸化反応が十分に進行する。ま た、該脱酸素剤に均一に水分を供給することができるため、均一な脱酸素性能を得 ることができるとともに脱酸素剤の通気性を損なわないため、被酸ィ匕性金属を効率良 く酸化反応させ、より少な!ヽ量で高!ヽ脱酸素性能が得られる。  When the electrolytic mass contained in the oxygen scavenger and the moisture content of the oxygen scavenger are within such ranges, sufficient water can be secured to sustain the oxidation reaction, and the oxidation reaction proceeds sufficiently. In addition, since water can be uniformly supplied to the oxygen scavenger, uniform oxygen scavenging performance can be obtained and air permeability of the oxygen scavenger is not impaired. Oxidation reaction is good, and the amount of deoxygenation can be increased with less amount and high amount.
[0024] 前記電解質には、従来力 この種の脱酸素剤に通常用いられている電解質を特に 制限なく用いることができる。該電解質としては、例えば、アルカリ金属、アルカリ土類 金属若しくは重金属の硫酸塩、炭酸塩、塩ィ匕物又は水酸ィ匕物等が挙げられる。そし てこれらの中でも、導電性、化学的安定性、生産コストに優れる点から塩ィ匕ナトリウム 、塩ィ匕カリウム、塩ィ匕カルシウム、塩化マグネシウム、第一塩化鉄、第二塩化鉄等の 各種塩ィ匕物が好ましく用いられる。これらの電解質は、単独で又は二以上を組み合 わせて用いることもできる。  [0024] As 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 sulfates, carbonates, salts, hydroxides, and the like of alkali metals, alkaline earth metals, or heavy metals. Among them, various kinds such as sodium chloride sodium, sodium chloride potassium, sodium chloride calcium, magnesium chloride, ferrous chloride, ferric chloride are provided because of their excellent conductivity, chemical stability, and production cost. Salty salt is preferably used. These electrolytes can be used alone or in combination of two or more.
[0025] 前記被酸化性金属には、従来力 この種の脱酸素剤に通常用いられている被酸ィ匕 性金属を特に制限無く用いることができる。該被酸化性金属の形態は、取り扱い性、 成形性等の観点から粉体、繊維状の形態を有するものを用いることが好ま 、。 粉体の形態を有する被酸化性金属としては、例えば、鉄粉、アルミニウム粉、亜鉛 粉、マンガン粉、マグネシウム粉、カルシウム粉等が挙げられ、これらの中でも取り扱 い性、安全性、製造コストの点力 鉄粉が好ましく用いられる。該被酸化性金属には 、後述の繊維状物への定着性、反応のコントロールが良好なことから粒径 (以下、粒 径というときには、粉体の形態における最大長さ、又は動的光散乱法、レーザー回折 法等により測定される平均粒径をいう。）が 0. 1〜300 /ζ πιのものを用いることが好ま しぐ粒径が 0. 1〜150 mものを 50質量％以上含有するものを用いることがより好 ましい。  [0025] As the oxidizable metal, an oxidizable metal that is conventionally used for this type of oxygen scavenger can be used without particular limitation. As the form of the oxidizable metal, it is preferable to use a form having a powdery or fibrous form from the viewpoints of handleability and moldability. Examples of the oxidizable metal having a powder form include iron powder, aluminum powder, zinc powder, manganese powder, magnesium powder, and calcium powder. Among these, 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.
また、繊維状の形態を有する被酸化性金属としては、スチール繊維、アルミ繊維、 マグネシウム繊維等が挙げられる。これらのなかでも取り扱い性、安全性、製造コスト の点からスチール繊維、アルミ繊維等が好ましく用いられる。繊維状の形態を有する 被酸化性金属は、成形性や得られる脱酸素剤の機械的強度、表面の平滑性、脱酸 素性能の点から繊維長 0. l〜50mm、太さ 1〜1000 mのものを用いることが好ま しい。 Examples of the oxidizable metal having a fibrous form include steel fibers, aluminum fibers, and magnesium fibers. Among these, handling, safety, manufacturing cost From this point, steel fibers, aluminum fibers and the like are preferably used. 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.
[0026] 前記脱酸素剤中の前記被酸化性金属は、有効反応率が 75%以上であることが好 ましぐ 85%以上であることがより好ましい。有効反応率が斯かる範囲であると、脱酸 素剤製造時のスラリー調製中及び抄造中から被酸化性金属の酸化反応が抑制され ているため、包装仕様上必要な脱酸素能力を得るための脱酸素剤を小型 ·軽量ィ匕で きるほか、脱酸素剤の原料コストを安くすることができる。ここで有効反応率 (％)は、 下記式 1で表される脱酸素剤中における脱酸素に有効な被酸ィ匕性金属の割合を、 下記式 2で表される原材料段階における被酸化性金属の割合で除した下記式 3で求 められる値である。なお、該有効反応率の上限値は 100%である。  [0026] The oxidizable metal in the oxygen scavenger has an effective reaction rate of preferably 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 deoxidizing agent, so that the deoxygenation ability required for the packaging specification is obtained. The oxygen scavenger can be made small and light, 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 oxidizability at the raw material stage represented by the following formula 2. This is the value obtained by the following formula 3 divided by the metal ratio. The upper limit of the effective reaction rate is 100%.
[0027] 脱酸素に有効な被酸化性金属の質量 Z脱酸素剤の質量 =Α· · '式 1  [0027] Mass of oxidizable metal effective for deoxidation Mass of Z oxygen scavenger = Α ·· 'Equation 1
原材料段階における被酸化性金属の質量 Ζ脱酸素剤の質量 =Β· · '式 2 脱酸素剤の有効反応率 (％) = (Α/Β) X 100· · ·式 3  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
ここで、脱酸素剤の質量は脱酸素剤を窒素雰囲気中で 100°C付近まで加熱して、 水分を蒸発させた絶乾質量を用いるが、水分を含んだ状態での質量のままでも良い 。ただし、式 1と式 2での脱酸素剤の水分の状態を合わせておく必要がある。  Here, the mass of the oxygen scavenger is the dry mass obtained by heating the oxygen scavenger to near 100 ° C in a nitrogen atmosphere to evaporate the water, but the mass in a state containing water may be used as it is. . However, the oxygen content of the oxygen scavenger in Equation 1 and Equation 2 must be matched.
また、上記の包装仕様とは、例えば食品等とともに本願の脱酸素剤をバウチ等の袋 に充填して製造された製品の厚みや重量が、脱酸素剤の為に厚すぎたり重過ぎたり することなく性能を発揮できる、食品保存の為に必要な脱酸素能力のことである。  In addition, the above packaging specification means that, for example, the thickness and weight of a product manufactured by filling a bag such as a 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.
[0028] 以下に被酸化性金属に鉄粉、繊維状物に木材パルプを用いた脱酸素剤を例に、 熱重量測定法 (Thermogravimetry、略称 TG)と振動試料型磁力計 (Vibrating Sample Magnetometer,略称 VSM)を用いて有効反応率を求める方法にっ 、て説明する。  [0028] 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 abbreviation VSM) will be described.
[0029] 熱重量測定法により、原材料段階での鉄粉の質量比率を求めることができる。脱酸 素剤から試料を作成し、この試料をサンプル容器に入れ窒素雰囲気中で室温から徐 々に温度を上げていくと、 100°C付近で脱酸素剤に含まれていた水分が蒸発し、 35 0°C付近で急激に質量が減少する。この質量減少分は木材パルプ中に含まれるセル ロース分解量である。さらに温度を上げて 550°Cから空気を導入し、 1000°Cまでカロ 熱すると木材パルプが燃焼し、最終的には酸化鉄と木材パルプに由来する灰分の みサンプル容器に残留する。木材パルプに由来する灰分は木材パルプ単体で熱重 量測定法を用いることにより求めることができる。上記、脱酸素剤の場合と同様に加 熱することにより、セルロース分解量と木材パルプ由来の灰分の関係を求めることが できる。よって酸化鉄の質量はサンプル容器残留分から、セルロース分解量力ゝら算 出した木材パルプ由来の灰分を引 、たものになる。 [0029] The mass ratio of the iron powder at the raw material stage can be determined by thermogravimetry. When a sample was prepared from the deoxidizer, and the sample was placed in a sample container and gradually raised from room temperature in a nitrogen atmosphere, the water contained in the deoxidizer evaporated near 100 ° C. , Mass rapidly decreases around 350 ° C. This mass loss is the cell contained in the wood pulp. It is the amount of roast degradation. When the temperature is further raised and air is introduced from 550 ° C and heated to 1000 ° C, the wood pulp burns and eventually 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 described above, 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 content derived from wood pulp calculated from the residual amount of cellulose in the sample container.
[0030] この酸化鉄の質量を元に試料中に含まれて!/、た鉄粉の質量を求めることができる。 [0030] Based on the mass of iron oxide, the mass of iron powder contained in the sample can be determined.
酸ィ匕鉄の質量力 原材料の鉄粉の質量を求めるための補正係数は一般的には鉄の 酸化反応式より、補正係数が得られるが、通常、原材料メーカーから供給される鉄粉 は純鉄 100%ではないので、補正係数は実験的に求める。鉄粉の試料をサンプル 容器に入れ、 600°Cまで窒素雰囲気中で絶乾させた後、空気をカ卩えて 1000°Cまで 加熱し、酸化鉄を生成させる。この生成させた酸化鉄の質量と原料の鉄粉の質量と の関係力 補正係数を求めることができる。この実験によって得られた補正係数を用 The mass coefficient of acid iron iron The correction coefficient for obtaining the mass of iron powder of the raw material is generally obtained from the iron oxidation reaction equation, but the iron powder supplied from the raw material manufacturer 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 mass of the iron oxide produced and the mass of the iron powder of the raw material can be obtained. The correction factor obtained from this experiment was used.
V、て酸ィ匕鉄の質量力も鉄粉の質量を求めることができ、試料の質量との割合力も原 材料段階での鉄粉の質量比率 (式 5)を求めることができる。 V, the mass force of ferrous iron can also determine the mass of the iron powder, and the ratio force with the mass of the sample can also determine the mass ratio of the iron powder at the raw material stage (Equation 5).
[0031] 次に振動試料型磁力計を用いて脱酸素剤中の脱酸素に有効な鉄粉の質量を求め る方法につ!ヽて説明する。鉄粉を試料として振動試料型磁力計を用いて外部磁場を 印加すると鉄粉が磁化される。鉄粉の磁ィ匕量は外部磁場が大きくなると飽和し、この 飽和磁化量は鉄粉の試料の質量に比例する。また、この鉄粉の試料に酸素を吸収さ せると鉄粉が失活 (脱酸素能力を失うこと)していき、飽和磁ィ匕量は脱酸素に有効な鉄 粉に比例して減少していき、鉄粉がすべて酸化鉄に変化して脱酸素能力が無くなる と飽和磁ィ匕量もほとんどゼロになる。よって脱酸素剤の試料の飽和磁ィ匕量を測定す ることにより、脱酸素剤の試料中に含まれる脱酸素に有効な鉄粉の質量を求めること ができる。脱酸素に有効な鉄粉の質量を試料の質量で割ると脱酸素剤中における酸 素吸収に有効な鉄粉の割合を求めることができる (式 4)。脱酸素剤の試料の有効反 応率は、下記式 4で表される脱酸素剤中における脱酸素に有効な鉄粉の割合を、下 記式 5で表される原材料段階における鉄粉の割合で除した下記式 6で求められる値 である。 [0031] 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 iron powder is used as a sample and an external magnetic field is applied using a vibrating sample magnetometer, 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 amount of saturation magnetism decreases in proportion to the iron powder effective for deoxygenation. As the iron powder changes to iron oxide and the deoxygenation 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. By dividing the mass of iron powder effective for deoxygenation by the mass of the sample, the ratio of iron powder effective for oxygen absorption in the oxygen scavenger can be obtained (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 expressed by the following formula 4, and the ratio of iron powder in the raw material stage expressed by formula 5 below. The value obtained by the following formula 6 divided by It is.
[0032] 脱酸素に有効な鉄粉の質量 Z脱酸素剤の試料質量 =C' · '式 4  [0032] Mass of iron powder effective for deoxygenation Sample mass of Z deoxidizer = C '·' Equation 4
原材料段階での鉄粉の質量 Z脱酸素剤の試料質量 =D' · '式 5  Mass of iron powder at raw material stage Sample mass of Z oxygen scavenger = D '·' Equation 5
脱酸素剤の有効反応率 (％) = (C/D) X 100· · ·式 6  Effective reaction rate of oxygen scavenger (%) = (C / D) X 100 ··· Equation 6
[0033] 前記脱酸素剤中間体中の前記被酸ィ匕性金属の配合量は、 10〜98質量％である ことが好ましぐ 30〜90質量％であることがより好ましい。被酸化性金属の配合量が 斯かる範囲であると、所望の脱酸素性能が得られる。また、前記脱酸素剤中間体を 構成する後述の繊維状物、接着成分 (凝集剤等)の増加を抑えることができ、硬くな らず使用感に優れる。また、得られる脱酸素剤中間体を脱酸素剤としたときに、その 表面に被酸化性金属等の酸化皮膜が形成されても通気性が損なわれることがなぐ その結果脱酸素剤の内部まで反応が起こり易くなつて高い脱酸素性能が得られる。 また、酸ィ匕反応によって被酸ィ匕性金属が膨張'凝結して硬くなり過ぎることがない。ま た、被酸ィ匕性金属の脱落も抑えることができる。また、脱酸素剤中間体を形成する後 述の繊維状物、接着成分が十分含まれることとなるため、曲げ強度や引張強度等の 機械的強度の低下を抑えることができる。ここで、脱酸素剤中間体中の被酸化性金 属の配合量は、 JIS P8128に準じる灰分試験や前記熱重量測定法で求めることが できる。また、例えば、鉄の場合は外部磁場を印加すると磁ィ匕が生じる性質を利用し て前記振動試料型磁力計を用いて試料型磁ィ匕測定試験等により定量することができ る。  [0033] 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.
[0034] 前記繊維状物としては、例えば、天然繊維状物としては植物繊維 (コットン、カボッ ク、木材パルプ、非木材パルプ、落花生たんぱく繊維、とうもろこしたんぱく繊維、大 豆たんぱく繊維、マンナン繊維、ゴム繊維、麻、マニラ麻、サイザル麻、ニュージーラ ンド麻、羅布麻、椰子、いぐさ、麦わら等）、動物繊維（羊毛、やぎ毛、モヘア、カシミ ァ、アルカノく、アンゴラ、キャメル、ビキューナ、シルク、羽毛、ダウン、フェザー、アル ギン繊維、キチン繊維、ガゼイン繊維等）、鉱物繊維 (石綿等）が挙げられ、合成繊維 状物としては、例えば、半合成繊維 (アセテート、トリアセテート、酸化アセテート、プロ ミックス、塩ィ匕ゴム、塩酸ゴム等)、金属繊維、炭素繊維、無機繊維 (例えばガラス繊 維、セラミック繊維等)等が挙げられる。また、高密度ポリエチレン、中密度ポリェチレ ン、低密度ポリエチレン、ポリプロピレン等のポリオレフイン、ポリエステル、ポリ塩化ビ ユリデン、デンプン、ポリビュルアルコール若しくはポリ酢酸ビュル又はこれらの共重 合体若しくは変性体等の単繊維、又はこれらの榭脂成分を鞘部に有する芯鞘構造 の複合繊維を用いることができる。そしてこれらの中でも、繊維どうしの接着強度が高 ぐ繊維どうしの融着による三次元の網目構造を作り易すぐパルプ繊維の発火点よ りも融点が低い点からポリオレフイン、変性ポリエステルが好ましく用いられる。また、 枝分かれを有するポリオレフイン等の合成繊維も被酸化性金属との定着性が良好な ことから好ましく用いられる。これらの繊維は、単独で又は二以上を組み合わせて用 いることができる。また、これらの繊維は、その回収再利用品を用いることもできる。そ して、これらの中でも、前記被酸化性金属の定着性、得られる抄造体の柔軟性、空隙 の存在力 くる酸素透過性、製造コスト等の点から、木材パルプ、コットンが好ましく 用いられる。 [0034] Examples of the fibrous material include plant fibers (cotton, caboch, 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, Salt fiber rubber, hydrochloric acid rubber, etc.), metal fibers, carbon fibers, inorganic fibers (e.g. glass fibers, ceramic fibers, etc.) Can be mentioned. High density polyethylene, medium density polyethylene Polyolefin such as polyethylene, low density polyethylene, polypropylene, etc., polyester, polyvinylidene chloride, starch, polybulal alcohol or polyacetic acid bull, or a single fiber such as a copolymer or a modified product thereof, or a coconut resin component thereof. The composite fiber having a core-sheath structure 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 preferably used from the viewpoints of fixability of the oxidizable metal, flexibility of the resulting papermaking, oxygen permeability due to the presence of voids, production cost, and the like.
前記繊維状物は、そのカナディアン ·スタンダード 'フリーネス（CSF: Canadian S tandard Freeness)力 600ml以下であることが好ましぐ 450ml以下であることが より好ましい。 CSFが 600ml以下であると、繊維状物と被酸化性金属等の成分との 定着性が良好であり、所定の配合量を保持できて得られる脱酸素剤が脱酸素性能に 優れるものとなる。また、均一な厚みの脱酸素剤中間体が得られる等、成形性も良好 となる。また、繊維状物と該成分との定着が良好であるため、該成分の脱落、該成分 と該繊維状物との絡み合い、水素結合に由来する結合強度が得られる。このため、 曲げ強度や引張強度等の機械的強度が保たれ、加工性も良好となる。  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. . In addition, moldability is improved, such as obtaining an oxygen scavenger intermediate with a uniform thickness. In addition, since the fixing between the fibrous material and the component is good, it is possible to obtain a bond strength derived from the removal of the component, the entanglement between the component and the fibrous material, and hydrogen bonding. For this reason, mechanical strength such as bending strength and tensile strength is maintained, and workability is also improved.
前記繊維状物の CSFは、低い程好ましいが、通常のパルプ繊維のみの抄紙では、 繊維状物以外の成分比率が低い場合、 CSFが 100ml未満であると濾水性が非常に 悪ぐ脱水が困難となって均一な厚みの抄造体が得られな力つたり、乾燥時にブリス ター破れが生じたりする等の成形不良となったりする。一方、本発明においては、繊 維状物以外の成分比率が高いことから、 CSFが 100ml未満であっても濾水性も良好 で均一な厚みの脱酸素剤中間体を得ることができる。また、 CSFが低い程、フイブリ ルが多くなるため、繊維状物と該繊維状物以外の成分との定着性が良好となり、高い 強度の脱酸素剤中間体を得ることができる。 繊維状物の CSFの調整は、叩解処理などによって行うことができる。 CSFの低い繊 維と高い繊維とを混ぜ合わせ、 CSFの調整を行っても良い。なお、 CSFiお IS P81 21 (パルプのろ水度試験方法）に示す方法で測定することにより得ることができ、 0以 上の値を示す繊維状物の水切れの程度を表す指標である。 The lower the CSF of the fibrous material, the better. However, in the case of ordinary pulp fiber-only paper, if the component ratio other than the fibrous material is low, if the CSF is less than 100 ml, the drainage will be very poor and difficult to dewater. As a result, it becomes difficult to obtain a paper product having a uniform thickness, or a molding failure such as blister breakage occurs during drying. On the other hand, in the present invention, since the ratio of components other than the fibrous material is high, an oxygen scavenger intermediate with good drainage and uniform thickness can be obtained even if the CSF is less than 100 ml. Further, the lower the CSF, the more fibrils, the better the fixability between the fibrous material and components other than the fibrous material, and a high-strength oxygen scavenger intermediate can be obtained. Adjustment of the CSF of the fibrous material can be performed by a beating process or the like. CSF may be adjusted by mixing low and high CSF fibers. It is an index that represents the degree of water breakage of a fibrous material that can be obtained by measuring by the method shown in CSFi and IS P81 21 (pulp freeness test method).
[0036] 前記繊維状物は、その表面電荷がマイナス (負）であることが好ま 、。表面電荷が マイナスに強く帯電するに従い、繊維状物への被酸化性金属等の粉体成分の定着 性が良好であり、粉体の保持性が高くなり、得られる脱酸素剤の脱酸素性能がより高 められる。また、湿式抄紙工程における排水に被酸化性金属等の粉体成分が多量 に混じることが抑えられ、生産性や環境保全に悪影響を及ぼすことがない。特に、得 られる脱酸素剤中間体の歩留まりを一層高める点からは、前記繊維状物は、その電 荷量が 2. 5 X 10— 6eq/g以下であることが好ましぐ電荷量が 4. O X 10"6eq/g 以下がより好ましい。ここで、繊維状物の電荷量は、コロイド滴定により測定される。ま た、荷電粒子界面と溶液間のずり面における見掛けの電位であるゼータ電位にぉ ヽ ても同様であり、これは流動電位法や電気泳動法等により測定される。 [0036] Preferably, the fibrous material has a negative (negative) surface charge. As the surface charge is strongly negatively charged, the fixability of powder components such as oxidizable metals to the fibrous material is good, the powder retention is high, and the oxygen scavenger performance of the resulting oxygen scavenger Is increased. 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 it does not adversely affect productivity and environmental conservation. In particular, the the terms further increase the yield of the oxygen scavenger intermediates obtained, the fibrous material, the electric load amount 2. there is preferably instrument charge amount or less 5 X 10- 6 eq / g 4. OX 10 " 6 eq / g or less is more preferred. Here, the amount of charge of the fibrous material is measured by colloid titration. It is the apparent potential at the shear surface between the charged particle interface and the solution. The same applies to the zeta potential, which is measured by the streaming potential method, the electrophoresis method or the like.
[0037] 該繊維状物には、平均繊維長が 0. l〜50mmのものを用いることが好ましぐ 0. 2 〜20mmのものを用いることがより好ましい。平均繊維長が斯カる範囲であると、得ら れる脱酸素剤中間体の十分な曲げ強度や引張強度等の機械的強度が得られる。ま た、紙層が密に形成され過ぎず、脱酸素剤中間体の通気性が損なわれないため、酸 素供給が良好となって脱酸素性に優れる。また、脱酸素剤中間体中に該繊維状物 が均一に分散し、一様な機械的強度が得られる。また、均一な肉厚の脱酸素剤中間 体が得られ、繊維間隔が広くなりすぎず、繊維による前記被酸化性金属等の成分の 保持能力が得られるため、該成分の脱落が抑えられる。  [0037] The fibrous material preferably has an average fiber length of 0.1 to 50 mm, more preferably 0.2 to 20 mm. When the average fiber length is within such a range, sufficient mechanical strength such as bending strength and tensile strength of the obtained oxygen scavenger intermediate can be obtained. Further, since the paper layer is not formed too densely and the air permeability of the oxygen scavenger intermediate is not impaired, the oxygen supply is good and the oxygen scavenging property is excellent. Further, the fibrous material is uniformly dispersed in the oxygen scavenger intermediate, and uniform mechanical strength can be obtained. In addition, an oxygen scavenger intermediate having a uniform thickness is obtained, the fiber spacing is not excessively wide, and the ability of the component such as the oxidizable metal to be retained by the fiber is obtained, so that dropping of the component is suppressed.
[0038] 前記脱酸素剤中間体中の前記繊維状物の配合量は、 2〜50質量％であることが 好ましぐ 5〜40質量％であることがより好ましい。該配合量が斯カる範囲内であると 、被酸化性金属の脱落防止効果が得られる。また、脱酸素剤中間体も柔軟なものと なる。また、得られる脱酸素剤中間体中の前記被酸化性金属等の成分の比率が低く ならず、所望の脱酸素性能が得られる。  [0038] The blending 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.
[0039] ここで、各成分の組成比は、例えば熱重量測定法により繊維状物の含有量や被酸 化性物質の含有量を求めことができる。 [0039] Here, the composition ratio of each component is determined by, for example, thermogravimetry, the content of the fibrous material or the acid content. The content of chemical substances can be determined.
[0040] 前記脱酸素剤中間体は、前記繊維状物以外の成分を 50質量％以上含んで 、るこ と力 子ましく、 70質量％以上含んでいることがより好ましぐ 80質量％以上含んでい ることがさらに好ましい。繊維状物以外の成分が 50質量％以上であると、脱酸素性 能が良好となる。繊維状物以外の成分は多い程好ましいが、脱酸素剤中間体の加 ェ性を維持するのに必要な強度を得る点から、その上限は、 98質量％程度とするこ とが好ましい。  [0040] The oxygen scavenger intermediate contains 50% by mass or more of components other than the fibrous material, more preferably 70% by mass or more, and more preferably 80% by mass. More preferably, it is contained. 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.
[0041] 前記脱酸素剤中間体には、後述するように凝集剤が添加されていてもよい。  [0041] As described later, a flocculant may be added to the oxygen scavenger intermediate.
また、前記脱酸素剤中間体には、必要に応じ、サイズ剤、着色剤、紙力増強剤、歩 留向上剤、填料、増粘剤、 pHコントロール剤、嵩高剤等の抄紙の際に通常用いられ る添加物を特に制限無く添加することができる。該添加物の添加量は、添加する添 加物に応じて適宜設定することができる。  In addition, the oxygen scavenger intermediate is usually used for paper making such as sizing agent, coloring agent, paper strength enhancer, yield improver, filler, thickener, pH control agent, bulking agent, etc. The additive used can be added without any particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.
[0042] また、製品の外観上、着色が必要な場合には、酸化チタンや炭酸カルシウム、アル ミナホワイト等の着色粉体を添加してもよい。さらに酸化反応促進や柔軟性の向上の ために、フローライト、イソライト、タルク等の粉体や前記セラミック繊維や合成繊維を 添カロすることちでさる。  [0042] 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, it can be done by adding powder of florite, isolite, talc, etc., or ceramic fibers and synthetic fibers.
[0043] 前記脱酸素剤中間体をシート状の形態に形成した場合には、その 1枚の厚みは 0.  [0043] When the oxygen scavenger intermediate is formed in a sheet form, the thickness of one sheet is 0.
08-1. 2mmであることが好ましぐ 0. 1〜0. 6mmであることがより好ましい。厚み が 0. 08mm以上であると脱酸素性能、機械的強度、前記被酸化性金属等の成分の 定着性も良好であり、安定した均一の肉厚、組成分布が得ることができる。また、ピン ホールの発生等によるシートの破壊等が発生し難ぐ生産性及び加工性に支障を来 すことがない。該厚みが 1. 2mm以内であると、脱酸素剤中間体の折曲強度の低下 も抑えられる。また、脆性破壊を起こし難ぐ柔らかいシートが得られる。また、生産性 においても、紙層形成時間や乾燥時間を短くできて、操業性に優れる。また、脱酸素 性能も良好である。また、割れや折れも起こり難いため、加工性に優れる。  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.
[0044] 前記脱酸素剤中間体をシート状の形態に形成した場合には、その 1枚の坪量は 10 〜1000gZm2であることが好ましぐ 50〜600gZm2であることがより好ましい。該坪 量が lOgZm2以上であると被酸ィ匕性金属等の中でも比重の大きなものを使用する場 合等において、特に安定したシートを形成することができる。該坪量が lOOOgZm2 以内であると軽くて使用感も良好である。また、生産性や操業性等も良好となる。 [0044] wherein when the oxygen scavenger intermediate was formed into a sheet form, the basis weight of one that is more preferably from 10 ~1000gZm 2 is preferably tool 50~600gZm 2. When the basis weight is lOgZm 2 or more, a metal having a high specific gravity is used among acid-oxidizing metals. In particular, a particularly stable sheet can be formed. When the basis weight is within lOOOgZm 2, it is light and feels good. In addition, productivity and operability are also improved.
[0045] 前記脱酸素剤中間体をシート状の形態に形成した場合には、その 1枚の裂断長は 100〜4000mであること力好ましく、 200〜3000mであること力より好ましい。該裂 断長が 100m以上であると、操業時にシートの破断や切断が生じることがなく安定的 にシートを形成できる。また、加工時にも同様の理由によって製品加工が良好に行え る。また、使用時においても、適度に腰があって使用感に優れる。該裂断長が 4000 m以内であると、シートを形成する繊維状物、接着成分が多くなりすぎず、柔軟で脱 酸素性能に優れるものとなる。ここで、裂断長は、シートから長さ 150mm X幅 15mm の試験片を切り出した後、 JIS P8113に準じ、該試験片をチャック間隔 100mmで 引っ張り試験機に装着し、引っ張り速度 20mmZminで引っ張り試験を行い、下記 計算式により算出される値である。  [0045] When the oxygen scavenger intermediate is formed into a sheet 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. Also, the product can be processed well for the same reason during processing. Further, even during use, it is reasonably comfortable and has a good feeling of use. When the breaking length is 4000 m or less, the fibrous material and adhesive component forming the sheet do not increase excessively, and the material is flexible and excellent in deoxygenation 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.
裂断長〔m〕 = (l/9.8) X (引張強さ〔N/m〕） X 106/ (試験片坪量〔g/m2〕）Breaking length [m] = (l / 9.8) X (Tensile strength [N / m]) X 10 6 / (Test piece basis weight [g / m 2 ])
[0046] 前記脱酸素剤中間体は、脱酸素反応を良好に進行させる点ゃ該能力の向上、ま た、電解液を添加する際により均一に電解液を含ませることができる点等を考慮する と、坪量 lOOgZm2当たりの透気度が 0. 1〜： LOOO秒 Z (6. 4cm2 ' 300ml)であるこ と力 S好ましく、 0. 1〜500秒 Z (6. 4cm2' 300ml)であることがより好ましい。 [0046] The oxygen scavenger intermediate allows the oxygen scavenging reaction to proceed satisfactorily, improving the ability, and taking into account the fact that 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: LOOO sec Z (6.4 cm 2 '300ml) S force, 0.1 to 500 sec Z (6.4 cm 2 ' 300ml) ) Is more preferable.
[0047] 前記脱酸素剤の厚みは、用途、形態 (例えば、前記脱酸素剤中間体がシート状の 場合には、複数枚重ねて使用する場合等）に応じて適宜設定される。加工性ならび に包装仕様等を考慮すると、 0. 08〜20mmが好ましぐ 0. 1〜： LOmmがより好まし い。  [0047] The thickness of the oxygen scavenger is appropriately set according to the use and form (for example, when the oxygen scavenger intermediate is in the form of a sheet, a plurality of sheets are used in a stacked manner). Considering processability and packaging specifications, 0.0 to 20mm is preferred. 0.1 to: LOmm is more preferred.
[0048] 次に、第 1発明の脱酸素剤を使用した脱酸素剤複合体の好ましい実施形態につい て説明する。  [0048] Next, a preferred embodiment of the oxygen scavenger complex using the oxygen scavenger of the first invention will be described.
本発明の脱酸素剤複合体は、前記第 1発明の脱酸素剤に機能層が設けられたも のである。  In the oxygen scavenger complex of the present invention, the oxygen scavenger of the first invention is provided with a functional layer.
[0049] 前記機能層は、前記脱酸素剤の固形成分の脱落防止、隠蔽、消臭、耐磁、水分バ リア若しくは油分バリアの機能又はこれらの機能が複数組み合わされた機能を有して いる。 [0050] 脱酸素剤の固形成分の脱落防止機能を有する機能層は、脱酸素剤の脱酸素性能 を発現させるための通気性は有する力 脱酸素剤に含有されている前記固形成分の 脱落による汚染を防ぐものである。斯カる機能を有する機能層は、紙、不織布、有孔 榭脂フィルム若しくはこれらの組み合わせた機能層用基材、又は該脱酸素剤に榭脂 組成物を塗工し乾燥することによって設けることができる。前記紙としては、紙パルプ 、合成ノルプまたはそれらの混合物等を湿式および乾式等の製法で製造されたもの が好ましい。前記不織布としては、湿式、乾式、スパンボンド等の製法で製造されたも のを用いることができる。不織布の材質は、ポリエチレン、ポリプロピレン等のポリオレ フィン、ナイロン等のポリアミド、ポリエチレンテレフタレート等のポリエステル、ポリテト ラフルォロエチレン等のポリフッ化ォレフイン等の熱可塑性榭脂の繊維力 なるもの が好ましい。前記有孔榭脂フィルムとしては、不織布の材質と同様に、ポリエチレン、 ポリプロピレン等のポリオレフイン、ナイロン等のポリアミド、ポリエチレンテレフタレート 等のポリエステル、ポリテトラフルォロエチレン等のポリフッ化ォレフイン等の熱可塑性 榭脂が好ましい。有孔榭脂フィルムには、多数の孔を形成するために前記熱可塑性 榭脂に水に不溶又は難溶性の無機又は有機のフィラーが含まれているものが用いら れる。該フイラ一としては、シリカ、炭酸カルシウム、アルミナ、チタン白硫酸バリウム、 ゼォライト、珪藻土、活性白土、酸性白土、タルク、ベントナイト、酸化鉄等が好適に 用いられる。フィラーの粒度は、糸田力、いほど好ましい力 0. Ol-lOO ^ m,特に 0. 1 〜50 mが好ましい。前記榭脂組成物としては、澱粉、カルボキシメチルセルロース 、グァーガム等の天然榭脂組成物、ポリビュルアルコール系、変性セルロース系、塩 化ビュル系、アクリル系、シリコーン系、シリコーンアクリル系、ポリアミド系、ポリエステ ル系、ポリオレフイン系、フエノール系、エチレン '酢酸ビュル共重合体、ポリブタジェ ン系等の合成樹脂の単体若しくは共重合体又はこれらの混合物からなる榭脂組成 物が挙げられる。 [0049] The functional layer has a function of preventing solid components of the oxygen scavenger from falling off, concealing, deodorizing, anti-magnetic, moisture barrier or oil barrier, or a combination of these functions. [0050] The functional layer having a function of preventing the solid component of the oxygen scavenger from falling off has a gas permeability for expressing the oxygen scavenging performance of the oxygen scavenger. The solid component contained in the oxygen scavenger is removed. Prevents contamination. 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 substrate for a functional layer in combination thereof, or the oxygen scavenger and drying. Can do. The paper is preferably a paper pulp, a synthetic norp 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 made of 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, thermoplastics such as polyolefin such as polyethylene and polypropylene, polyamide such as nylon, polyester such as polyethylene terephthalate, polyfluorinated polyolefin such as polytetrafluoroethylene, etc. Fat 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 barium sulfate, zeolite, diatomaceous earth, activated clay, acid clay, talc, bentonite, iron oxide and the like are preferably used. The particle size of the filler is preferably an Itoda force, more preferably 0. Ol-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 alcohols, modified celluloses, salted bulls, acrylics, silicones, silicone acrylics, polyamides, polyesters. Examples thereof include a resin composition comprising a single resin or a copolymer of a synthetic resin such as a rubber, polyolefin, phenol, ethylene butyl acetate copolymer, polybutadiene, or a mixture thereof.
[0051] 脱酸素剤の隠蔽機能を有する機能層は、脱酸素剤の脱酸素性能を発現させるた めの通気性は有するが、脱酸素剤の有する色が外部力 視認できないように隠蔽す るものである。斯カる機能を有する機能層は、白色若しくは有色の顔料を含む、紙、 不織布、有孔榭脂フィルム若しくはこれらの組み合わせた機能層用基材、又は該顔 料を含む榭脂ェマルジヨンを塗工し乾燥した層によって設けることができる。顔料とし ては、白色顔料としては、酸化チタン、酸化亜鉛、炭酸カルシウム、タルク、カオリン、 アルミナシリケート、クレー、石膏、アルミナホワイト等が挙げられる。有色顔料として は、カーボンブラック、ベンガラ、モリブデートオレンジ、群青等の無機顔料、ァゾ系、 イソインドリノン系、フタロシアノニン系、キナクリドン系の有機顔料が挙げられる。顔料 を含ませた層の外表面側にさらに顔料を含まない無着層を設けて衝撃性や強度、ヒ ートシール性やタック性を高めることもできる。遮蔽機能を有する機能層に用いられる これらの紙、不織布、有孔榭脂フィルム及び榭脂ェマルジヨンには、上記固形成分の 脱落防止機能を有する機能層と同様の材質を適宜選択することができる。 [0051] 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.
[0052] 脱酸素剤の消臭機能を有する機能層は、脱酸素性能を発現させるための通気性 は有するが、脱酸素剤から発せられる臭い成分を吸着若しくは分解して消臭するも のである。斯カる機能を有する機能層は、消臭剤を含む、紙、不織布、有孔榭脂フィ ルム若しくはこれらの組み合わせた層、又は榭脂ェマルジヨンの塗工層によって設け ることができる。消臭機能を有する機能層に用いられるこれらの紙、不織布、有孔榭 脂フィルム及び榭脂ェマルジヨンには、上記固形成分の脱落防止機能を有する機能 層と同様の材質を適宜選択することができる。消臭剤としては、各種活性炭、珪藻土 、各種アルミノ珪酸塩、活性アルミナ、酸ィ匕チタン等が挙げられる。また、活性炭は、 含水率が 10%以下 CFIS K1470)のドライ炭が好ましい。酸添着又はアルカリ添着 等の処理を施したものを用いることもできる。アルミノ珪酸塩としては、各種の天然若 しくは合成ゼォライトのようなテクト珪酸塩、天然若しくは合成のフイロ珪酸塩を用いる ことができる。フイロ珪酸塩としては、フイロ珪酸マグネシウム、フイロ珪酸亜鉛、ベント ナイト、活性白土、酸性白土等が挙げられる。消臭剤は、基材への分散性等を考慮 すると、 0. 01〜： LOO /z m 特に 0. 1〜 50 mの粒径を有するものが好ましい。また、 吸着により消臭を発揮する消臭剤は、比表面積が 50〜5000m2/gのもの、特に 10 0〜4000m2Zgのものが好まし ヽ。 [0052] The functional layer having a deodorizing function of the oxygen scavenger has air permeability for expressing the oxygen scavenging performance, but deodorizes it 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.
[0053] 脱酸素剤の耐磁機能を有する機能層は、珪素、アルミナ等の耐磁性の繊維状物又 は粉体を榭脂中に分散したものゃ該粉体が繊維状物に担持されたもの等が好適に 用いられる。 [0054] 脱酸素剤の水分バリア機能、油分バリア機能を有する機能層は、例えばレトルト食 品のような水分の多い食品の保存に脱酸素剤を使用した場合に起こり得る脱酸素剤 による食品の汚染防止や食品からの水分による脱酸素剤の汚染防止を行うものであ る。該水分バリア機能等を有する機能層は、熱可塑性榭脂フィルムでできたものを用 いることができる。熱可塑性榭脂としては、たとえばポリエチレン、ポリプロピレン、ポリ メチルペンテン等のポリオレフイン、ナイロン等のポリアミド、ポリエチレンテレフタレー ト等のポリエステル、ポリテトラフルォロエチレン等のポリフッ化ォレフインなどが好適 に用いられる。また熱可塑性榭脂には水難溶性フイラ一を含有していてもよい。水難 溶性フイラ一とは、水に不溶若しくは難溶性の無機物又は有機物である。水難溶性 フイラ一としては、たとえばシリカ、炭酸カルシウム、アルミナ、チタン白硫酸バリウム、 ゼォライト、珪藻土、活性白土、酸性白土、タルク、ベントナイト、酸化鉄等が好適に 用いられる。なお、当該水分バリア機能等を有する機能層は耐水性、耐油性を有す る紙パルプ、合成パルプ、合成繊維またはそれらの混合物等を湿式および乾式等の 製法で製造されたものを用いることもできる。 [0053] The functional layer of the oxygen scavenger having a magnetic resistance function is obtained by dispersing a magnetically resistant fibrous material or powder such as silicon or alumina in a resin, and the powder is supported on the fibrous material. A thing etc. are used suitably. [0054] The functional layer having a moisture barrier function and an oil content barrier function of the oxygen scavenger is used for the food product by the oxygen scavenger that may occur when the oxygen scavenger is used for the preservation of foods with a high water content such as retort foods. It prevents pollution and contamination of oxygen scavenger by moisture 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. Further, the thermoplastic resin may contain a poorly water-soluble filler. The poorly water-soluble filler is an inorganic or organic substance that is insoluble or hardly soluble in water. As the poorly water-soluble filler, for example, silica, calcium carbonate, alumina, titanium white barium sulfate, zeolite, diatomaceous earth, activated clay, acid clay, talc, bentonite, iron oxide and the like are preferably used. In addition, the functional layer having the moisture barrier function or the like may be a paper pulp, synthetic pulp, synthetic fiber, or a mixture thereof having water resistance and oil resistance manufactured by a manufacturing method such as a wet type or a dry type. it can.
[0055] 前記機能層の厚みは、その有する機能、脱酸素剤複合体の形態に応じて適宜設 定される。加工性、包装仕様等を考慮すると、 1〜： LOOOO /z mが好ましく、 10〜： L00 がより好ましい。 [0055] 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.
[0056] 前記機能層は、前記脱酸素剤の表面に部分的に設けられていてもよぐ全面に設 けられていてもよい。前記機能層は、後述するように、脱酸素剤の表面に積層、塗工 又は含浸によって設けることができる。機能層を積層によって設ける場合には、後述 するように、接着層を介して脱酸素剤に積層することが好ましい。  [0056] The functional layer may be provided on the entire surface of the oxygen scavenger or may be provided on the entire surface. As described later, the functional layer can be provided on the surface of the oxygen scavenger by lamination, coating, or impregnation. When the functional layer is provided by lamination, it is preferably laminated on the oxygen scavenger via an adhesive layer, as will be described later.
[0057] 前記接着層は、脱酸素剤の脱酸素性能に特に悪影響を及ぼさずに脱酸素剤と機 能層とを接着できるものであれば材質、形態に特に制限はないが、通気性を有して いることが好ましい。このような通気性を有する接着剤層は、粘着剤や接着剤を筋状 、網目状等のパターンで脱酸素剤又は機能層の一方又は両方に塗工してそれらを 積層する方法、榭脂繊維、有孔榭脂フィルムの熱溶融性の榭脂材を脱酸素剤又は 機能層の一方又は両方に配して熱ラミネートする方法、或いは、熱溶融性の榭脂を 脱酸素剤又は機能層の一方又は両方に配して該榭脂を筋状に押し出してこれらをラ ミネートする方法によって設けることができる。前記粘着剤としては、ウレタン系ゃァク リル系の粘着剤が好ましい。前記接着剤としては、ホットメルト接着剤やドライラミネ一 シヨン用の接着剤が好ましい。前記熱溶融性の榭脂材を構成する榭脂としては、ポリ ォレフィン系榭脂、ポリエチレン榭脂等が挙げられる。 [0057] The adhesive layer is not particularly limited in material and form as long as it can adhere the oxygen scavenger and the functional layer without adversely affecting the oxygen scavenging performance of the oxygen scavenger. It is preferable to have it. Such an air-permeable adhesive layer is a method in which a pressure-sensitive adhesive or an adhesive is applied to one or both of an oxygen scavenger or a functional layer in a streak-like or mesh-like pattern, and laminated. A method of thermally laminating a fiber, a porous resin film with a heat-meltable resin material disposed on one or both of the oxygen absorber or the functional layer, or a heat-meltable resin film with an oxygen absorber or a functional layer And place it on one or both of these to extrude the fat in a streak It can be provided by a method of minating. The pressure-sensitive adhesive is preferably a urethane-based pressure-sensitive adhesive. As the adhesive, a hot melt adhesive or an adhesive for dry lamination is preferable. Examples of the resin constituting the heat-meltable resin material include polyolefin resin and polyethylene resin.
[0058] 前記脱酸素剤複合体の厚みは、その形態に応じて適宜設定される。加工性や包装 仕様を考慮すると、 0. 08〜30mmが好ましぐ 0. 5〜20mmがより好ましい。  [0058] The thickness of the oxygen scavenger complex is appropriately set according to the form. In consideration of processability and packaging specifications, 0.0 to 30 mm is preferable, and 0.5 to 20 mm is more preferable.
[0059] 次に、第 1発明の脱酸素剤及びそれを使用した脱酸素剤複合体の製造方法をそ の好ま ヽ実施形態に基づ ヽて説明する。  [0059] 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.
先ず、前記被酸化性金属、前記繊維状物、及び水を含む原料組成物 (スラリー)を 調製する。  First, a raw material composition (slurry) containing the oxidizable metal, the fibrous material, and water is prepared.
[0060] 前記原料組成物には、前記凝集剤を添加することが好ま 、。  [0060] It is preferable to add the flocculant to the raw material composition.
該凝集剤としては、硫酸バンド、ポリ塩ィ匕アルミニウム、塩化第二鉄、ポリ硫酸第二 鉄、硫酸第一鉄等の金属塩力もなる無機凝集剤;ポリアクリルアミド系、ポリアクリル酸 ナトリウム系、ポリアクリルアミドのマン-ッヒ変性物、ポリ（メタ）アクリル酸アミノアルキ ルエステル系、カルボキシメチルセルロースナトリウム系、キトサン系、デンプン系、ポ リアミドエピクロヒドリン系等の高分子凝集剤；ジメチルジァリルアンモ-ゥムクロライド 系若しくはエチレンィミン系のアルキレンジクロライドとポリアルキレンポリアミンの縮合 物、ジシアンジアミド 'ホルマリン縮合物等の有機凝結剤；モンモリロナイト、ベントナイ ト等の粘土鉱物；コロイダルシリカ等の二酸化珪素若しくはその水和物；タルク等の含 水ケィ酸マグネシウム等が挙げられる。そして、これら凝集剤の中でもシートの表面性 、地合い形成、成形性の向上、前記被酸化性金属等の成分の定着率、紙力向上の 点からァ-オン性のコロイダルシリカやベントナイト等とカチオン性のデンプンゃポリ アクリルアミド等の併用ゃァ-オン性のカルボキシメチルセルロースナトリウム塩と力 チオン性のポリアミドェピクロルヒドリン系のカチオン性とァ-オン性の薬剤の併用が 特に好ましい。上述の組み合わせ以外でも、これらの凝集剤は単独で又は二以上を 併用することちでさる。  Examples of the flocculant include inorganic flocculants having metal salt strength, such as sulfate band, polyaluminum chloride aluminum, ferric chloride, polyferric sulfate, and ferrous sulfate; polyacrylamide-based, sodium polyacrylate-based, Polymer flocculating agents such as polyacrylamide Mannheim modified products, poly (meth) acrylic acid aminoalkyl ester series, sodium carboxymethyl cellulose, chitosan series, starch series, polyamide epichlorohydrin series; dimethyl diallyl Organic coagulants such as ammonium chloride or ethyleneimine alkylene dichloride and polyalkylene polyamine condensates, dicyandiamide and formalin condensates; clay minerals such as montmorillonite and bentonite; silicon dioxide such as colloidal silica or hydrates thereof; Hydrous silicate, such as talc Or the like. Among these flocculants, ionic colloidal silica, bentonite, and the like are used in order to improve sheet surface properties, texture formation, formability, fixing rate of components such as the oxidizable metal, and paper strength. It is particularly preferable to use a combination of a cationic starch-polyhydramide-based cationic carboxymethyl cellulose sodium salt and a thione polyamide-epoxychlorohydrin-based cationic and a cationic drug. In addition to the above combinations, these flocculants can be used alone or in combination of two or more.
[0061] 前記凝集剤の添加量は、原料組成物の固形分に対して、 0. 01〜5質量％である ことが好ましぐ 0. 05〜3質量％であることがより好ましい。該添カ卩量が斯カる範囲で あると、凝集効果が得られ、抄紙時の前記被酸化性金属等の成分の脱落が抑えられ る。また、原料組成物が均一になり、肉厚及び組成の均一な抄造体を得ることができ る。また、乾燥時に乾燥手段への貼りつき、破れ、焼け、焦げを発生させることもなぐ 生産性に悪影響を及ぼすこともない。また、原料組成物の電位バランスが保たれ、抄 紙時の白水への該成分の脱落量が抑えられる。また、抄造体の酸化反応が進行し、 脱酸素特性や強度等の保存安定性が低下する。 [0061] The addition amount of the flocculant is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 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 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.
[0062] 原料組成物の濃度は、 0. 05〜15質量％が好ましぐ 0. 1〜2質量％がより好まし い。斯かる濃度であると、大量の水を必要とせず、抄造体の成形に時間を要しない。 また、原料組成物が均一に分散されるため、得られる抄造体の表面性が良好であり、 均一な厚みの抄造体が得られる。  [0062] 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.
[0063] 次に、前記原料組成物を抄造して抄造体を抄造する。  [0063] Next, the raw material composition is made into a paper.
前記抄造体をシート状の形態に抄造する場合の抄造方法には、例えば、連続抄紙 式である円網抄紙機、長網抄紙機、短網抄紙機、ツインワイヤー抄紙機などを用い た抄紙方法、バッチ方式の抄紙方法である手漉法等が挙げられる。更に、前記原料 組成物と、該原料組成物と異なる組成の組成物とを用いた多層抄き合わせによって 抄造体を成形することもできる。また、前記原料組成物を抄紙して得られたシートどう しを多層に貼り合わせたり、該シートに該原料組成物と異なる組成を有する組成物か ら得られたシート状物を貼り合わせることによって、多層のシートを成形することもでき る。抄造体をシート状の形態以外に抄造する場合には、従来力 パルプモールド法 にお 、て使用されて 、る湿式抄造方法によって、立体形状を賦形することができる。  Examples of the papermaking method when the papermaking is made into a sheet form include, for example, a continuous papermaking type circular paper machine, long paper machine, short net paper machine, twin wire paper machine and the like. In addition, there is 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 the raw material composition. In addition, the sheets obtained by papermaking the raw material composition are laminated in multiple layers, or a sheet-like material obtained from a composition having a composition different from the raw material composition is laminated on the sheet. A multilayer sheet can also be formed. When the papermaking body is made in a form other than the sheet form, the three-dimensional shape can be formed by the wet papermaking method that is conventionally used in the pulp molding method.
[0064] 前記抄造体は、抄紙後における形態を保つ (保形性)点や、機械的強度を維持す る点から、含水率 (質量含水率、以下同じ。）が 70%以下となるまで脱水させることが 好ましぐ 60%以下となるまで脱水させることがより好ましい。抄造後の抄造体の脱水 方法は、例えば、吸引による脱水のほか、加圧空気を吹き付けて脱水する方法、カロ 圧ロールや加圧板で加圧して脱水する方法等が挙げられる。  [0064] From the viewpoint of maintaining the form after paper making (shape retention) and maintaining the mechanical strength, the papermaking body has a moisture content (mass moisture content, the same shall apply hereinafter) until 70% or less. It is preferable to dehydrate it. It is more preferable to dehydrate until it is 60% or less. Examples of the dewatering method of the papermaking after papermaking include dehydration by suction, spraying with pressurized air, dehydration by pressing with a caloric pressure roll or pressure plate, and the like.
[0065] 本実施形態においては、前記被酸化性金属を含有する抄造体を、積極的に乾燥 させて水分を分離することにより、製造工程中における被酸化性金属の酸化抑制、 長期の保存安定性に優れた脱酸素剤中間体を得ることが可能となる。さらに、乾燥 後の前記繊維状物への被酸ィ匕性金属の担持力を高めてその脱落を抑える点に加え 、熱溶融成分、熱架橋成分の添加による機械的強度の向上が期待できる点から、前 記抄造体の抄造後で前記電解質を含有させる前に該抄造体を乾燥させることが好ま しい。ここで乾燥手段として、加熱乾燥、真空乾燥、凍結乾燥等、適宜使用すること ができる。 [0065] In the present embodiment, the paper-making body containing the oxidizable metal is actively dried to separate moisture, thereby suppressing oxidation of the oxidizable metal during the manufacturing process and long-term storage stability. It is possible to obtain an oxygen scavenger intermediate having excellent properties. Furthermore, dry In addition to increasing the supporting ability of the oxidizable metal to the fibrous material later and suppressing its falling off, it is possible to expect improvement in mechanical strength by adding a hot melt component and a thermal crosslinking component. It is preferable to dry the papermaking after the papermaking and before containing the electrolyte. Here, as drying means, heat drying, vacuum drying, freeze drying and the like can be used as appropriate.
[0066] 前記抄造体は加熱乾燥によって乾燥することが生産速度、設備費用等の点で好ま しい。この場合、加熱乾燥温度は、 60〜300°Cであることが好ましぐ 80〜250°Cで あることがより好ましい。該乾燥温度が斯カる温度範囲であると、乾燥時間が長くなり 過ぎず、水分の乾燥とともに、被酸化性金属の酸化反応が促進されることもない。こ のため、脱酸素剤の脱酸素性能の低下を引き起こすこともない。また、脱酸素剤中間 体の表裏層のみ被酸化性金属の酸化反応が促進されることもなぐうす茶色への変 色が抑えられる。また、脱酸素剤の脱酸素効果の低下を抑えることができる。また、脱 酸素剤中間体内部で急激に水分が気化して脱酸素剤中間体の構造が破壊されたり することちない。  [0066] 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.
[0067] 乾燥後における脱酸素剤中間体の含水率は、 20%以下であることが好ましぐ 10 %以下であることがより好ま 、。含水率が 20%以下であると長期保存安定性に優 れ、例えばシート状に形成し、巻きロール状態で一時保存しておく場合等該ロール の厚み方向で水分の移動が起こり難ぐ脱酸素性能や機械的強度の変化を抑えるこ とがでさる。  [0067] 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.
[0068] 前記抄造体の乾燥方法は、抄造体の形態、乾燥前の抄造体の処理方法、乾燥前 の含水率、乾燥後の含水率等に応じて適宜選択することができる。該乾燥方法として は、例えば、加熱構造体 (発熱体)との接触、加熱空気や蒸気 (過熱蒸気)の吹き付 け、真空乾燥、電磁波加熱、通電加熱等の乾燥方法が挙げられる。また、前述の脱 水方法と組み合わせて同時に実施することもできる。  [0068] The drying method of the papermaking body can be appropriately selected according to the form of the papermaking body, the processing method of the papermaking body before drying, the moisture content before drying, the moisture content after drying, and the like. Examples of the drying method include drying methods such as contact with a heating structure (heating element), spraying of heated air or steam (superheated steam), vacuum drying, electromagnetic wave heating, and electric heating. It can also be carried out simultaneously with the above-mentioned dewatering method.
[0069] 本実施形態にお!、ては、抄造体及び脱酸素剤中間体の成形は、上述のように抄 造体及び脱酸素剤中間体に酸化反応助剤となる電解質を含有して!/ヽな ヽので、通 常の空気雰囲気下で成形を行うことができる。このため、製造設備を簡略化すること ができる。また、必要に応じて、クレープ処理、スリット加工、トリミングを施したり、加工 処理により形態を変更する等の加工を施すこともできる。得られた脱酸素剤中間体は 、高い強度を有しているので、シート状の形態に形成した場合には、必要に応じ、口 ール状に巻き取ることができる。また、脱酸素剤中間体をシート状の形態に形成した 場合には、単独若しくは重ねて又は紙、布 (織布又は不織布）、榭脂フィルム等の他 のシートと重ねて、加圧したり、さらには加圧しエンボス力卩ェゃニードルパンチ加工を 行うことにより、複数のシートを積層一体化させたり、凹凸状の賦型ゃ孔あけを行うこ ともできる。また、前記原料組成物に熱可塑性榭脂成分や熱水溶解成分を含有させ ることにより、ヒートシール力卩ェを施して貼り合わせ等を行い易くすることもできる。 [0069] In the present embodiment, the papermaking body and the oxygen scavenger intermediate are molded, as described above, containing the 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, the manufacturing equipment can be simplified. Also, if necessary, creping, slitting, trimming, processing Processing such as changing the form by processing can also 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.
[0070] 前記脱酸素剤中間体には前記機能層を設ける。機能層を設けない脱酸素剤単体 の製造工程では、以下の機能層を設ける工程は行わず、後述するように脱酸素剤中 間体に電解質を含有させる工程を行う。  [0070] The functional layer is provided on the oxygen scavenger intermediate. In the manufacturing process of the oxygen scavenger alone without providing the functional layer, the following functional layer is not provided, but the process of incorporating an electrolyte into the oxygen scavenger intermediate is performed as described later.
[0071] 前記機能層は、脱酸素剤中間体の形態に応じて選択することができる。脱酸素剤 中間体をシート状に形成する場合には、ラミネーシヨン加工法、特にウエットラミネー シヨン、ドライラミネーシヨン、押出しラミネーシヨンによって機能層を設けることが好ま しい。ラミネーシヨン加工法を採用することによって、脱酸素剤の基材となるシート状 の脱酸素剤中間体の抄造工程に合わせて、ウエットラミネーシヨン、ドライラミネーショ ン、押出しラミネーシヨンを選択してインラインで組み込んで、脱酸素剤の表面に必要 に応じて接着剤を介して機能層を設けることができる。前述したような前記各機能層 を設けるための榭脂組成物を脱酸素剤の表面に塗布、乾燥することによって機能層 を設けることもできる。また、前述した榭脂組成物を含浸させることによって、脱酸素 剤の表面および内部に機能層を設けることができる。この方法は、シート状以外の形 態に脱酸素剤中間体を形成した場合に有効である。例えば、湿潤状態の抄造体又 は乾燥状態の脱酸素剤中間体を押出成形、加圧成形、打錠成形等を用い、球状や ヌードル状、繊維状等の形状に加工した後に榭脂組成物を含浸することもできる。前 述のように前記機能層を設ける前に前記脱酸素剤中間体を加熱乾燥することが好ま しいが、機能層を積層又は塗工して設けた後に、加熱乾燥を行うこともできる。  [0071] 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.
[0072] 次に、前記脱酸素剤中間体に前記電解質を含有させる。この電解質を含有させる 工程は、窒素、アルゴン等の不活性ガス雰囲気下で行うことが好ましいが、後述のよ うに電解質をその電解液の含浸により添加する場合には、添加直後の酸ィ匕反応がゆ るや力なため、通常の空気雰囲気下で該電解質を含有させることもできる。 [0072] Next, the electrolyte is contained in the oxygen scavenger intermediate. The step of containing the electrolyte is preferably performed in an inert gas atmosphere such as nitrogen or argon. Thus, when an electrolyte is added by impregnation of the electrolyte, the acid-oxidation reaction immediately after the addition is weak, so the electrolyte can be contained in a normal air atmosphere.
[0073] 前記脱酸素剤中間体へ前記電解質を含有させる方法は、抄造後における当該脱 酸素剤中間体の処理方法、含水率、形態等に応じて適宜設定することができる。該 電解質を含有させる方法としては、例えば、前記脱酸素剤中間体に、前記電解質の 所定濃度の電解液を含浸させる方法、前記電解質の所定粒径のものを固体のまま 添加して脱酸素剤中間体に含有させる方法等が挙げられ、これらの中でも、脱酸素 剤中間体に電解質を均一に含有させることができる点、含水率の調整が同時に行え る点から、所定濃度の電解液を含浸させる方法が好まし ヽ。  [0073] 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 as a solid to the oxygen scavenger. Examples of the method include the method of inclusion in an intermediate, and among these, the oxygen scavenger intermediate can contain an electrolyte uniformly, and the water content can be adjusted at the same time. I prefer the way to let go.
[0074] 電解液は、水又は水とアルコールの混合液に電解質を電解させたものを用いること が好ましい。取り扱い性の点では水のみの電解液が好ましぐ自力反応型の脱酸素 性能をより高める上では水とアルコールの混合液が好まし 、。水とアルコールの混合 割合は、水 Zアルコール（質量比率）で、 80〜10%Z20〜90%が好ましぐ 70〜2 0%Z30〜80%がより好ましい。  [0074] The electrolytic solution is preferably water or a mixture of water and alcohol obtained by electrolyzing an electrolyte. From the standpoint of ease of handling, a water-alcohol mixture is preferred in order to further enhance the self-reactive deoxygenation performance, in which a water-only electrolyte is preferred. 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%.
[0075] 上述のように前記電解質をその電解液で脱酸素剤中間体に含浸させる場合、その 含浸方法は、脱酸素剤中間体の形態、含水率に応じて適宜選択することができる。 該含浸方法には、該電解液を該脱酸素剤中間体にスプレー塗工する方法、該電解 液をシリンジ等で該脱酸素剤中間体の一部分に注入し、前記繊維状物の毛管現象 を利用して該脱酸素剤中間体に浸透させる方法、刷毛等で塗工する方法、該電解 液に浸漬する方法、グラビアコート法、リバースコート法、ドクターブレード法等が挙げ られ、これらの中でも、電解質を均一に分布でき、簡便で、設備コストも比較的少なく て済む点からスプレー塗工する方法が好ましい。また、複雑な形状、層構成の商品 においては生産性が向上する点や、最終仕上げを別工程とできることにより生産のフ レキシブル性が向上する点、設備が簡便となる点からは、所定濃度の電解液をシリン ジ等で注入する方法が好ましい。この電解液を注入する方法は、該脱酸素剤中間体 を例えば酸素透過性の収容体等に収容した後に行うこともできる。  [0075] When the oxygen absorber is impregnated with the electrolyte with the electrolyte as described above, the impregnation method can be appropriately selected according to the form of the oxygen absorber intermediate and the water content. In the impregnation method, the electrolytic solution is spray-coated on the oxygen scavenger intermediate, and the electrolyte is injected into a part of the oxygen scavenger intermediate with a syringe or the like to reduce the capillary action of the fibrous material. Examples thereof include a method of making use of the oxygen scavenger intermediate, 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. A spray coating method is preferred because it can distribute the electrolyte uniformly, is simple, and requires relatively low equipment costs. 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.
[0076] 上述のように脱酸素剤中間体に電解質を含有させた後、必要に応じて含水率を調 整し、安定化させて脱酸素剤とすることができる。そして必要に応じ、トリミング、シート 状の形態の場合には二枚以上積層化等の処理を施し、所定の大きさに加工すること ができる。 [0076] After the electrolyte is contained in the oxygen absorber intermediate as described above, the moisture content can be adjusted and stabilized as necessary to obtain an oxygen absorber. And trimming, sheet if necessary In the case of a shape, it can be processed into a predetermined size by performing a process such as stacking two or more sheets.
[0077] 上述のようにして得られた脱酸素剤及び脱酸素剤複合体は、その表面を、酸素透 過性を有する被覆層で被覆することが好ましい。該被覆層は、その全面に酸素透過 性を有していてもよぐ部分的に酸素透過性を有していてもよい。該被覆層には酸素 透過性を有するものであればその材質に特に制限はない。該被覆層は、例えば、紙 、不織布、多微孔質膜、微細な孔を設けた榭脂フィルム等を脱酸素剤の表面に積層 して設けることができる。また、合成樹脂塗料やエマルシヨン塗料等を脱酸素剤に含 浸あるいは塗布させて設けることもできる。  [0077] The surface of the oxygen scavenger and oxygen scavenger complex obtained as described above is preferably coated with a coating layer having oxygen permeability. The coating layer may have oxygen permeability on the entire surface, or may partially have oxygen permeability. The material of the coating layer is not particularly limited as long as it has oxygen permeability. The coating layer can be provided, for example, by laminating paper, a nonwoven fabric, a multi-porous film, a resin film provided with fine pores, etc. on the surface of the oxygen scavenger. Further, a synthetic resin paint, an emulsion paint, or the like can be provided by impregnating or applying in an oxygen scavenger.
[0078] また、該被覆層の酸素透過性、水蒸気透過性により、脱酸素特性を任意に制御す ることもできる。酸素透過性の一つの指標としては、酸素透過係数等が用いられる。 また水蒸気透過性の一つの指標としては、水蒸気透過係数等が用いられる。例えば 、酸素透過係数や水蒸気透過係数の高い被覆層を選定することで、短時間で高い 脱酸素特性を有する脱酸素剤を得ることができ、酸素透過係数や水蒸気透過係数 の低い被覆層を選定することで、長時間に亘つて脱酸素特性の緩や力な脱酸素剤 を得ることができる。  [0078] In addition, the oxygen removal property can be arbitrarily controlled by the oxygen permeability and water vapor permeability of the coating layer. An oxygen permeability coefficient or the like is used as one index of oxygen permeability. Further, as one index of water vapor permeability, a water vapor transmission coefficient or the like is used. For example, by selecting a coating layer with a high oxygen permeability coefficient or water vapor permeability coefficient, a deoxygenating agent with high oxygen scavenging properties can be obtained in a short time, and a coating layer with a low oxygen permeability coefficient or water vapor permeability coefficient is selected. By doing so, it is possible to obtain a deoxidizing agent having a slow deoxidizing characteristic and a strong force over a long period of time.
[0079] 得られた脱酸素剤及び脱酸素剤複合体は、使用するまでに酸素と接触するのを避 けるため、非酸素透過、非水分透過性の包装袋等に収容されて提供される。  [0079] 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. .
[0080] 以上説明したように、本実施形態の脱酸素剤及び脱酸素剤複合体は、被酸化性金 属を効率良く酸化反応させ、より少ない量で高い脱酸素性能が得られる。また、高い 強度を有し、薄くした場合には破れにくぐ柔軟性を備えているので、加工性、生産 性にも優れている。また、保持できる水分量を幅広く設定できるため、幅広い水分活 性の物品にも適用することができる。また、被酸化性金属の含有率を上げたり、電解 液の量や濃度を調整することによって、酸素吸収速度を速くすることができるため、フ ライドポテトやフライドチキンなどの含油性食品を含む含油性の物品の油の酸ィ匕劣化 による当該物品の品質低下を防ぐことができる。また、電子レンジ等のマイクロ波加熱 装置で使用しても、発火することがないので、レトルト食品等の鮮度維持に使用する ことができる。 [0081] また、上述のように、前記原料組成物中に酸化助剤となる電解質が含まれていない ので、懸濁液中でのイオン濃度が低くなることによって、当該原料組成物中における 被酸ィ匕性金属の分散性が良好となる。そして、原料組成物の調製中において被酸 化性金属と繊維状物とを実質的に接触させることにより、繊維状物の表面に被酸ィ匕 性金属が均一に定着され、得られる脱酸素剤の脱酸素特性が向上する。 [0080] As described above, the oxygen scavenger and oxygen scavenger complex of the present embodiment efficiently oxidizes the 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, since the amount of water that can be held can be set widely, it can also be applied to articles having a wide range of water activity. In addition, by increasing the content of oxidizable metals and adjusting the amount and concentration of the electrolyte, the oxygen absorption rate can be increased, so 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. In addition, since it does not ignite even when used in a microwave heating apparatus such as a microwave oven, it can be used to maintain the freshness of retort foods. [0081] 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 coating in the raw material composition is reduced. Dispersibility of the acid metal 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.
例えば、酸化助剤となる電解質が配合された懸濁液中では、該系内の塩濃度が高 くなることにより、前記被酸ィヒ性金属等の成分並びに繊維状物の界面の電気二重層 が圧縮されるため、該成分と繊維状物との接触が著しく阻害され、繊維状物の表面 に該成分が定着することが困難となり、肉厚が薄く且つ該成分が多く充填されたシー トを成形することが困難となる。また、上記のような塩濃度が高い系では、凝集剤によ る定着も同様の理由により非常に困難となり、得られる脱酸素剤の脱酸素特性は著 しく劣るものとなる。また、水中の酸素と反応して酸ィ匕を引き起こし、脱酸素性能の低 下を引き起こす場合がある。さらに、抄造体は、空気中の酸素と反応し易ぐ長期保 存安定性に劣ったり、抄紙機等の成形機、加工機が鲭び易くなる場合がある。  For example, in a suspension in which an electrolyte that serves as an oxidation aid is blended, the concentration of the salt in the system increases, so that the components such as the oxidizable metal and the electrical interface at the interface of the fibrous material are increased. Since the multilayer is compressed, contact between the component and the fibrous material is remarkably inhibited, and it becomes difficult to fix the component on the surface of the fibrous material, and the sheet is thin and filled with a large amount of the component. It becomes difficult to mold the mold. 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 properties of the oxygen scavenger obtained are significantly 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, and may easily form a molding machine or a processing machine such as a papermaking machine.
[0082] さらに、電解質を含まない脱酸素剤中間体を予め乾燥成形するために、脱酸素剤 中間体の強度を保つことができ、 2次加工が容易になる他、裁断用の刃物の鲭の発 生や摩耗を抑制することができる。また、電解質の含浸においては、脱酸素剤に含 有させる電解質量及び脱酸素剤の含水率を容易に制御することができるほか、ある 任意の形状にパターン含浸を行うことにより、同一面上において反応する部分としな い部分とに分けることができたり、製造工程中における被酸ィ匕性金属の酸ィ匕を極力 抑えることができ、良好な脱酸素特性を有する脱酸素成形体を得ることができる。  [0082] 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 edge of the cutting blade 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 in a certain arbitrary shape can be performed on the same surface. It is possible to obtain a deoxygenated molded article that can be divided into non-reacting parts and non-reactive parts, and can suppress as much as possible the acidity of the oxidizable metal during the production process. Can do.
[0083] また、本実施形態の脱酸素剤複合体によれば、前記効果が奏される脱酸素剤に前 記機能層の有する種々の機能を付与することができる。  [0083] 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.
[0084] 次に、第 2発明の脱酸素剤を、その好ましい実施形態に基づき図面を参照しながら 説明する。なお、以下の説明においては、第 2発明の脱酸素剤についての特徴部分 について説明し、第 1発明の脱酸素剤と共通する部分についての説明は省略する。 よって、特に説明のない部分については、上記第 1発明における説明が適宜適用さ れる。 [0085] 第 2発明の脱酸素剤は、被酸化性金属、保水剤、及び繊維状物を含む抄造体を乾 燥してなる脱酸素剤中間体に、酸ィ匕反応助剤となる電解質を含ませたものである。本 実施形態の脱酸素剤は、脱酸素剤自身の有する水分で被酸化性金属の酸化反応 が生じる!/、わゆる自力反応型の脱酸素剤である。 [0084] 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, characteristic parts of the oxygen scavenger of the second invention will be described, and description of 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 a portion not particularly described. [0085] The oxygen scavenger of the second invention is an electrolyte that serves as an acid-oxidation reaction aid to an oxygen scavenger intermediate formed by drying a papermaking product containing an oxidizable metal, a water retention agent, and a fibrous material. Is included. The oxygen scavenger of the present embodiment is a so-called self-reactive oxygen scavenger that causes an oxidation reaction of the oxidizable metal with the water content of the oxygen scavenger itself!
[0086] 本実施形態の脱酸素剤に含まれる電解質には、前記第 1発明の脱酸素剤の実施 形態における電解質の説明が適用される。  [0086] The description of the electrolyte in the embodiment of the oxygen scavenger of the first invention is applied to the electrolyte contained in the oxygen scavenger of the present embodiment.
[0087] 本実施形態の脱酸素剤に含まれる被酸化性金属には、前記第 1発明の脱酸素剤 の実施形態における被酸化性金属の説明が適用される。  [0087] The description of the oxidizable metal in the oxygen scavenger embodiment of the first invention is applied to the oxidizable metal contained in the oxygen scavenger of the present embodiment.
[0088] 前記保水剤には、従来力 脱酸素剤に通常用いられている保水剤を特に制限無く 用いることができる。該保水剤は、水分保持剤として働く他に、被酸化性金属への酸 素保持 Z供給剤としての機能も有している。該保水剤としては、例えば、活性炭 (椰 子殻炭、木炭粉、暦青炭、泥炭、亜炭)、カーボンブラック、アセチレンブラック、黒鉛 、ゼォライト、パーライト、バーミキユライト、シリカ、カンタリナイト、フローライト等が挙 げられ、これらの中でも保水能、酸素供給能、触媒能を有する点から活性炭が好まし く用いられる。該保水剤には、被酸化性金属との有効な接触状態を形成できる点か ら粒径が 0. 1〜500 111の粉体状のものを用ぃることが好ましぐ0. 1〜200 /ζ πιの ものを 50質量％以上含有するものを用いることがより好ましい。保水剤には、上述の ような粉体状以外の形態のものを用いることもでき、例えば、活性炭繊維等の繊維状 の形態のものを用いることもできる。  [0088] 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 retention agent include activated carbon (rice husk charcoal, charcoal powder, calendar bituminous coal, peat, lignite), carbon black, acetylene black, graphite, zeolite, perlite, vermiculite, silica, cantalinite, fluorite, and the like. Among them, 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 a particle size of 0.1 to 500 111 from the viewpoint that an effective contact state with an oxidizable metal can be formed. It is more preferable to use a material containing 50% by mass or more of 200 / ζ πι. As the water retention agent, it is possible to use a form other than the powder form as described above, for example, a form of a fibrous form such as activated carbon fiber.
[0089] 前記脱酸素剤中間体中の前記保水剤の配合量は、 0. 5〜60質量％であることが 好ましぐ 1〜50質量％であることがより好ましい。保水剤の配合量が斯カる範囲であ ると、所望の脱酸素効果を得るための被酸化性金属の酸化反応に必要な水分を脱 酸素剤中に蓄積できる。また、脱酸素剤中間体の通気性が損なわれず、酸素供給が 良好で脱酸素効率に優れる。また、保水剤の脱落の発生も抑えられる。また、脱酸素 剤中間体を構成する後述の繊維状物や接着成分が少なくならず、曲げ強度や引張 強度等の機械的強度も保たれる。  [0089] 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 deoxygenation effect can be accumulated in the deoxygenation agent. Also, 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. Further, the fibrous materials and adhesive components described later constituting the oxygen scavenger intermediate are not reduced, and mechanical strength such as bending strength and tensile strength is also maintained.
[0090] 本実施形態の脱酸素剤に含まれる繊維状物には、前記第 1発明の脱酸素剤の実 施形態における繊維状物の説明が適用される。 [0091] 前記脱酸素剤中間体には、第 1発明の実施形態におけると同様に、凝集剤が添加 されていてもよいし、必要に応じ、サイズ剤、着色剤、紙力増強剤、歩留向上剤、填 料、増粘剤、 pHコントロール剤、嵩高剤等の抄紙の際に通常用いられる添加物を特 に制限無く添加することができる。該添加物の添加量は、添加する添加物に応じて 適宜設定することができる。 [0090] 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. [0091] As in the embodiment of the first invention, the oxygen scavenger intermediate may be added with a flocculant, and if necessary, a sizing agent, a colorant, a paper strength enhancer, a step. Additives usually used in paper making such as a retention improver, filler, thickener, pH control agent, bulking agent and the like can be added without particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.
[0092] 脱酸素剤を電子レンジ等のマイクロ波加熱装置で使用可能とするためには、例え ば、耐磁性の高い珪素、アルミナ等の繊維状物又は粉体を脱酸素剤中間体に添カロ するのが好ましい。また、製品の外観上、着色が必要な場合には、酸化チタンや炭酸 カルシウム、アルミナホワイト等の着色粉体を添加してもよい。さらに酸化反応促進や 柔軟性の向上のために、フローライト、イソライト、タルク等の粉体や前記セラミック繊 維や合成繊維を添加することもできる。  [0092] In order to make the oxygen scavenger usable 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.
[0093] 本実施形態の脱酸素剤中間体をシート状の形態に形成した場合の厚み、坪量、 1 枚の裂断長、坪量 lOOgZm2当たりの透気度は、前記第 1発明の実施形態における 説明が適用される。 [0093] When the oxygen scavenger intermediate of the present embodiment is formed into a sheet-like form, the thickness, basis weight, tear length of one sheet, and air permeability per basis weight lOOgZm 2 are the same as those of the first invention. The description in the embodiment is applied.
[0094] 前記脱酸素剤の厚みは、前記第 1発明の実施形態における脱酸素剤の厚みの説 明が適用される。  As the thickness of the oxygen scavenger, the description of the thickness of the oxygen scavenger in the embodiment of the first invention is applied.
[0095] 次に、第 2発明の脱酸素剤を使用した脱酸素剤複合体の好ましい実施形態につい て説明する。  [0095] Next, a preferred embodiment of the oxygen scavenger complex using the oxygen scavenger of the second invention will be described.
本実施形態の脱酸素剤複合体は、前記第 2発明の脱酸素剤に機能層が設けられ たものである。  The oxygen scavenger complex of the present embodiment is obtained by providing a functional layer on the oxygen scavenger of the second invention.
[0096] 第 2発明の脱酸素剤を使用した脱酸素剤複合体の前記機能層及び接着層、該脱 酸素剤複合体の厚み、には、前記第 1発明の脱酸素剤を使用した脱酸素剤複合体 の実施形態における前記機能層及び前記接着層、前記脱酸素剤複合体の厚みの 説明が適用される。  [0096] The functional layer and the adhesive layer of the oxygen scavenger complex using the oxygen scavenger of the second invention, and the thickness of the oxygen scavenger complex are desorbed 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 oxygen agent complex applies.
[0097] 次に、第 2発明の脱酸素剤及びそれを使用した脱酸素剤複合体の製造方法をそ の好ま ヽ実施形態に基づ ヽて説明する。  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.
先ず、前記被酸化性金属、前記保水剤、前記繊維状物、及び水を含む原料組成 物 (スラリー)を調製する。 [0098] 前記原料組成物への凝集剤の添加については、第 1発明の脱酸素剤の製造方法 の実施形態において説明した前記凝集剤の添加が適用される。 First, a raw material composition (slurry) containing the oxidizable metal, the water retention agent, the fibrous material, and water is prepared. [0098] For the addition of the flocculant to the raw material composition, the addition of the flocculant described in the embodiment of the oxygen scavenger production method of the first invention is applied.
[0099] 原料組成物の濃度は、 0. 05〜15質量％が好ましぐ 0. 1〜2質量％がより好まし い。斯かる濃度であると、大量の水を必要とせず、抄造体の成形に時間を要しない。 また、原料組成物が均一に分散されるため、得られる抄造体の表面性が良好であり、 均一な厚みの抄造体が得られる。  [0099] 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.
[0100] 次に、前記原料組成物を抄造して抄造体を抄造する。  [0100] Next, the raw material composition is made into a paper.
前記抄造体をシート状の形態に抄造する場合の抄造方法には、前記第 1発明の脱 酸素剤における説明が適用される。  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.
[0101] 前記抄造体の含水率、脱水方法、乾燥方法、乾燥後における脱酸素剤中間体の 含水率には、前記第 1発明における説明が適用される。  [0101] The description in 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.
[0102] 本実施形態においては、抄造体及び脱酸素剤中間体の成形は、上述のように抄 造体及び脱酸素剤中間体に酸化反応助剤となる電解質を含有して!/ヽな ヽので、通 常の空気雰囲気下で成形を行うことができる。このため、製造設備を簡略化すること ができる。また、必要に応じて、クレープ処理、スリット加工、トリミングを施したり、加工 処理により形態を変更する等の加工を施すこともできる。得られた脱酸素剤中間体は 、高い強度を有しているので、シート状の形態に形成した場合には、必要に応じ、口 ール状に巻き取ることができる。また、脱酸素剤中間体をシート状の形態に形成した 場合には、単独若しくは重ねて又は紙、布 (織布又は不織布）、榭脂フィルム等の他 のシートと重ねて、加圧したり、さらには加圧しエンボス力卩ェゃニードルパンチ加工を 行うことにより、複数のシートを積層一体化させたり、凹凸状の賦型ゃ孔あけを行うこ ともできる。また、前記原料組成物に熱可塑性榭脂成分や熱水溶解成分を含有させ ることにより、ヒートシール力卩ェを施して貼り合わせ等を行い易くすることもできる。  [0102] In the present embodiment, the papermaking body and the oxygen scavenger intermediate are formed by containing an electrolyte as an oxidation reaction aid in the papermaking body and the oxygen scavenger intermediate as described above. As a result, molding can be performed in a normal 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 necessary when formed into a sheet. In addition, when the oxygen scavenger intermediate is formed into a sheet-like form, it can be used alone or in layers, or on 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.
[0103] 前記脱酸素剤中間体には前記機能層を設ける。機能層を設けない脱酸素剤単体 の製造工程では、以下の機能層を設ける工程は行わず、後述するように脱酸素剤中 間体に電解質を含有させる工程を行う。  [0103] The functional layer is provided on the oxygen scavenger intermediate. In the manufacturing process of the oxygen scavenger alone without providing the functional layer, the following functional layer is not provided, but the process of incorporating an electrolyte into the oxygen scavenger intermediate is performed as described later.
[0104] 前記脱酸素剤中間体に設ける機能層には、第 1発明の脱酸素剤の実施形態にお ける説明が適用される。 [0105] 次に、前記脱酸素剤中間体に前記電解質を含有させる。この電解質を含有させる 工程には、第 1発明の脱酸素剤の実施形態における説明が適用される。 [0104] The description in the embodiment of the oxygen scavenger of the first invention is applied to the functional layer provided in the oxygen scavenger intermediate. [0105] 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.
[0106] 上述のようにして得られた脱酸素剤及び脱酸素剤複合体は、その表面を、酸素透 過性を有する被覆層で被覆することが好ましい。該被覆層には、前記第 1発明の脱 酸素剤及びそれを使用した脱酸素剤複合体における被覆層の説明が適宜適用され る。  [0106] 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 oxygen scavenger according to the first invention is appropriately applied to the coating layer.
[0107] 得られた脱酸素剤及び脱酸素剤複合体は、使用するまでに酸素と接触するのを避 けるため、非酸素透過、非水分透過性の包装袋等に収容されて提供される。  [0107] 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. .
[0108] 以上説明したように、本実施形態の脱酸素剤及び脱酸素剤複合体は、素早 、時間 で高い脱酸素性能が得られる。また、高い強度を有し、薄くした場合には破れにくぐ 柔軟性を備えているので、加工性、生産性にも優れている。また、保持できる水分量 を幅広く設定できるため、幅広い水分活性の物品にも適用することができる。また、被 酸化性金属の含有率を上げたり、電解液の量や濃度を調整することによって、酸素 吸収速度を速くすることができるため、フライドポテトやフライドチキンなどの含油性食 品を含む含油性の物品の油の酸ィ匕劣化による当該物品の品質低下を防ぐことがで きる。  [0108] As described above, the oxygen scavenger and oxygen scavenger complex of the present embodiment can provide high oxygen scavenging performance quickly and in time. In addition, since it has high strength and is flexible enough to resist tearing when thinned, it has excellent workability and productivity. Moreover, since the amount of water that can be retained can be set widely, it can be applied to articles having a wide range of water activity. In addition, by increasing the content of oxidizable metals and adjusting the amount and concentration of the electrolyte, the oxygen absorption rate can be increased, so that oil-containing foods including oil-containing foods such as French fries and fried chicken are included. The deterioration of the quality of the product due to the deterioration of the acidity of the oil of the product can be prevented.
[0109] また、上述のように、前記原料組成物中に酸化助剤となる電解質が含まれていない ので、懸濁液中でのイオン濃度が低くなることによって、当該原料組成物中における 被酸ィ匕性金属の分散性が良好となる。そして、原料組成物の調製中において被酸 化性金属と繊維状物とを実質的に接触させることにより、繊維状物の表面に被酸ィ匕 性金属が均一に定着され、得られる脱酸素剤の脱酸素特性が向上する。  [0109] 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 coating in the raw material composition is reduced. Dispersibility of the acid metal 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.
例えば、酸化助剤となる電解質が配合された懸濁液中では、該系内の塩濃度が高 くなることにより、前記被酸化性金属や前記保水剤等の成分並びに繊維状物の界面 の電気二重層が圧縮されるため、該成分と繊維状物との接触が著しく阻害され、繊 維状物の表面に該成分が定着することが困難となり、肉厚が薄く且つ該成分が多く 充填されたシートを成形することが困難となる。また、上記のような塩濃度が高い系で は、凝集剤による定着も同様の理由により非常に困難となり、得られる脱酸素剤の脱 酸素特性は著しく劣るものとなる。また、水中の酸素と反応して酸化を引き起こし、脱 酸素性能の低下を引き起こす場合がある。さらに、抄造体は、空気中の酸素と反応し 易ぐ長期保存安定性に劣ったり、抄紙機等の成形機、加工機が鯖び易くなる場合 がある。 For example, in a suspension in which an electrolyte serving as an oxidation aid is blended, the salt concentration in the system increases, so that the components such as the oxidizable metal and the water retention agent and the interface of the fibrous material are increased. Since the electric double layer is compressed, contact between the component and the fibrous material is remarkably hindered, and it becomes 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 becomes very difficult for the same reason, and the oxygen scavenging property of the resulting oxygen scavenger is extremely inferior. It also reacts with oxygen in the water to cause oxidation and release. May cause reduced oxygen performance. In addition, the papermaking body may easily react with oxygen in the air and may have poor long-term storage stability, and a molding machine or a processing machine such as a papermaking machine may be easily crushed.
[0110] さらに、電解質を含まない脱酸素剤中間体を予め乾燥成形するために、脱酸素剤 中間体の強度を保つことができ、 2次加工が容易になる他、裁断用の刃物の鲭の発 生や摩耗を抑制することができる。また、電解質の含浸においては、脱酸素剤に含 有させる電解質量及び脱酸素剤の含水率を容易に制御することができるほか、ある 任意の形状にパターン含浸を行うことにより、同一面上において反応する部分としな い部分とに分けることができたり、製造工程中における被酸ィ匕性金属の酸ィ匕を極力 抑えることができ、良好な脱酸素特性を有する脱酸素成形体を得ることができる。  [0110] Further, 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 cutting blades are used for cutting. 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 in a certain arbitrary shape can be performed on the same surface. It is possible to obtain a deoxygenated molded article that can be divided into non-reacting parts and non-reactive parts, and can suppress as much as possible the acidity of the oxidizable metal during the production process. Can do.
[0111] また、本実施形態の脱酸素剤複合体によれば、前記効果が奏される脱酸素剤に前 記機能層の有する種々の機能を付与することができる。  [0111] 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-described effects.
[0112] 本発明は、前記実施形態に制限されるものではなぐ本発明の趣旨を逸脱しない 範囲において適宜変更することができる。  [0112] The present invention is not limited to the embodiment described above, and can be modified as appropriate without departing from the spirit of the present invention.
[0113] 上述の脱酸素剤複合体の製造方法では、ともに脱酸素剤中間体の表面に前記機 能層を設けた後に電解質を含ませたが、製造順序はこれに限定されるものではなぐ 脱酸素剤中間体に電解質を含ませて脱酸素剤を製造してから前記機能層を設けて もよい。また前述した様に、榭脂組成物を含浸することによって、脱酸素剤の表面お よび内部に機能層を設けることもできる。例えばポリビニルアルコール水溶液を脱酸 素剤に含浸させた後に脱酸素剤を必要とする含水率まで加熱乾燥させるとともにポリ ビュルアルコールを架橋させることにより、脱酸素剤に含まれる鉄粉等の脱落を防ぐ 機會をちたせることもできる。  [0113] In the method for producing the oxygen scavenger complex described above, the electrolyte is included after providing the functional layer on the surface of the oxygen scavenger intermediate, but the production order is not limited to this. The functional layer may be provided after producing an oxygen scavenger by adding an electrolyte to the oxygen scavenger intermediate. 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 a dehydrating agent with an aqueous polyvinyl alcohol solution, it is dried by heating to a moisture content that requires the deoxidizing agent, and crosslinking of polybutyl alcohol prevents iron powder contained in the deoxidizing agent from falling off. You can also have a chance.
[0114] 本発明の脱酸素剤及びそれらを脱酸素剤複合体は、切断する等して所定の形態 に成形し、容器に収容物とともに収容して用いることが好ましいが、柔軟性を有してい るため脱酸素剤又は脱酸素剤複合体で袋やバウチ等の容器を形成することもできる し、プレス成形して所望の立体形状を賦形して脱酸素機能を備えた容器とすることも できる。また、容器の基材シートに貼り合わせて板紙容器ゃパゥチに成形して用いる こともできるし、筒状やボトル状等の中空形状やカートン、トレイ形状等の容器形状と いったシート状以外の形態に脱酸素剤中間体を抄造することによって、これらの容器 に合わせた形態を有する脱酸素機能を備えた容器を製造することができる。 [0114] It is preferable that the oxygen scavenger of the present invention and the oxygen scavenger complex of them are molded into a predetermined form by cutting or the like, and housed in a container together with the contents, but have flexibility. Therefore, it is possible to form a container such as a bag or a vouch with an oxygen scavenger or oxygen scavenger complex, or to form a desired three-dimensional shape by press molding into a container having a oxygen scavenging function. You can also. In addition, it can be used by bonding it to the base sheet of the container and forming it into a paperboard container, a hollow shape such as a cylindrical shape or a bottle shape, or a container shape such as a carton or tray shape. By making the oxygen scavenger intermediate in a form other than the sheet form, a container having a deoxygenating function having a form adapted to these containers can be produced.
[0115] また、本発明の脱酸素剤又は脱酸素剤複合体は製造後に押出成形、加圧成形、 打錠成形等を用い、球状やヌードル状、繊維状等の形状に加工することもできる。  [0115] 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. .
[0116] 本発明の脱酸素剤及び脱酸素剤複合体は、食品の鮮度維持、医療用器具等の酸 化防止、金属の防鲭、寝具、衣類、美術品等の防かび、防虫等の用途に適用するこ とがでさる。  [0116] The oxygen scavenger and oxygen scavenger complex of the present invention are used for maintaining the freshness of food, preventing oxidation of medical equipment, anti-mold of metal, bedding, clothes, anti-fungals for art, etc. It can be applied to applications.
実施例  Example
[0117] 以下、実施例により本発明をさらに具体的に説明する。  [0117] Hereinafter, the present invention will be described more specifically with reference to Examples.
下記実施例 1— 1、 1— 2、 2— 1及び 2— 2並びに比較例 1— 1、 2— 1及び 2— 2の ようにして脱酸素剤を作製し、その脱酸素性能を調べた。表 1 1及び 2— 1に脱酸 素剤の組成比率と坪量、表 1 2及び 2— 2に原料組成物中の固形分の配合比率と 抄造歩留まり、表 1 3及び 2— 3に脱酸素剤中の鉄粉の有効反応率、 VSM力 求 められた酸素吸収に寄与する有効鉄粉量及び TG力 求められた固形分の組成比 率をそれぞれ示した。  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 1 and 2-1 show the composition ratio and basis weight of the deoxidizing agent, Tables 1 and 2 and 2 show the blending ratio of the solid content in the raw material composition and the papermaking yield, and Tables 1 and 3 show the removal ratio. The effective reaction rate of iron powder in the oxygen agent, the amount of effective iron powder contributing to oxygen absorption determined by VSM force, and the composition ratio of solid content determined by TG force are shown.
[0118] 〔実施例 1 1〕 [Example 1 1]
<原料組成物配合 >  <Raw material composition>
繊維状物：パルプ繊維 (NBKP、製造者:フレッチャー チャレンジ カナダ、商品 名「Mackenzie」、 CSF150ml、 ) 17質量0 /0 The fibrous material: pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, the trade name of "Mackenzie", CSF150ml,) 17 mass 0/0
被酸化性金属:鉄粉 (同和鉄粉鉱業 (株)製、商品名「RKH」）83質量％ 凝集剤:上記原料組成物 100質量部に対し、下記カチオン性凝集剤 1. 0質量部 及び下記ァ-オン性凝集剤 0. 2質量部  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
カチオン性凝集剤:ポリアミドェピクロロヒドリン榭脂（星光 PMC (株)製、商品名「W S4020」;>  Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hokko PMC Co., Ltd., trade name “W S4020”;>
ァ-オン性凝集剤：カルボキシメチルセルロースナトリウム (第一工業製薬 (株)製、 商品名 HE1500F、エーテルィ匕度 1. 45、粘度 2500〜3500mPa，s)  Char-on flocculant: sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
水：工業用水、固形分濃度 1. 25質量％となるまで添カロ  Water: Industrial water, solid content 1.25% by mass until added
[0119] <原料調製条件 > 実機による抄造プロセスを想定し、上記スラリーを JISパルパ一を用い、 JIS P820 9に準じて攪拌を行 、、支持目盛り 1000でストップした。 [0119] <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.
[0120] <抄造条件 > [0120] <Conditioning conditions>
上記配合の原料組成物を用い、 0. 11質量％になるまで希釈し、 JIS P8209に準 じて幅 250 X 250mmの角形シートマシーン (熊谷理機工業 (株)製)を用いて、抄紙 して湿潤状態のシート状の抄造体を作製した。  Using the raw material composition of the above composition, 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.
[0121] <乾燥条件 > [0121] <Drying conditions>
KRK回転型乾燥機 (熊谷理機工業 (株)製)を用いて、含水率が 1質量％以下とな るように乾燥を行ってシート状の脱酸素剤中間体を得た。  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.
[0122] <電解液添加条件 > [0122] <Electrolytic solution addition conditions>
上記脱酸素剤中間体 100質量部に対して下記電解液を 55質量部添加して所望の 脱酸素剤を得た。得られた脱酸素剤の含水率は表 1 1に示すように 35. 1質量％ であった。  55 parts by mass of the following electrolyte was added to 100 parts by mass of the oxygen scavenger intermediate to obtain a desired oxygen scavenger. The moisture content of the obtained oxygen scavenger was 35.1% by mass as shown in Table 11.
[0123] <電解液 > [0123] <Electrolyte>
電解質:精製塩 (NaCl)  Electrolyte: Purified salt (NaCl)
水：工業用水  Water: Industrial water
電解液濃度： 1質量％  Electrolyte concentration: 1% by mass
[0124] [表 1-1] [0124] [Table 1-1]
Figure imgf000029_0001
Figure imgf000029_0001
[0125] 〔実施例 1 2〕 [Example 1 2]
原料調製条件を JISパルパ一を用いず、約 15秒の手による攪拌で調製した以外は 実施例 1 1と同様に脱酸素剤を作製した。  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.
[0126] 〔比較例 1 1〕 [Comparative Example 1 1]
<原料組成物配合 >  <Raw material composition>
繊維状物：パルプ繊維 (NBKP、製造者:フレッチャー チャレンジ カナダ、商品 名「Mackenzie」、 CSF150ml、 ) 17質量0 /0 Fibrous material: Pulp fiber (NBKP, Manufacturer: Fletcher Challenge Canada, commodity The name "Mackenzie", CSF150ml,) 17 mass 0/0
被酸化性金属:鉄粉 (同和鉄粉鉱業 (株)製、商品名「RKH」）83質量％ 凝集剤:上記原料組成物 100質量部に対し、下記カチオン性凝集剤 1. 0質量部 及び下記ァ-オン性凝集剤 0. 2質量部  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
カチオン性凝集剤:ポリアミドェピクロロヒドリン榭脂（星光 PMC (株)製、商品名「W Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hokko PMC Co., Ltd., trade name “W
S4020」;> S4020 '';>
ァ-オン性凝集剤：カルボキシメチルセルロースナトリウム (第一工業製薬 (株)製、 商品名 HE1500F、エーテルィ匕度 1. 45、粘度 2500〜3500mPa，s)  Char-on flocculant: sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
水：工業用水、固形分濃度 1. 25質量％となるまで添カロ  Water: Industrial water, solid content 1.25% by mass until added
食塩:上記スラリー 100質量部に対し、食塩を 1. 0質量部  Salt: 1.0 part by weight of salt per 100 parts by weight of the slurry
[0127] <原料調製条件 > [0127] <Raw material preparation conditions>
実機による抄造プロセスを想定し、上記スラリーを JISパルパ一を用い、 JIS P820 9に準じて攪拌を行 、、支持目盛り 1000でストップした。  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.
[0128] <抄造条件 > [0128] <Conditioning conditions>
上記配合の原料組成物を用い、 0. 11質量％になるまで希釈し、 JIS P8209に準 じて幅 250 X 250mmの角形シートマシーン (熊谷理機工業 (株)製)を用いて、抄紙 後、圧搾して湿潤状態のシート状の抄造体を作製した。また、希釈水は 1質量％のN aCl水溶液を用いた。得られた脱酸素剤の含水率は表 1—1に示すように 34. 7質量 %であった。  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.
[0129] <脱酸素剤の形態 > [0129] <Form of oxygen scavenger>
得られた脱酸素剤は、その 1枚の厚みが 0. 2〜0. 4mm、坪量 194〜263gZm2で あった。なお、厚みは、 JIS P8118に準じ、脱酸素剤の 5点以上を測定し、その平均 値を厚みとして算出し、坪量は、少なくとも 100cm2以上の面積の脱酸素剤重量を測 定し、その面積で除すことにより算出した。 The obtained oxygen scavenger had a thickness of 0.2 to 0.4 mm and a basis weight of 194 to 263 gZm 2 . The thickness is measured in accordance with JIS P8118 at 5 points or more of the oxygen scavenger, the average value is calculated as the thickness, and the basis weight is measured at the weight of the oxygen scavenger at an area of at least 100 cm 2 . It was calculated by dividing by the area.
[0130] 〔脱酸素剤の脱酸素性能の測定〕 [0130] [Measurement of oxygen scavenger performance of oxygen scavenger]
実施例 1— 1及び比較例 1— 1の脱酸素剤 10gを、酸素透過性を有する被覆層で 被覆しない状態で空気容積 5. 5リットルのデシケータ中に設置し、該デシケータ中の 酸素濃度を測定して脱酸素性能を調べた。酸素濃度は泰榮電器株式会社製酸素モ ユタ OM— 25MS01を用いて測定した。それらの結果を図 1に示す。 An oxygen scavenger of Example 1-1 and Comparative Example 1-1 was installed in a desiccator having an air volume of 5.5 liters without being covered with an oxygen-permeable coating layer, and the oxygen concentration in the desiccator was determined. Measurements were made to determine the deoxygenation performance. Oxygen concentration is made by Taiho Electric Co., Ltd. It was measured using Utah OM-25MS01. The results are shown in Fig. 1.
[0131] 〔VSMによる脱酸素剤中の脱酸素に有効な鉄粉量の測定〕  [0131] [Measurement of iron powder effective for deoxygenation in oxygen absorber by VSM]
VSMとして東栄工業株式会社製の VSM-P7-15を使用して脱酸素剤中の脱酸素 に有効な鉄粉量を測定した。その結果を表 1 3に示す。  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.
[0132] 〔TGによる脱酸素剤の組成比率の測定〕  [0132] [Measurement of composition ratio of oxygen scavenger by TG]
TGとしてセイコーインスツルメンッ株式会社製高温型示差熱熱重量同時測定装置 T GZDTA— 6300及びオートサンプラユニット AST— 2を使用して脱酸素剤の組成 比率を測定した。また、サンプル容器は 1000°Cの高温に耐えるように、 Pt製 φ 5mm 、高さ 5mm品を用いた。その結果を表 1 3に示す。  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.
[0133] [表 1-2]  [0133] [Table 1-2]
Figure imgf000031_0001
Figure imgf000031_0001
[0134] [表 1-3] [0134] [Table 1-3]
Figure imgf000031_0002
Figure imgf000031_0002
[0135] 図 1および表 1 2、 1 3に示したように、実施例 1 1の鉄粉の有効反応率は実 施例 1 2の手で攪拌した試料に近い有効反応率を示しており、ほとんど酸化反応が 進行していないことがわ力つた。それに比べ、比較例 1—1は、反応助剤となる電解 質を抄造の段階で含んでいるため、酸化反応が進行してしまい、鉄粉の有効反応率 が低いことが明ら力となった。よって、実施例 1—1の限界酸素濃度は 0%になるのに 対し、比較例 1—1は 6%で飽和する結果となった。また、抄造歩留まりにおいても、 実施例 1 1、 1 2は反応助剤となる電解質を抄造の段階で含んでいないため、抄 造歩留まりが高ぐ工業的にも安定かつ高品質、低コストで製造することが可能であ ることがわかった。 [0135] As shown in Fig. 1 and Tables 12 and 13, the effective reaction rate of the iron powder of Example 1 1 shows an effective reaction rate close to that of the sample stirred by hand of Example 1 2. It was clear that the oxidation reaction was hardly progressing. 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. Therefore, the limiting oxygen concentration of Example 1-1 was 0%, whereas Comparative Example 1-1 was saturated at 6%. Also in paper making yield, Since Examples 1 1 and 1 2 do not contain an electrolyte as a reaction aid at the stage of papermaking, they can be manufactured at a stable, high quality, and low cost industrially with a high papermaking yield. I understood it.
[0136] 〔実施例 2— 1〕 [Example 2-1]
<原料組成物配合 >  <Raw material composition>
繊維状物：パルプ繊維 (NBKP、製造者:フレッチャー チャレンジ カナダ、商品 名「Mackenzie」、 CSF150ml、 ) 15質量0 /0 The fibrous material: pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, the trade name of "Mackenzie", CSF150ml,) 15 mass 0/0
被酸化性金属:鉄粉 (同和鉄粉鉱業 (株)製、商品名「RKH」）75質量％ 保水剤：活性炭 (日本エンバイ口ケミカル (株)製、商品名「カルボラフィン」 ) 10質量 Oxidizable metal: Iron powder (made by Dowa Iron Mining Co., Ltd., trade name “RKH”) 75% by weight Water retention agent: Activated carbon (produced by Nippon Enviguchi Chemical Co., Ltd., trade name “Carborafyn”)
% %
凝集剤:上記原料組成物 100質量部に対し、下記カチオン性凝集剤 1. 0質量部 及び下記ァ-オン性凝集剤 0. 2質量部  Flocculant: The following cationic flocculant 1.0 parts by mass and the following ion flocculant 0.2 parts by mass with respect to 100 parts by mass of the above raw material composition
カチオン性凝集剤:ポリアミドェピクロロヒドリン榭脂（星光 PMC (株)製、商品名「W S4020」;>  Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hokko PMC Co., Ltd., trade name “W S4020”;>
ァ-オン性凝集剤：カルボキシメチルセルロースナトリウム (第一工業製薬 (株)製、 商品名 HE1500F、エーテルィ匕度 1. 45、粘度 2500〜3500mPa，s)  Char-on flocculant: sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
水：工業用水、固形分濃度 1. 25質量％となるまで添カロ  Water: Industrial water, solid content 1.25% by mass until added
[0137] <原料調製条件 > [0137] <Raw material preparation conditions>
実機による抄造プロセスを想定し、上記スラリーを JISパルパ一を用い、 JIS P820 9に準じて攪拌を行 、、支持目盛り 1000でストップした。  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.
[0138] <抄造条件 > [0138] <Conditioning conditions>
上記配合の原料組成物を用い、 0. 11質量％になるまで希釈し、 JIS P8209に準 じて幅 250 X 250mmの角形シートマシーン (熊谷理機工業 (株)製)を用いて、抄紙 して湿潤状態のシート状の抄造体を作製した。  Using the raw material composition of the above composition, 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.
[0139] <乾燥条件 > [0139] <Drying conditions>
KRK回転型乾燥機 (熊谷理機工業 (株)製)を用いて、含水率が 1質量％以下とな るように乾燥を行ってシート状の脱酸素剤中間体を得た。  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.
[0140] <電解液添加条件 > 上記脱酸素剤中間体 100質量部に対して下記電解液を 55質量部添加して所望の 脱酸素剤を得た。得られた脱酸素剤の含水率は表 2— 1に示すように 35. 1質量％ であった。 [0140] <Electrolytic solution addition conditions> 55 parts by mass of the following electrolyte was added to 100 parts by mass of the oxygen scavenger intermediate to obtain a desired oxygen scavenger. The moisture content of the obtained oxygen scavenger was 35.1% by mass as shown in Table 2-1.
[0141] く電解液〉 [0141] Ku Electrolyte>
電解質:精製塩 (NaCl)  Electrolyte: Purified salt (NaCl)
水：工業用水  Water: Industrial water
電解液濃度: 1質量％  Electrolyte concentration: 1% by mass
[0142] [表 2-1] [0142] [Table 2-1]
Figure imgf000033_0001
Figure imgf000033_0001
[0143] 〔実施例 2— 2〕 [Example 2-2]
原料調製条件を JISパルパ一を用いず、約 15秒の手による攪拌で調製した以外は 実施例 2— 1と同様に脱酸素剤を作製した。  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.
[0144] 〔比較例 2— 1〕 [Comparative Example 2-1]
<原料組成物配合 >  <Raw material composition>
繊維状物：パルプ繊維 (NBKP、製造者:フレッチャー チャレンジ カナダ、商品 名「Mackenzie」、 CSF150ml、 ) 17質量0 /0 The fibrous material: pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, the trade name of "Mackenzie", CSF150ml,) 17 mass 0/0
被酸化性金属:鉄粉 (同和鉄粉鉱業 (株)製、商品名「RKH」）83質量％ 凝集剤:上記原料組成物 100質量部に対し、下記カチオン性凝集剤 1. 0質量部 及び下記ァ-オン性凝集剤 0. 2質量部  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
カチオン性凝集剤:ポリアミドェピクロロヒドリン榭脂（星光 PMC (株)製、商品名「W S4020」;>  Cationic flocculant: Polyamide epoxy hydrin rosin (manufactured by Hokko PMC Co., Ltd., trade name “W S4020”;>
ァ-オン性凝集剤：カルボキシメチルセルロースナトリウム (第一工業製薬 (株)製、 商品名 HE1500F、エーテルィ匕度 1. 45、粘度 2500〜3500mPa，s)  Char-on flocculant: sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name HE1500F, etherity 1.45, viscosity 2500-3500mPa, s)
水：工業用水、固形分濃度 1. 25質量％となるまで添カロ 食塩:上記スラリー 100質量部に対し、食塩を 1. 0質量部 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
[0145] <原料調製条件 > [0145] <Raw material preparation conditions>
実機による抄造プロセスを想定し、上記スラリーを JISパルパ一を用い、 JIS P820 9に準じて攪拌を行 、、支持目盛り 1000でストップした。  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.
[0146] <抄造条件 > [0146] <Conditioning conditions>
上記配合の原料組成物を用い、 0. 11質量％になるまで希釈し、 JIS P8209に準 じて幅 250 X 250mmの角形シートマシーン (熊谷理機工業 (株)製)を用いて、抄紙 後、圧搾して湿潤状態のシート状の抄造体を作製した。また、希釈水は 1質量％のN aCl水溶液を用いた。得られた脱酸素剤の含水率は表 2—1に示すように 34. 7質量 %であった。  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 2-1.
[0147] 〔比較例 2— 2〕 [Comparative Example 2-2]
三菱ガス化学 (株)製、商品名エージレス SA (自力反応型、速効タイプ)を用いた。  The product name Ageless SA (self-reactive type, fast-acting type) manufactured by Mitsubishi Gas Chemical Co., Ltd. was used.
[0148] <脱酸素剤の形態 > [0148] <Form of oxygen scavenger>
得られた脱酸素剤は、表 2— 1に示すように、その 1枚の厚みが 0. 2〜0. 4mm、坪 量 194〜302g/m2であった。なお、厚みは、 JIS P8118に準じ、脱酸素剤の 5点 以上を測定し、その平均値を厚みとして算出し、坪量は、少なくとも 100cm2以上の 面積の脱酸素剤重量を測定し、その面積で除すことにより算出した。 As shown in Table 2-1, the obtained oxygen scavenger had a thickness of 0.2 to 0.4 mm and a basis weight of 194 to 302 g / m 2 . 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.
[0149] 〔脱酸素剤の脱酸素性能の測定〕 [Measurement of oxygen scavenger performance of oxygen scavenger]
実施例 2—1及び比較例 2—1、 2— 2の脱酸素剤 10gを、酸素透過性を有する被 覆層で被覆しない状態で空気容積 5. 5リットルのデシケータ中に設置し、該デシケ ータ中の酸素濃度を測定して脱酸素性能を調べた。酸素濃度は泰榮電器株式会社 製酸素モニタ OM— 25MS01を用いて測定した。それらの結果を図 2に示す。  10 g of the oxygen scavengers of Example 2-1 and Comparative Examples 2-1 and 2-2 were not covered with an oxygen-permeable covering layer and placed in a desiccator having a volume of 5.5 liters. Deoxygenation performance was examined by measuring the oxygen concentration in the sensor. The oxygen concentration was measured using an oxygen monitor OM-25MS01 manufactured by Taiho Electric Co., Ltd. The results are shown in Fig. 2.
[0150] 〔VSMによる脱酸素剤中の脱酸素に有効な鉄粉量の測定〕 [0150] [Measurement of amount of iron powder effective for deoxygenation in oxygen absorber by VSM]
VSMとして東栄工業株式会社製の VSM-P7-15を使用して脱酸素剤中の脱酸素 に有効な鉄粉量を測定した。その結果を表 2— 3に示す。  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.
[0151] 〔TGによる脱酸素剤の組成比率の測定〕 [0151] [Measurement of composition ratio of oxygen scavenger by TG]
TGとしてセイコーインスツルメンッ株式会社製高温型示差熱熱重量同時測定装置 TGZDTA— 6300及びオートサンプラユニット AST— 2を使用して脱酸素剤の組成 比率を測定した。また、サンプル容器は 1000°Cの高温に耐えるように、 Pt製 φ 5mm 、高さ 5mm品を用いた。その結果を表 2— 3に示す。 Composition of oxygen scavenger 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 ratio was measured. 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.
[0152] [表 2- 2] [0152] [Table 2-2]
Figure imgf000035_0001
Figure imgf000035_0001
[0153] [表 2-3] [0153] [Table 2-3]
Figure imgf000035_0002
Figure imgf000035_0002
[0154] 図 2及び表 2— 2、 2— 3に示したように、実施例 2— 1で得られた脱酸素剤は、反応 助剤となる電解質を抄造の段階で含んでいないため、酸化反応が進行せず、鉄粉の 有効反応率が高いことが明らかとなった。よって、限界酸素濃度は実施例 2—1では 0%になるのに対し、比較例 2—1では 6%で飽和する結果となった。さらに、実施例 2 1は保水剤を有しているため、比較例 2— 1と比較すると素早い時間で酸素を吸収 する能力を有していることがわ力つた。また、抄造歩留まりにおいても、実施例 2—1 は反応助剤となる電解質を抄造の段階で含んでいないため、抄造歩留まりが高ぐ 工業的にも安定かつ高品質、低コストで製造することが可能である。さらに比較例 2 2の保水剤が含まれた市販の粉体型脱酸素剤との比較においても素早い時間で 高 、脱酸素性能が得られることがわ力つた。 [0154] As shown in Fig. 2 and Tables 2-2 and 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. Therefore, the critical oxygen concentration was 0% in Example 2-1 while it was saturated at 6% in Comparative Example 2-1. Furthermore, since Example 21 has a water retention agent, it was found that it had the ability to absorb oxygen in a quicker time than Comparative Example 2-1. Also, in terms of papermaking yield, Example 2-1 does not contain an electrolyte as a reaction aid at the papermaking stage, so the papermaking yield is high and it can be manufactured at an industrially stable, high quality and low cost. Is possible. Furthermore, in comparison with a commercially available powder-type oxygen scavenger containing the water retention agent of Comparative Example 22 or 2, it was found that high oxygen scavenging performance was obtained in a quick time.
産業上の利用可能性  Industrial applicability
[0155] 第 1発明の脱酸素剤によれば、被酸化性金属を効率良く酸化反応させ、より少ない 量で高い脱酸素性能が得られる。また、本発明の脱酸素剤複合体によれば、上記脱 酸素剤の有する脱酸素性能に機能層の有する種々の機能を付与することができる。 本発明の脱酸素剤及び脱酸素剤複合体の製造方法は、酸化反応助剤となる電解質 を含まず、被酸化性金属及び繊維状物からなるスラリーを調製し製造を行うことで、ス ラリー調製中、供給中及び或いは成形中の被酸化性金属の酸化による脱酸素性能 の劣化を最小限に抑えることができ、上記脱酸素剤及び脱酸素剤複合体を好適に 製造することができる。 [0155] According to the oxygen scavenger of the first invention, the oxidizable metal is efficiently oxidized to reduce the amount. High deoxygenation performance is obtained in quantity. 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 production method of the oxygen scavenger and oxygen scavenger complex of the present invention does not include an electrolyte that serves as an oxidation reaction aid, and prepares and manufactures a slurry made of an oxidizable metal and a fibrous material. It is possible to minimize the deterioration of the oxygen removal performance due to the oxidation of the oxidizable metal during preparation, supply and / or molding, and the oxygen absorber and oxygen absorber complex can be preferably produced.
第 2発明の脱酸素剤によれば、素早い時間で高い脱酸素性能が得られる。また、 本発明の脱酸素剤複合体によれば、上記脱酸素剤の有する脱酸素性能に機能層 の有する種々の機能を付与することができる。本発明の脱酸素剤及び脱酸素剤複合 体の製造方法は、酸化反応助剤となる電解質を含まず、被酸化性金属、保水剤、及 び繊維状物からなるスラリーを調製し製造を行うことで、スラリー調製中、供給中及び 或 ヽは成形中の被酸化性金属の酸化による脱酸素性能の劣化を最小限に抑えるこ とができ、上記脱酸素剤及び脱酸素剤複合体を好適に製造することができる。  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

請求の範囲 The scope of the claims
[I] 被酸化性金属及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸 化反応助剤となる電解質を含ませた脱酸素剤であって、  [I] 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,
前記電解質を 0. 1〜10質量％含み且つ含水率が 5〜70質量％である脱酸素剤。  An oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass.
[2] 前記繊維状物の CSFが 600ml以下である請求の範囲第 1項に記載の脱酸素剤。 [2] The oxygen absorber according to claim 1, wherein the fibrous material has a CSF of 600 ml or less.
[3] 前記被酸化性金属の有効反応率が 75%以上である請求の範囲第 1項又は第 2項 に記載の脱酸素剤。 [3] The oxygen scavenger according to claim 1 or 2, wherein an effective reaction rate of the oxidizable metal is 75% or more.
[4] 請求の範囲第 1項〜第 3項の何れかに記載の脱酸素剤に使用する脱酸素剤中間 体であって、被酸化性金属及び繊維状物を含み抄造体を乾燥してなる脱酸素剤中 間体。  [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] 請求の範囲第 1項〜第 3項の何れかに記載の脱酸素剤に機能層が設けられている 脱酸素剤複合体。  [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] 前記機能層が接着層を介して積層されている請求の範囲第 5項に記載の脱酸素 剤複合体。  [6] The oxygen scavenger complex according to claim 5, wherein the functional layer is laminated via an adhesive layer.
[7] 前記機能層が固形成分の脱落防止、隠蔽、消臭、耐磁、水分バリア若しくは油分 ノリアの機能又はこれらの機能が複数組み合わされた機能を有している請求の範囲 第 5項又は第 6項に記載の脱酸素剤複合体。  [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] 請求の範囲第 1項に記載の脱酸素剤の製造方法であって、被酸化性金属及び繊 維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反応助剤となる電解 質を含ませる脱酸素剤の製造方法。  [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] 請求の範囲第 5項に記載の脱酸素剤複合体の製造方法であって、被酸化性金属 及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、前記機能層を設け た後、酸化反応助剤となる電解質を含ませる脱酸素剤複合体の製造方法。  [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] 請求の範囲第 5項に記載の脱酸素剤複合体の製造方法であって、被酸化性金属 及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反応助剤とな る電解質を含ませて脱酸素剤を製造した後、該脱酸素剤に前記機能層を設けた脱 酸素剤複合体の製造方法。  [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.
[I I] 被酸化性金属、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中 間体に、酸化反応助剤となる電解質を含ませた脱酸素剤であって、 [II] In an oxygen scavenger obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material An oxygen scavenger containing an electrolyte as an oxidation reaction aid in the intermediate body,
前記電解質を 0. 1〜10質量％含み且つ含水率が 5〜70質量％である脱酸素剤。  An oxygen scavenger containing 0.1 to 10% by mass of the electrolyte and having a water content of 5 to 70% by mass.
[12] 前記繊維状物の CSFが 600ml以下である請求の範囲第 11項に記載の脱酸素剤 [12] The oxygen absorber according to claim 11, wherein the fibrous material has a CSF of 600 ml or less.
[13] 前記被酸ィ匕性金属の有効反応率が 75%以上である請求の範囲第 11項又は第 12 項に記載の脱酸素剤。 [13] The oxygen scavenger according to [11] or [12], wherein an effective reaction rate of the oxidizable metal is 75% or more.
[14] 請求の範囲第 11項〜第 13項の何れかに記載の脱酸素剤に使用する脱酸素剤中 間体であって、被酸化性金属、保水剤、及び繊維状物を含む抄造体を乾燥してなる 脱酸素剤中間体。  [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] 請求の範囲第 11項〜第 13項の何れかに記載の脱酸素剤に機能層が設けられて いる脱酸素剤複合体。  [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] 前記機能層が接着層を介して積層されている請求の範囲第 15項に記載の脱酸素 剤複合体。  16. The oxygen scavenger complex according to claim 15, wherein the functional layer is laminated via an adhesive layer.
[17] 前記機能層が固形成分の脱落防止、隠蔽、消臭、耐磁、水分バリア若しくは油分 ノリアの機能又はこれらの機能が複数組み合わされた機能を有している請求の範囲 第 15項又は第 16項に記載の脱酸素剤複合体。  [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] 請求の範囲第 11項項に記載の脱酸素剤の製造方法であって、被酸化性金属、保 水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反応助 剤となる電解質を含ませる脱酸素剤の製造方法。 [18] The method for producing an oxygen scavenger according to claim 11, wherein the oxygen scavenger intermediate is obtained by drying a paper product containing an oxidizable metal, a water retention agent, and a fibrous material. And a method for producing an oxygen scavenger, which contains an electrolyte as an oxidation reaction aid.
[19] 請求の範囲第 15項に記載の脱酸素剤複合体の製造方法であって、被酸化性金属[19] The method for producing the oxygen scavenger complex according to claim 15, wherein the oxidizable metal
、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、前記機 能層を設けた後、酸化反応助剤となる電解質を含ませる脱酸素剤複合体の製造方 法。 , 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] 請求の範囲第 15項に記載の脱酸素剤複合体の製造方法であって、被酸化性金属 、保水剤、及び繊維状物を含む抄造体を乾燥してなる脱酸素剤中間体に、酸化反 応助剤となる電解質を含ませて脱酸素剤を製造した後、該脱酸素剤に前記機能層 を設けた脱酸素剤複合体の製造方法。  [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. A method for producing an oxygen scavenger complex in which an oxygen scavenger is produced by adding an electrolyte as an oxidation reaction aid, and then the functional layer is provided on the oxygen scavenger.
PCT/JP2006/321339 2005-10-27 2006-10-26 Oxygen scavenger, oxygen scavenger intermediate, oxygen scavenger composite, and process for producing the same WO2007049676A1 (en)

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US9120817B2 (en) 2010-03-23 2015-09-01 Viiv Healthcare Company Process for preparing (4R,12aS)-7-methoxy-4-methyl-6,8-dioxo-3,4,6,8,12,12a-hexahydro-2H-pyrido[1′ ,2′:4,5]pyrazino[2,1-b][1,3]oxazine-9-carboxylic acid

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JPS62234544A (en) * 1985-06-26 1987-10-14 Mitsubishi Gas Chem Co Inc Sheet type oxygen scavenger
JP2003102761A (en) * 2001-09-28 2003-04-08 Kao Corp Method of manufacturing heating compact
JP2004332180A (en) * 2003-05-12 2004-11-25 Kao Corp Exothermic formed article

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JPS62234544A (en) * 1985-06-26 1987-10-14 Mitsubishi Gas Chem Co Inc Sheet type oxygen scavenger
JP2003102761A (en) * 2001-09-28 2003-04-08 Kao Corp Method of manufacturing heating compact
JP2004332180A (en) * 2003-05-12 2004-11-25 Kao Corp Exothermic formed article

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9120817B2 (en) 2010-03-23 2015-09-01 Viiv Healthcare Company Process for preparing (4R,12aS)-7-methoxy-4-methyl-6,8-dioxo-3,4,6,8,12,12a-hexahydro-2H-pyrido[1′ ,2′:4,5]pyrazino[2,1-b][1,3]oxazine-9-carboxylic acid

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