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WO2007049676A1 - Desoxygenant, produit intermediaire desoxygenant, composite desoxygenant et procede de production correspondant - Google Patents

Desoxygenant, produit intermediaire desoxygenant, composite desoxygenant et procede de production correspondant 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
Prior art date
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Ceased
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PCT/JP2006/321339
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English (en)
Japanese (ja)
Inventor
Yoshiaki Kumamoto
Masataka Ishikawa
Taijun Yoshida
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Kao Corp
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Kao Corp
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Classifications

    • 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
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B2/708—Preservation of foods or foodstuffs, in general 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
    • A23B2/712—Preservation of foods or foodstuffs, in general 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
    • A23B2/717—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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Food Science & Technology (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract

La présente invention concerne un désoxygénant qui comprend: un produit intermédiaire désoxygénant obtenu par séchage d'une feuille constituée d'un métal oxydable et d'un matériau fibreux et formée selon un procédé de fabrication du papier; et un électrolyte utilisé en tant qu'auxiliaire d'oxydation incorporé dans le produit intermédiaire. Le désoxygénant contient de 0,1 à 10% en masse d'électrolyte et il présente une teneur en eau comprise entre 5 et 70% en masse. Le matériau fibreux présente, de préférence, un CSF égal ou inférieur à 600 mL. De préférence, le métal oxydable représente au moins 75% de la matière réagissant efficacement.
PCT/JP2006/321339 2005-10-27 2006-10-26 Desoxygenant, produit intermediaire desoxygenant, composite desoxygenant et procede de production correspondant Ceased WO2007049676A1 (fr)

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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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62234544A (ja) * 1985-06-26 1987-10-14 Mitsubishi Gas Chem Co Inc シ−ト状脱酸素剤
JP2003102761A (ja) * 2001-09-28 2003-04-08 Kao Corp 発熱成形体の製造方法
JP2004332180A (ja) * 2003-05-12 2004-11-25 Kao Corp 発熱成形体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62234544A (ja) * 1985-06-26 1987-10-14 Mitsubishi Gas Chem Co Inc シ−ト状脱酸素剤
JP2003102761A (ja) * 2001-09-28 2003-04-08 Kao Corp 発熱成形体の製造方法
JP2004332180A (ja) * 2003-05-12 2004-11-25 Kao Corp 発熱成形体

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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