WO2006095640A1 - Powdery oxygen absorbent material and process for producing the same - Google Patents

Powdery oxygen absorbent material and process for producing the same Download PDF

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Publication number
WO2006095640A1
WO2006095640A1 PCT/JP2006/304044 JP2006304044W WO2006095640A1 WO 2006095640 A1 WO2006095640 A1 WO 2006095640A1 JP 2006304044 W JP2006304044 W JP 2006304044W WO 2006095640 A1 WO2006095640 A1 WO 2006095640A1
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Prior art keywords
oxygen
absorbing material
step
powdery
thermoplastic polymer
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PCT/JP2006/304044
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French (fr)
Japanese (ja)
Inventor
Hideki Hayashi
Toshiaki Oono
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Asahi Kasei Chemicals Corporation
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409Preservation 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
    • A23L3/3418Preservation 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
    • A23L3/3427Preservation 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
    • A23L3/3436Oxygen absorbent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/261Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/264Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2309/00Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06Copolymers with styrene

Abstract

A powdery oxygen absorbent material that has the properties of being responsive to metal detectors, being responsive to microwave ovens and moisture unwanted, and that exhibits an amount of oxygen absorbed and rate of oxygen absorption equal to or greater than those of iron based oxygen absorbent materials. There is provided a powdery oxygen absorbent material characterized by containing thermoplastic polymer (A) of 10 to 400 Mooney viscosity which in the measuring by differential scanning calorimeter (DSC) has no crystal melting peak or has a melting point of < 75°C, the thermoplastic polymer containing an allyl hydrogen and/or a hydrogen bonded with tertiary carbon in its molecule, and oxidation accelerating component (B), and characterized by having a specific surface area of ≥ 60 cm2/g.

Description

Specification

Powdery oxygen-absorbing material and their preparation

Technical field

[0001] The present invention, metal products, food, pharmaceutical, photographic film, manuscripts, paintings, suitably Yore is related powdery oxygen-absorbing material for storing and electronic products.

BACKGROUND

[0002] The metal products, food, pharmaceutical, photographic film, manuscripts, typified by painting and electronic products, for the purpose of preventing deterioration of easy various articles degenerated under the influence of oxygen and these articles were retract and deoxidizer is used conventionally to perform the oxygen removal of the packaging container and the packaging bag.

[0003] As the deoxidizer is iron based oxygen absorber is mainly used, catechol, Asuko Rubin acid, oxygen absorbent and oxygen easily reacts with the resin as a main component has been proposed.

[0004] Factors that iron based oxygen absorber is mainly used, the oxygen absorption amount per iron based oxygen absorber lg is 68Cc, oxygen absorption rate is excellent 18cc / (g 'hr) and oxygen absorption performance it is the main factor.

[0005] On the other hand, iron-based oxygen absorber, which is likely to discharge or firing at heating when applied to the package of food such as by metal detectors foreign object detection by the can such les ,, microwave, etc. also of the problem has been pointed out.

[0006] For this problem, catechol, oxygen absorbent has been proposed that the reaction tends resin Asukorubin acid and oxygen as a main component. In particular, the oxygen-absorbing material mainly composed of oxygen and easily reacts resin, so also take advantage under low humidity environment without requiring moisture oxygen absorbing reaction, it is expected future developments.

[0007] Patent Document 1, butadiene polymer liquid, tall oil fatty acid, soybean oil fatty acid cobalt consisting preparative and zeolite powder oxygen absorbing material (hereinafter, referred to conventional art 1), butadiene oligomer in Patent Document 2, cobalt stearate and an organic peroxide (di 2-t-butyl peroxide O carboxymethyl isopropylbenzene) was added powdered oxygen absorbent were crosslinked (hereinafter, referred to as conventional technology 2), obtained by emulsion polymerization in Patent Document 3 syndiotactic 1, 2 poly butadiene spherical particles (hereinafter, prior referred art 3) has been proposed. These oxygen intake Osamuzai may be oxygen-absorbing without the need for water. While with force, the prior art 1, the prior art 2, in the prior art 3, the oxygen absorption performance of the iron-based oxygen absorber, i.e. the amount of oxygen absorbed per oxygen absorber 1 g is 68Cc, and the oxygen absorption rate ferrous not been obtained only inferior compared to the oxygen-absorbing material 18cc / (g * hr) is reality.

[0008] Patent Document 1: JP-A-4 one 29741 JP

Patent Document 2: JP 11 - 70331 JP

Patent Document 3: JP 9 one 291 120 JP

Disclosure of the Invention

Problems that the Invention is to you'll solve

[0009] The present invention can correspond to a metal detector, adaptable to microwave and retain the characteristics such as moisture required, and an iron based oxygen absorber or more oxygen absorption rate and the oxygen absorption amount that having a flour and to provide a Jo oxygen absorber.

Means for Solving the Problems

[0010] The present inventors, as a result of extensive investigations to solve the above problems, the Mooney viscosity

Is 10 to 400, and differential scanning calorimetry and no crystalline melting peak when measured by a differential scanning calorimeter (DSC) or melting point is below 75 ° C, i.e. not substantially crosslinked, substantially amorphous of using a thermoplastic resin having a hydrogen bound to a Ariru hydrogen and / or tertiary carbon in the molecule, by applying the formulation and suitable shape suitable additives, iron unattainable in the prior art It found that powdery oxygen-absorbing material is obtained with a system oxygen absorbing material equal to or higher than the oxygen absorption rate and the oxygen absorption amount, the present invention has been accomplished.

[0011] Namely, the present invention is as follows.

(1) Mooney viscosity of 10 to 400, and differential run 查熱 meter when measured by a differential scanning calorimeter (DSC) no crystal melting peak or a melting point less than 75 ° C, Ariru hydrogen and Z or tertiary comprising a thermoplastic polymer having a hydrogen attached to the carbon in the molecule (a) and oxidation promoting component (B), powdered oxygen absorbent, characterized in that a specific surface area force S60cm 2 Zg above.

(2) powdery oxygen-absorbing material according to the above (1) to beam one hundred twenty-one viscosity of the thermoplastic polymer (A) is characterized in that 20 to 150.

(3) a thermoplastic polymer (A) is powdered oxygen absorbent according to (1) or (2) characterized in that it is a polymer or copolymer containing butadiene units 50 wt% or more.

(4) a thermoplastic polymer (A) consists of 50 to 99 wt% of butadiene units and 1 to 50% by weight of styrene units, characterized in that it is a copolymer block or random structure, the (1 ) Les to (3), powdery oxygen absorbing member according to any misalignment.

(5) 50 in the thermoplastic polymer (A):! A feature in that it contains antioxidants OOOppm the (C), the (1) to (4) Re, according to whether the deviation powdery oxygen-absorbing material.

(6) a thermoplastic polymer (A), and also contains the oxidation promoting component (B), and a thermoplastic polymer (A) to hardly adhere to each other but having adhesion of the fine particles (D), the average wherein the particle size at 10 xm to 5 mm, and is located at least partially (a) and (B) the force becomes the surface of the powder of the fine particles (D), (1) to (5) powdered oxygen intake Osamuzai according to any one of.

(7) The following method for manufacturing a powdered oxygen absorbent consisting of steps.

Step (X): a beam one hundred twenty-one viscosity 10 to 400, and differential scanning calorimetry (DSC) Ariru hydrogen and no crystalline melting peak or a melting point as measured is less than 75 ° C in / the thermoplastic polymer or the having hydrogen bound to tertiary carbon in the molecule (a) and oxidation promoting component (B) heating a molten state Niore, mixing molten Te

Step (Y): step process for Kona碎 the resulting melt mixture (X)

Step (Z): step (X) with resulting melt mixture or exposing the step (Y) obtained pulverized material into 2 Kirogu ray or radiation

Step (S): a step of storing the molten mixture or flour 碎物 hypoxic atmosphere

Effect of the invention

Powdery oxygen-absorbing material of the present invention, that it can be used with low humidity is a characteristic of the resin based oxygen-absorbing material environment, that can foreign matter detection by a metal detector, can also be used without problems put in a microwave oven It has the effect of both the characteristics of such a point, excellent oxygen absorption amount and the oxygen absorption rate than the iron based oxygen absorber. Furthermore, conventional iron-based, unlike organic-based oxygen absorbers has an effect of oxygen absorption even under a carbon dioxide atmosphere, particularly preferred because it can apply to the gas exchange packaging using carbon dioxide.

BRIEF DESCRIPTION OF THE DRAWINGS [0013] FIG. 1 is a diagram showing the oxygen absorption curve of Example 1 and Comparative Examples 1-4.

FIG. 2 is a view to showing the relationship of the induction period of the amount and powdery oxygen-absorbing material of the antioxidant of Example 3 (C).

DESCRIPTION OF SYMBOLS

[0014] 1 oxygen absorption curve of powdery oxygen-absorbing materials of Examples 1

Oxygen absorption curve of the second comparative example 1 powdered oxygen absorbent

3 oxygen absorption curve of powdery oxygen-absorbing material of Comparative Example 2

4 oxygen absorption curve of powdery oxygen-absorbing material of Comparative Example 3

5 Oxygen absorption curve of the iron-based oxygen-absorbing material of Comparative Example 4

♦ When using the phenol-based antioxidant as an antioxidant of Example 3

□ When using Iou antioxidant as an antioxidant of Example 3

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The present invention is specifically described below.

[0016] First, that the present invention is excellent in oxygen absorption performance over the prior art 1-3 show with reference to FIG.

[0017] Figure 1, in accordance with the oxygen absorption amount measurement method described below, the vertical axis represents the oxygen absorption amount obtained from the oxygen density for each elapsed time in the vessel which encloses the respective powdery oxygen-absorbing material, the lateral elapsed time it is a view taken on the axis. Oxygen absorption curve of the oxygen absorption curve, curve 2 the prior art 1 pulverulent oxygen absorber (Comparative Example 1) powdered oxygen absorbent Curve 1 present invention in FIG. 1 (Example 1), curve 3 oxygen absorption curve of the prior art 2 powdery oxygen-absorbing material (Comparative example 2), oxygen absorption curve, curve 5 is a commercially available iron-based oxygen-absorbing powdery oxygen-absorbing material of curve 4 is the prior art 3 (Comparative example 3) an oxygen absorption curve of wood (specific Comparative Examples 4).

[0018] where the oxygen concentration is powdered oxygen absorbent "saturated oxygen absorption amount" oxygen absorption amount per lg of upon reaching saturation (in cc / g) and then, and the maximum slope of the oxygen absorption curve (the unit cc / (g 'hr)) "maximum oxygen absorption rate" the size of the defined as. It is possible to saturate the oxygen absorption amount is reduced and a large listening, the amount of oxygen absorbent material to be used, can in a shape which does not stand out products can cheaply cost, has advantages like. Also, when the short time of up to a maximum oxygen absorption rate is high and / or the oxygen absorption rate is at a maximum, especially good in the case of using buns, fruit cake, doll baked, fast foods and the like to the pain, such as a side dish or lunch class better tool 巿 sales pouch-type oxygen absorbent, generally the time until the oxygen absorption rate is maximized is set to be no greater than between 4:00.

[0019] In FIG. 1, the powdery oxygen-absorbing material of the present invention shown as curve 1 starts the measurement immediately after starting or et oxygen absorption, 0.5 after 5 hours was 18 cc / g oxygen-absorbing, 0.5 hours after oxygen absorption rate within a relatively short time a maximum of the maximum oxygen absorption rate was 38cc / (g 'hr). The 0.5 and later after 5 hours while gradually oxygen absorption rate is reduced, the oxygen absorption amount after 24 hours 190CcZg, at about 48 hours reached substantially saturated, saturated oxygen absorption capacity at that time reached 230ccZg .

[0020] On the other hand, in the commercially available iron-based oxygen-absorbing material shown as curve 5 in oxygen absorption rate to 5 hours after 0.5 is maximum 18cc / (g 'hr), oxygen uptake reached almost saturation after about 24 hours Te, saturated amount of oxygen absorbed during their was 68CcZg.

[0021] Thus, powdery oxygen-absorbing material of the present invention as compared to commercially available iron-based oxygen absorber, it is understood that excellent very oxygen-absorbing characteristics.

[0022] In contrast, in the prior art 1 shown as curve 2, at 4 hours after any oxygen uptake 2 cc / g, the maximum oxygen absorption rate at 16 hours after indicate the maximum oxygen absorption rate measurement start lc It was c / (g 'hr). The oxygen absorption amount is almost reached saturation after three days, the saturated oxygen absorption amount at that time was 41 cc / g.

[0023] Next, in the prior art 2 shown as curve 3, initial low ingredients maximum oxygen absorption rate than the oxygen absorption amount of commercially available iron-based oxygen absorber to the measurement starting after 8 hours 14cc / (g 'hr) in it has been filed. The oxygen absorption amount is almost reached saturation after three days, the saturated oxygen absorption amount at that time 13

Was 2cc / g.

[0024] Further, in the conventional art 3, shown as curve 4, exhibit little ability to absorb oxygen after 24 hours, the maximum oxygen absorption rate was approximately OccZ (g 'hr). The oxygen absorption amount is almost reached saturation after 30 days, the saturated oxygen absorption amount at that time was 18 cc / g.

[0025] As described above, the present invention over the prior art, it is found to have a remarkable effect.

[0026] Further powdery oxygen-absorbing material of the present invention, unlike the conventional iron-based oxygen absorber Ya organic oxygen absorber, oxygen absorbent in an atmosphere of carbon dioxide is present. Carbon dioxide in order to have a bacteriostatic effect, often used in gas exchange packaging is one of the CA packaging intended for freshness (Controlled Atmosphere P ackaging) or MA packaging (Modified Atomosphere Packaging). Therefore powdery oxygen-absorbing material of the present invention, the conventional oxygen intake Osamuzai can be applied to the gas exchange packaging which has not available les, earthenware pots features have les, Ru.

[0027] For components constituting the powdery oxygen-absorbing material of the present invention will be described below.

(1 one 1) thermoplastic resin (A)

The thermoplastic resin having a hydrogen bound to a Ariru hydrogen and Z or tertiary carbon in the molecule fat (A), polybutadiene, polyisoprene, butadiene / isoprene copolymers, scan styrene / butadiene copolymer, styrene Z isoprene copolymers, butadiene / isoprene emission / styrene copolymers, copolymers of ethylene and cyclic alkylene, resins containing cyclohexene group cycloheteroalkyl, polypropylene, ethylene Z propylene copolymer, MXD6 polyamide (meta-xylene / adipic acid nylon ) of at least one and principal component resin selected from the group consisting of such as it is exemplified. Polybutadiene, as such as polyisoprene, 1, 2-bond, 1, 4 which bond is present, each may be a mixture in a single. Moreover, Cis, which Trans structures are also present, each may be a mixture in a single.

[0028] Of this such, from the viewpoint of the oxygen absorption amount and the oxygen absorption rate is high, Poributaji E down, polyisoprene, styrene / butadiene copolymer desirability tool butadiene units 5 0 wt% or more, including polymers or copolymer is more preferable.

[0029] Of this such, from the viewpoint of the oxygen absorption rate is high, is preferably co-polymer of a block or random structure consisting of 50 to 99 wt% of butadiene units and 1 to 50% by weight of styrene units instrument 60 copolymers of block structure consisting of 80 weight 0/0 of butadiene units and 20 to 40 weight 0/0 of styrene unit are more preferred. The reason is not clear, for styrene unit part is improved transmission paths and become oxygen diffusivity of oxygen, the oxygen absorption rate is expected to increase. Further, by containing the styrene unit as a copolymerization component, the thermoplastic polymer (A) and also from the viewpoint of the mixture brittle becomes pulverization step of oxidation promoting component (B) is easy, preferably.

[0030] Further, isotactic, syndiotactic, those take different tacticity such Atakuchikku, each may be a mixture in a single. Among these, from the viewpoint of oxygen absorbing performance, Shi preferred those having a structure of Atakuchikku les.

[0031] In addition, copolymers of ethylene and cyclic alkylene, also preferably a resin containing a cyclohexene group cycloheteroalkyl, particularly preferably hexene copolymer to ethylene / vinylcyclohexane, ethylene / cyclopentene copolymer, ethylene / cyclopentene / 4 - Byurushikuro hexene copolymer the polymer to, ethylene / methyl Atari rate Z cycloheteroalkyl hexenyl methyl Atari rates copolymer, hexenyl cyclohexane methyl Atari rate / ethylene copolymer, hexenyl methyl meth Tarireto Z styrene copolymer cyclohexane , or hexenyl methyl Atari rate homopolymer cycloheteroalkyl can be mentioned hexenyl methyl Atari rates copolymer to the methyl Atari rate z cycloalkyl.

[0032] Also the thermoplastic resin (A), the purpose or the like to improve the properties, a random copolymer or a block copolymer with Yogu other monomer may be a homopolymer Les, such may be also a blend with other polymers Yogumataso.

[0033] Thermoplastic resin (A) of the present invention, the Mooney viscosity over to exhibit excellent oxygen absorption performance is 10 to 400. In this range, the thermoplastic resin (A) is capable of retaining the shape of the well powdered oxygen absorbent rather is supported, etc. on a carrier, it can exhibit excellent oxygen absorption performance. Also, the handling of powdered oxygen-absorbing material also becomes good. Furthermore, fried difficulty occurs fusion of particles with each other, it is possible to exhibit excellent high-temperature storage suitability. The Mooney viscosity rather preferably is 20 to 300, more preferably 20: is 150.

[0034] Mooney viscosity, molecular weight of the polymer, molecular weight distribution, branching structure, undergo Karamigore, stippling, influenced by various factors like. Since these various factors affecting the complex Mooney viscosity, it is difficult to determine these uniquely only from the value of the Mooney viscosity.

[0035] The substantially by irradiation or the addition of peroxide to the thermoplastic resin (A), or by heating the thermoplastic resin (A), even in the thermoplastic resin (A) with an electron beam or radiation or the like that manner is cross-linking, the Mooney viscosity exceeds 400. Here, the "substantially crosslinked" refers to conditions do not want to dissolve even when the thermoplastic resin was subjected to crosslinking treatment was immersed for 24 hours in toluene 25 ° C. Powdery oxygen-absorbing material of the present invention is readily soluble when immersed in toluene

[0036] Incidentally, Le in the present invention, the U arm one hundred twenty-one viscosity, powdery oxygen absorbed by dissolution reprecipitation method the thermoplastic resin (A) constituting the powdered oxygen absorbent of the present invention as described below separated from wood, preheating time of 1 minute according to JIS K6 300, rotation time of 4 minutes of the rotor is a value measured by a Mooney viscometer at conditions of a test temperature 100 ° C.

[0037] Here arm one hundred twenty-one viscosity of the thermoplastic resin (A), since there is little influence also contain, if an amount within the range of the present invention the oxidation promoting components to be described later (B), in the case where the According, it is measured by Les, situations that by oxidation promoting component (B) remains in the.

[0038] In addition, by absorbing oxygen absorber of oxygen until subjected to the measurement, if there is a concern that the Mooney viscosity resulting in strange turned into a Fourier transform infrared spectrophotometer (hereinafter, FT abbreviated) measured oxygen absorbing reaction product peaks of the carboxyl group (for example by at _IR, divided by the peak of the 1, 4 trans groups l peak of YlOcnT 1) the thermoplastic resin (a) (967Cm- 1) determine the oxygen absorption amount value from the following formula 1 from the value, it is necessary to correct the Mooney viscosity before absorbing oxygen based on this value. 1, 4 when the peak of the transformer group is unclear, using peaks of the 1, 4 cis group and Bulle group.

(Equation 1) Oxygen absorption amount value (cc / g) = {FT -IR peak height of 1710 cm _ 1 was measured (cm) / FT-967 cm _ 1 peak height measured by IR (cm)} X factor H

Factor H is a value determined by experiments, the thermoplastic resin (A) is polybutadiene cases, for example, 504.

[0039] Thermoplastic resin (A) of the present invention is a no crystal melting peak when measured by differential scanning calorimetry (DSC) on to exhibit excellent oxygen absorption performance, or the crystal melting peak Yes If it that is a melting point of less than 75 ° C.

[0040] has a crystal melting peak, if the melting point is above 75 ° C, the molecular motion of the resin is restricted not preferable because the oxygen absorption performance is deteriorated. For the same reason, preferably the melting point force ¾5 ° less than C, more preferably a melting point less than 50 ° C, more preferably that les, such have a crystal melting peak.

[0041] The thermoplastic resin (A) of the present invention, from the viewpoint of preventing the molecular motion of the resin is limited oxygen absorbing ability deteriorates, crystal melting energy is preferably less than LOOmjZm g . For the same reason, preferably less than crystal melting energy 50 mj / mg, more preferably crystalline melting energy 20MjZmg, still more preferably to have no crystal melting peak. [0042] and the crystal melting peak (melting point) and crystal melting energy in the present invention is that obtained from the DSC curve measured by differential scanning calorimetry, this measurement method is provided as shown in the figure below.

[0043] By dissolving reprecipitation method the thermoplastic resin constituting the powdery oxygen-absorbing material of the present invention (A) was separated from the powdery oxygen-absorbing material, according to JIS K7121, a sample of about lOmg from _ 50 ° C 200 ° the temperature was raised at a 10 ° C / min rate among and C, further after lowering the temperature at 10 ° C / min between _ 50 ° C from 200 ° C was held for 5 minutes and held for 5 minutes _ 50 for the second time the temperature was raised at 10 ° CZ minute speed between ° C to 200 ° C the crystal melting peak temperature of the DSC curve obtained by heating and melting. Further, according to JIS K7122, and the energy per unit weight of the area surrounded by the linear baseline drawn between the DSC curve to the melting completion temperature of the melting initiation temperature and the crystal melting Enenoregi scratch.

[0044] Here, DSC measurement of the thermoplastic resin (A), there is no little influence also contain, if an amount within the range of the present invention the oxidation promoting components to be described later (B), in the case where its it may be measured in a state in which oxidation promoting Ingredient (B) is remained.

(1 2) oxidation promoting component (B)

Oxidation promoting component (B), having a catalytic action that to promote the oxidation of the thermoplastic resin (A) in the presence of oxygen. The oxidation promoting component (B), as is known at the autoxidation of ordinary organic compounds, transition metal catalysts, acid catalysts such as zinc compounds and aluminum compounds are preferably used. Further, photoinitiator, initiator and heating agent, such as a thermal initiator and the like can be mentioned.

[0045] The herein the transition metal catalyst, the first of the periodic table, in the second or third selected from transition series metal salts, those which are readily mutual conversion between at least two oxidation states preferred specifically, manganese (II) or (111), iron (II) or (111), cobalt (II) or (III), nickel (II) or (III), copper (I) or (II) , rhodium (II), and the like (III) or (IV), silver (I) or (II) and Noreteniumu (II) or (III). Oxidation state of the metal when introduced is not limited to the active form. The metal of suitable counterions to the Shioi 匕物 I O emissions, acetate, stearate ion, palmitic acid ion, hexanoate I O emissions to 2 Echiru, neodecanoic acid ion, Orein acid ion, linoleate ion, linolenic acid ion, OTA chill acid ion or naphthenic acid ion and the like. The salt of this like, 2-E Ji Le hexanoic acid cobalt (II), Orein cobalt (II), cobalt neodecanoate (II), naphthoquinone Antheraea yamamai cobalt, copper naphthenate, iron naphthenate, and the like exemplified it can. Further, silver oxide, titanium oxide, zinc oxide, zinc naphthenate, antibacterial agent containing silver ions may also be mentioned as a preferred example.

[0046] Also, when oxidation promoting component (B) such as metal fatty acid salts, those containing carbon Ichisumi containing unsaturated bonds in the fatty acid moiety, oxidation promoting component in the powdery oxygen-absorbing material (B) There order to be incorporated into the resin structure, the less the leakage of powdery oxygen-absorbing material component force catalysts, preferred.

[0047] The oxidizing catalyst of aluminum compounds such as, tri E chill aluminum, triisobutyl aluminum, Jefferies Chill aluminum chloride, E chill sesquichloride click port chloride, E chill aluminum dichloride, tri - n_ OTA alkyl aluminum Yu chill aluminum beam, and the like can be exemplified.

The [0048] photoinitiators, radical photopolymerization initiator, a cationic photopolymerization initiator, include such Anion photopolymerization initiators, include benzophenone, anthraquinone, naphthoquinone, Le Shi preferred Ben Zokinon Examples It is.

[0049] The content of the oxidation promoting component (B) is preferably set to in the thermoplastic resin (A) 0. 0001 wt% to 5 by weight% or less. Preferably 3 wt% or less 0.001% by weight or more. Qian For transfer metal catalyst, the metal content (ligand, excluding counterions, etc.) based on the, in hot-friendly plastic 榭脂 (A), preferably 0.0001 wt% to 5 wt% or less , more preferably 0.0 01 wt% to 2 wt%, more preferably 0.01% to: 1. the range of 5 wt%.

[0050] However, since powdered oxygen absorbent of the present invention which increases reactivity with oxygen by increasing the specific surface area, the more oxidation-promoting component has a large specific surface area (B) is less Yogu the thermoplastic remaining in the resin (a) alone polymerization catalyst les, Ru trace, it may be an effective oxidation catalyst.

(1 one 3) Other components

Powdery oxygen-absorbing material of the present invention may include components exemplified in various below. (1 one 3-1) antioxidant (C) an antioxidant (c) is, in all material to prevent oxidative degradation or cross-linking of the polymer, Hue Nord antioxidants, phosphate antioxidants, Iou antioxidants, Hindadamin antioxidants, and Rataton antioxidant can be exemplified.

[0051] In the powdery oxygen-absorbing material of the present invention, mosquitoes preferred Rere be 50ppm~1000ppm containing antioxidant (C) in the thermoplastic polymer (A).

[0052] In order to preclude the presence of the antioxidant (C) is too much oxygen absorption reaction of the powdery oxygen-absorbing material, the induction period will be summer very long. On the other hand, when the abundance is too small, oxygen as preferred powdery oxygen-absorbing material thermoplastic polymer will powdery oxygen absorbing material was oxidized to the molded Caro E Secondary such as melt mixing step in the preparation method of the present invention to be described later or absorbing performance accidentally reduced, and the induction period is too short to react with oxygen in the atmosphere until the package with the article forces foods by exposure to oxygen when the user uses (the user's work time) oxygen absorption properties or've been drain in. For these reasons, added Caro amount of antioxidant Hitoshi IJ (C) is, 50Ppm~1000ppm force S Preferably, arbitrary preferred over 100ppm~800ppm force S.

[0053] Here, the induction period refers to the time until the start of useful oxygen absorption from the time the powdery oxygen-absorbing material is exposed to oxygen. That is, the user is that of the period of the oxygen absorption effect from the start using a desired and powdery oxygen-absorbing material to begin to express useful oxygen absorbing performance, by the waiting period to effect expression in the user is there. The induction period, it is preferable that the force generally depends on the application is within hours to days. In particular, buns, fruit cake, doll baked, if you want to use in the fast food of the pain, such as prepared foods and lunch boxes, and the like, this induction period is shorter is 6 hours or less is good as an example Yogu. Further, the induction period is too short to less oxygen until the user packaged with easy various articles degenerated under the influence of oxygen from exposing the powdered oxygen absorbent material in oxygen (user's work time) the absorption characteristics is consumed, preferably 30 minutes or more as a certain length or preferably fixture example.

[0054] In order to control the induction period wherein the antioxidant (C) is preferably from the preferred instrument what radical scavenging effect in which a par O alkoxy radical scavenging effect. As these to be, phenol-based antioxidants, hindered amine antioxidants. To exemplify [0055] phenol antioxidants, 2, 6-bis (2 '- hydroxy-3' - t-butyl-5-methylbenzyl) -4-methyl phenol, 4, 4 Mechiren bis one (6- t-butyl-2- methyl phenol), 4, 4 Mechiren bis- (2, 6-di-t Buchinore phenol), 2, 6-di _t_ butyl _4_ methyl phenol, 4, one Chio one bis one (6_T_ butyl _3_ methyl phenol), 4, one butylidenebis one (6_T_ butyl _3_ methyl phenol), 2, 2 '- methylene one bis one (4-methyl _6_t_ Buchirufue Nord), 2, 2' - methylene one bis one (4 Echiru _ 6 _t _-butylphenol), 2, 6 - di _t_ butyl _4_ Echirufuenoru, 1, 1, 3- tris (2-methyl _4- hydroxy shea _5_t_ butylphenyl) butane, n- Okutadeshiru one 3_ (4-hydroxy - 3, 5 - di _t_ butylphenyl) professional Onato, tetrakis [methylene one 3_ (3, 5-di _t_ butyl _4- hydroxyphenyl) propionate] methane, 2, 5_ di one t- amyl hydroxamate non, 2, 5_ di one t- butylhydroquinone, hydroquinone, p- methoxy phenol, 2_T butyl hydroquinone, n Okutadeshiru 3- (-hydroxy 3, 5 - di t Buchirufue two Honoré) propionate, triethylene glycol bis [3- (3-t butyl Honoré one 5-methyl-4-hydroxyphenyl) propionate], 1, hexanediol to 6-- bis [3- (3, 5-di-one t-butyl 4-hydroxyphenyl) propionate], 2, 4-bis one (n- Okuchiruchio) -6- (4-hydroxy 3, 5 - di t Buchiruanirino) -1, 3, 5-Toriajin, pentaerythrityl one tetrakis [3- (3, 5-di-one t Buchinore 4-hydroxy-phenylene Honoré Propionate], 2, 2 Chio chromatography diethylene bis [3- (3, 5 - di-one t-butyl 4-hydroxyphenyl) propionate], Okutadeshiru 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, N, N '- to Kisamechire Nbisu (3, 5-di _t_ butyl _4- hydroxy one hydro cinnamic amide), 3, 5_ di one t - butyl _4- hydroxy one benzyl phosphonate one oxygenate chill ester, 1 , 3, 5 - Torimechinore one 2, 4, 6_ tris (3, 5_ di one-butyl _4- hydroxybenzyl) benzene, 2, 4_ bis [(Okuchiruchio) methyl] _O_ cresol, other non such one tocopherols tocol derivatives, and the like.

[0056] To exemplify the phosphorus-based antioxidant, triflumizole We alkenyl phosphite, tris (to 2 Echiru carboxymethyl Honoré) phosphite, tri deci Honoré phosphite, tris (Torideshinore) phosphite, tetra (tridecyl Honoré) 4 , A '- isopropylidene one Jifue two Norre one Jihosufuaito, trilauryl one Torichio phosphite, tris (2, 4-di one t butylphenyl) phosphite, tris (Nonireitido - phenylene Honoré) phosphite, distearyl pentaerythritol phosphite , 2, 2-methylcarbamoyl Renbisu (4, 6-di-_t _ butylphenyl) O Chi le phosphite, bis (2, 6-di-_t _ butyl one Mechirufuweniru) pentaerythritol one diphosphite and the like.

[0057] To exemplify Iou antioxidant, tetrakis [methylene-_ 3 _ (dodecylthio) pro Pioneto] methane, Ni _ dibutyl one Jichio Ichiriki Rubameto, Zn_ dibutyl one Jichio - force Rubameto, Cd_ Echiru one phenyl one Jichio Ichiriki Rubameto, Chio urea, 2 _ Menore mercapto - benzimidazole, dilauryl thiodipropionate, distearyl Jipu port Pioneto the like.

[0058] As the hindered amine-based antioxidants, dimethyl _ 1 _ succinate (2-Hidorokishechi Honoré) _ 4-hydroxy one 2, 2, 6, 6-tetramethylpiperidine polycondensate, poly [{(6 1, 3, 3-tetramethylbutyl) Amino one 1, 3, 5 triazine one 2, 4-Jiiru)} {((2, 2, 6, 6-tetramethyl-one 4-piperidyl) Kisamechiren to imino} {(2, 2, 6, 6 tetramethylene chill one 4-piperidyl) Imino}], N, N '- bis (3-Aminopuropiru) Echirenjiamin one 2, 4-bis [N Buchinore one N-(1, 2, 2, 6, 6- pentamethyl one 4-piperidyl) Amino] 6-chloro-1, 3, and a 5-triazine condensate.

[0059] As the Rataton antioxidants like 3-hydroxy 5, 7-di-t-butyl over furan-2-one and the reaction product of o-xylene.

[0060] When formulated in combination of two or more antioxidants, the blending 50 Ppm~1000ppm the phenolic antioxidant is blended more than 50ppm other types of antioxidants, processing was cheap boss preferred for easy to achieve both sex and high oxygen absorbing performance.

(1 3 2) fine particles (D)

Fine particles (D) is heat main ingredient suitable shape imparted and maintained comprising a thermoplastic resin (A) and oxidation promoting component (B), before under the conditions during production and storage of at least powdered oxygen absorbent Symbol base resin has a function of hardly adhere to each other.

[0061] so as to be positioned on at least a portion of at least some force the main agent of the surface of the microparticle (D) is integrated with the main agent. This makes it possible to prevent adhesion of said base material to each other. Preferably is to allowed to position the fine particles (D) on the entire surface of the base material.

[0062] fine particles (D) preferably has an average particle size of the primary particles is 0. 01 μ m~lmm, more preferably 0. 05 μ m~500 μ m, more preferably 0. 1 mu m~100 is a μ m. In such a range, the unevenness occurs on the surface of the powdery oxygen-absorbing material, Ya is prevented adhesion of powdery oxygen-absorbing material mutually immediately result, large surface area is ensured.

By [0063] the same reason, the average particle size of the base material, it forces S preferably is a value forces S1.:!~ 500000 divided by primary particle size of the fine particles (D), more preferably 2 to: 10000, further preferred properly is 5: 1000. In this range, fine particles (D) to form irregularities on the surface of the oxygen-absorbing material (A), adhesion between the powdery oxygen-absorbing material particles is less likely to occur.

[0064] As the fine particles (D), a high-temperature environment (e.g., 40 ° C) if the solid particles adhere hardly normal to each other in Yogu inorganic particles (D1) also organic particles (D2) But may a record,. Incidentally, another difficult determination of whether deposition, the primary particles of fine particles (D) to enter is the vessel was allowed to stand for one day to 40 ° C, the secondary particle child by observation with an optical microscope or electron microscope Bruno; can be determined by whether agglomeration occurs.

[0065] The deposited here, Les mechanical interaction, physical interactions, chemical interaction, electrostatic by the force of interaction such as the type of two different materials to stick together Les, the Rukoto, cormorant.

The content of fine particles (D) in the [0066] powdered oxygen absorbent, the content of fine particles (D) in terms of increasing the stoichiometric amount of oxygen absorbed per unit weight of the oxygen-absorbing material is small nearly as preferred, tend to adhere prevention effect of powdered oxygen absorbent particles between the content is small particles (D) is reduced. Range of the content of fine particles (D), relative to the thermoplastic resin (A) 100 parts by weight of in the powdery oxygen-absorbing material, 10: 1000 parts by weight rather preferable than preferably tool is 30 to 450 wt it is a part. The inorganic particles (D1), a metal, metal compound, the particles of the other inorganic substances.

[0067] as a particle of metal is iron powder, aluminum powder, Hiroshi gold powder, copper powder, magnesium powder, mug Nariumu powder (alloy powder aluminum and magnesium), etc., and preferably, iron powder, aluminum Niumu powder it is.

The particles of the [0068] metal compound, oxides, hydroxides, aluminates, Aruminokei, sulfates, particle such as phosphates. Preferably, Ri Ah with particles of aluminum compound, and more preferred are particles of oxides and hydroxides of aluminum. The oxide and hydroxide of aluminum particles, alpha-alumina, .gamma.-alumina, r? Anoremina, [delta] alumina, chi alumina, [rho alumina, and anhydrous aluminum compounds such as activated alumina, Al (OH) or Al_〇 - gibbsite represented by 3H O, Baiyaraito, Norusutoranda

3 2 3 2

Trihydrate and aluminum compounds such as site, expressed in Arufa1_rei (ΟΗ) or Al_〇-Ita_〇

2 3 2

Behenate one chromite, and monohydrate of aluminum compounds such Daiasupoa, further Todaito (

5A1 Omicron · Ita_〇) and include particles such Anoreminagenore (A1_rei · ηΗ Ο). Still more preferably

2 3 2 2 3 2

As had example, boehmite, particle of activated alumina. Other include particles Zeoraito such as a preferred example.

[0069] As particles of other inorganic materials, silica gel, activated clay, activated carbon, pearlite, sand, rocks, metamorphic, igneous, sedimentary, granite, carbide Kei arsenide, chromium oxide, diamond, nitriding Kei arsenide, Jirukoyua, boron nitride , include particles etc. are preferably activated carbon include particles such as pearlite.

[0070] As the organic particles (D2), resin powder, food powder, particles of other organic materials like et be.

[0071] Yogu example in particles of the thermosetting resin in the particles of the thermoplastic resin as the resin powder, polyethylene, poly 4 fluorinated modified styrene, polypropylene, polyvinylidene chloride Biel, polystyrene, Po polyvinyl alcohol, polyacrylonitrile, 1 butene, polyvinyl acetate Bulle, polyvinylidene mold sulfonyl, poly 4-methylpentene-1, polyvinylidene chloride, polyvinylidene fluoride, Porimetatari Honoré methyl, polychlorinated trifluoride modified styrene, polybutadiene, polyisoprene, Porikuroropure emissions, poly 3-hydroxybutyrate , poly 3-hydroxyvalerate, polylactic acid, ε force Purorakuto down, polyethylene succinate, polybutylene succinate, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Over DOO, poly 1-4-xylylene terephthalate cyclohexane, polyamide 6, polyamide 12, polyamide bromide 46, polyamide 66, polyamide 610, Porino La phenylene terephthalate Honoré amide, Porimetafue two isophthalamide, polyoxymethylene, polyethylene O Kishido, Porifue two Renoki Sid, Porifue two Rensurufuido, polyether sulfone, polyether ether ketone, dimethylcarbamoyl Honoré polysiloxane, polycarbonate, polyurethane, polyimide, epoxy resin, urea resin, melamine resin, phenol resin, unsaturated polyester resin, an acrylonitrile one butadiene one styrene, styrene acrylonitrile, ethylene acetate Biel include powder like. Moreover, natural rubber latex, styrene-butadiene rubber latex, Two Torirugomurate Ttasu, chloroprene rubber latex, isoprene rubber latex, DPL (depolymerization latex), EPDM (ethylene propylene diene rubber), acrylic E Mar Ji, latex of polyurethane-based also latex described as preferable examples.

[0072] The food powder, anchovy, kelp, pulverized such sesame or Sakuraebi or flour, powdery mildew, buckwheat flour, powder or the like, such as ground coffee or tea powder may be mentioned as examples, rather preferably the flour and the like. As particles of other organic materials, powders or the like of paper or grass and the like.

(1 one 3_ 3) deodorant, deodorant (E)

The powdered oxygen absorbent of the present invention may be added a deodorant or deodorant (E) during and after manufacture or production. This decomposition reaction when the oxidation reaction proceeds in the thermoplastic resin (A) occurs, there occur malodor, such as low molecular weight aldehydes, ketones, esters, because suitable for removing odor of its it is.

[0073] As the deodorant, there are for example activated carbon, Zeoraito, amorphous silica, cyclodextrins, sepiolite, ceramic, silica gel or the like, obtained by chemical treatment substances, such as amines on activated carbon, for example, Japanese ene by locating Mikano lez Co. the granular Shirasagi GAAx and preferred examples.

[0074] As the deodorant, polyalkylene I Min and polyethylene I Min, vitamin E, Tokofueno Lumpur, titanium oxide, hydrazine derivatives, Amin compound (Kisamin to pentaethylene, triethyl Chirentetoramin, poly Bulle O hexa ethylbenzthiazoline, etc.), an inorganic base compound (calcium oxide, water calcium oxide, calcium carbonate, etc.), flavonoid deodorants, polyphenol, turpentine oil, active aluminum oxide, Keisan magnesium, Kei aluminum, and the like

[0075] The following describes the structure of the powdery oxygen-absorbing material of the present invention.

(2 1) shape

Oxygen-absorbing material of the present invention is powdery. Here, the powdery a "Konano such a state (Iwanami Shoten Kojien than 2nd Edition)", Konato is "broken in those became fineness. Powder. (From Iwanami Kojien 2nd Edition)" is that of. If powdery, powder, particulate, granular, spherical, plate-like, columnar, cylindrical, acicular, granular, flake, may be any shape such as fiber, the specific surface area is large oxygen contact easily powdered and fine particulate, platy, acicular, and more preferred shape of the scaly like.

(2 2) the specific surface area

Powdery oxygen-absorbing material of the present invention, from the viewpoint of effective surface area should contribute to oxygen absorption is a sought specific surface forces 60cm 2 Zg Thus Kr gas adsorption method, preferably 600 cm 2 / g or more, more preferably 2000cm is 2 Zg or more.

(2-3) particle size

Powdery oxygen-absorbing material of the present invention, because of the powder leakage and difficulty, etc. when placed in oxygen absorbing performance and easy installation and sachets and the handling of the powdery oxygen-absorbing material, it was prompted by the method described below the average particle size generally is 0. 01 / im~5mm, preferably 0. 01 μ ΐη~1ιηπι.

[0076] In the particulate thermoplastic resin without containing (D) (Α) and an oxide promoter (beta) powdery oxygen-absorbing material, the primary particle diameter is 0. 01: is about 10 μ ΐη, preferably is 0. 01 μ ΐη~5 / ι m. The structure of these primary particles are formed aggregated particles to aggregate (agglomerate structure) is preferable from the viewpoints such as stabilization of the oxygen-absorbing performance and structure. The average particle size of in this aggregated particles generally is 0. 01 / im~5mm, preferably 0. l / im~3mm, more preferably 1 / im~: a 1 mm. In particular, at least a portion of the surface of the relatively large primary particles having a particle size of about 10 / im, a structure in which at least a portion of the primary particles having a relatively small particle size of less than 0. 1 μ ΐη is located Furthermore easily maintain the structure of powdery oxygen-absorbing material if there.

The powdered oxygen absorbent containing [0077] The fine particles (D), a primary particle diameter of the main agent composed of a thermoplastic resin (A) and oxidation promoting component (B) Ari is about 0.01 111-5111111, preferably is 0. 02~1 00 zm, more preferably 0. 05~: lO is xm. The average particle diameter of the agglomerated particles is usually 0. 01 μ πι~5ιηιη, preferably 10 μ m~5mm, more preferably 10 μ m~3mm der. [0078] The following describes a preferred method for producing powdery oxygen-absorbing material of the present invention.

[0079] The method for producing a powdered oxygen absorbent of the present invention comprises the steps of (X), (Y), (Z), the (S), (X), (Y) or (X), (Y ), (Z) or (X), (Z), (Y) or (X), (Y), (S) Moshiku is (X), (S), (Y) or (X), (Y ), (Z), (S) or (X), (Y), (s), (z) or (X), (Z), (Y), (S) or (X), (S), (Y), (Z) or (X), (Z), (S), (Y) if clause (X), (S), (Z), is preferably performed in the order of (Y).

Step (X): a step of mixing the thermoplastic resin (A) and oxidation promoting component (B),

Step (Y): The above mixture, the step of specific surface area to 60cm 2 / g or more powdered form, step (Z): a material obtained by the shape of the mixture or powder of the above, two or more kilogray radiation曝 to and / or heating, the

Step (S): a material obtained by the shape of the mixture or powder of the above, the following step of storing in a low oxygen atmosphere, will be described in detail each step.

(3 1) Step (X)

The step (X) in the present invention is a step of mixing or dissolving the above-mentioned thermoplastic resin (A) and oxidation promoting component (B) is physically or stirred, by heat or solvents.

[0080] As described above, if remaining in the thermoplastic resin (A) becomes Re, Ru traces of a polymerization catalyst only effective oxidation catalyst, this step (X) may be omitted.

[0081] Further, as described above, 50 ppm to respect the thermoplastic polymer (A):! Because it preferably contains OOOppm of Sani spoon inhibitor (C), when the abundance of the antioxidant is too small or an antioxidant (C) in the case abundance is too large, or reduce the antioxidant (C). The work of reducing the antioxidant (C), the thermoplastic resin (A) is dissolved in a good solvent for the thermoplastic resin (A), a poor solvent for Tsugire, in the thermoplastic resin (A) and oxide adding a good solvent is substance inhibitor (C), a method of precipitating only the thermoplastic resin (a), so-called dissolution reprecipitation method, such as detection using and Soxhlet extractor or the like is cut with illustration. When adding an oxidizing promotion component (B) is not matter even Re Izu before or after the step of separating the antioxidant (C), Shi preferred is better added after les.

[0082] preferably les step (X), the thermoplastic polymer (A) and a method of melt-mixing in a heated molten state oxidation promoting component (B) as methods. [0083] 溶溶 ToruToru mixed mixed city and ingredients specifically body specifically specific na way how methods of the order for the the merging mother ,, heat heat-friendly plastic-plastic properties tree resin fat ((AA)) ,, acid oxidation of 促促 SusumuSusumu formed components partial ((BB)) der Arere Baba Sosono other other of 添添 Jiajia the at distribution blending if the split ratio ,, 必 required main resembles the case of the here and there steady object was Toto both together in ,, f hen Nshi shell E Lulu ear Kiki Sasa chromatography ,, Lili Bobon Nbu shake Ren Sunda loaders over ,, VV type type Bubureren'ndada mixed in an one mag like evenly uniform scratch have not used use the the axial axis 混混 Nerineri 押押 Dede machine machine, and the like, such as very many of such mixed ze Tata distant future ,, Baban'nbabariri eleven Mimikikisasa ,, Ninidada ,, Rororuru ,, one single axis once again mother twenty-two shaft axis, etc.混混 混混 Nerineri soot Ruru better way method kneading kneading machine machine are not using use the there is Ruru Ki made of EXAMPLES Example 示示. .

[0084] equalizing ,, acid oxidation into during the time Ruru 混混 Zeze the uniform one 促促 SusumuSusumu formed components partial ((BB)) with the order for Ruru was allowed to dispersed dispersed evenly uniformly one half the, stream flow dynamic Papara rough Fi I Template Unless they already exist ((for example, even if Ebaba ,, pine Matsumura Muraishi petroleum oil research research Institute plant made made Susumomoiiruru, etc., etc.)) ,, ears Nene Lara Lulu Oh good Lulu ,, etc., etc. to a good'm Momoyo If you are pressurized death 添添 pressure. .

[0085] Temperature Temperature of the of 混混 Nerineri of each respective forming component parts is ,, heat heat-friendly plastic-plastic properties heavy polymer polymer material ((AA)) temperature is Lulu Nana in the can 溶溶 ToruToru mode When the door that is called der Arere Baba Yoyo at a temperature level is put input to the ,, tree Manzanillo to resin degradation deterioration of ,, rack cross-linking bridge of fat Yoruru Gegeruru the the Kaka, etc., etc. Remarks consideration into account capital good like we Shikukuhaha 228800 °° CC 以以 under under ,, good good Lili good like we Shikukuhaha 225500 °° CC Oh Ruru here and transgressions in under under 以以 is good to have demanded Nozomi. . Further more ,, 混混 Nerineri order ordering mechanism 及及 Bibi way how How each respective forming component parts is ,, heat heat-friendly plastic-plastic properties heavy polymer polymer material ((AA)) ,, acid oxidation of prompting promote SusumuNaru components partial ((BB)) other other become components partial to one batch batch and to have 混混 kneading kneading method -A ,, the ,, Sosono ((AA)) ,, ( (BB)) one another other to become adult component of its components content 含含 Me meth was Zanzan releases of some portion was 混混 Nerineri was the distant future ,, Sosono the inside in the in混混 kneading kneading method -A a minute, etc., etc. is Ruru Ki made of EXAMPLES Example 示示. .

((33 - 22)) as the engineering process ((YY))

As present present onset invention facie Nio only only Ruru Engineering step ((YY)) Totohaha ,, on the Symbol thermogravimetric friendly plastic-plastic properties heavy polymer polymer body of the ((AA)) 及及 Bibi acid oxidation of促促 SusumuSusumu formed components partial ((BB)) of the mixed mixed in the mixed mixture compound mixture in about the, in small pieces 碎碎 Mamata was good that sip after later predicates mother so sea urchin in the main polymerization if application step other other towards Manzanillo to method method Yoriri ,, baboon Table surface area product is the 6600ccmm 22 // gg以以on Ueno powder Sosono the method method such person Ruru give give a compound thereof Ruru Oh is in about engineering process that sip to the powder form of the form shape-like. . On the Symbol of the 混混 Gogo product of the form shapes like is ,, example example Ebaba Pepereretttoto like shape ,, Shishitoto like shape ,, Fufiirurumumu shaped like ,, liquid liquid form ,, mass lump form ,, Menmen shape Jo ,, 繊繊 維維-like shape ,, Beberuru-like shape ,, Susurarabubu-like shape ,, Fufurerekuku-like shape ,, Kukuraramumu-like shape ,, Papauudada shaped like a Do Dodo there is Ruru Ki made of EXAMPLES Example 示示. .

[0086] The present present onset invention and the light of the in small pieces 碎碎 is ,, example example Ebaba ,, aa Toto Mom good Zuzu Oxley ,, main merle Toto soot Phi Ninin ring grayed Oxley ,, times rotational rolling electrode pole Oxley Manzanillo to ,, machine machine 械械 manner manner Pupurorosesesusu Yoruru in small pieces 砕砕 ,, chemistry histological manner Pupurorosesesusu to Manzanillo Yoruru in small pieces 碎碎 ,, liquid cooling with cold refrigerant medium of the liquid body 窒窒 originally etc. etc. cooled retirement and Shi in small pieces 砕砕 method -A ((freezing frozen sintered powder grinding 砕法 method)) ,, etc. powder powder powder made producing granulation process method of such there is Ruru Ki can in take advantage utilized. . Good Good Mamashi to better process method and cities to have ,, machine machine 械械 manner specifically Pupurorosesesusu to Manzanillo Yoruru in small pieces 砕砕 slightly frozen frozen sintered powder grinding 砕法 method is Ruru Rarere galley like elevation. .

[0087] machine mechanical 械的 basis Pupurorosesesusu to Manzanillo Yoruru in small pieces mother ,, example in city and how to process more of 砕砕 example Ebaba di job ® over over click Clara Tsu Tsu Shisha turbocharger over over ,, Roro Rurumimiruru ,, took Tsu Tata over ear Lulu ,, ha ha Template Unless they already exist Mommy over ear Lulu ,, Pippin down ear Nono Lele ,, aa Toto mama good Zaza eleven ,, Bobo over over Nono Lele ear Nono Lele ,, 遊遊 Hoshiboshi Boborurumimi Lulu ,, soot dad good Lara Nono Lele ear Nono Lele ,, Iin'npeperara eleven Mimiruru ,, newly packaging guru belt tiger rack click lottery Jeffrey E Tsu Tsu Toto ear Lulu ,, Jijeetttoto '' Oomimiruru ,, MigakuMigaku 砕砕 formula formula Mimiruru ,, grayed Gras Rye Inn Sunda Dah over ,, stone millstone mortar ,, cold freezing frozen in small pieces 砕砕 Shishisusutetemumu ,, 窒窒 originally Gagasusu in small pieces 砕砕 Shishisusutetemumu ,, chemistry studies in small pieces 砕砕 shea Soot [0088] Further, as a method of obtaining the mixture in the polymerization step, a method of producing by suspension polymerization, a method of manufacturing by emulsion Polymerization A solution polymer prepared by solution polymerization is dissolved in a medium such as water how to have been to disperse by stirring vigorously, it is like how prepared by precipitation polymerization, as an emulsion polymerization and the like are preferable examples.

(3 3) a step (Z)

And the step (Z) in the present invention, a material obtained by the shape of the mixture or powder of the above, a 2 Kirogu ray exposure to more radiation and Z or heating.

[0089] Here, the radiation, gamma radiation, X-rays, alpha rays, beta rays, electron beam, accelerated I O emissions, include ionizing radiation neutron rays, preferably a gamma ray, an electron beam, is La preferably a gamma ray.

[0090] The absorbed dose, usually at least 2kGy more, preferably. 5 to: 1000 kGy, more preferably 2 0~300kGy. Induction period in the process in less than 2kGy is not much reduced, also there is a high possibility that low down and productivity such as reduction of the 10 oxygen absorbing performance generation of gel by more than a crosslinking reaction OOkGy is probably caused occurs Become.

[0091] As a method of exposure to radiation, for example, mixtures or powdery ones degassing conditions or nitrogen which is the shape of the carbon dioxide and partial pressure of less than 20% mixed gas thereof, and the oxygen needed for the a method of exposing to put radiological on a container or a bag can be exemplified in a state filled with inert gas such as in a mixed gas.

[0092] heating temperature, the force varies by time of heating generally at 100 ° C~30 0 ° C, preferably 110 ° C~200 ° C. 100 ° induction period in the process in less than C is not less shortened, also more than 300 ° C the thermal decomposition Ya fusion of a mixture or oxygen-absorbing material in which the shape of the powder described above occurs, lowering of productivity There is more likely to occur. During the time of heating is generally 1 second to 1 hour 0.1 to, preferably 0.5 seconds to 30 minutes, more preferably 1 second to 1 0 minutes.

[0093] The method of heating is, for example, containers Ya in the process, state-like filled with deaerated state or an inert gas blowing hot air directly inert gas to the oxygen-absorbing material in which the shape of the mixture or powder of the above method of applying heat in a bag, vacuum heating, and the like.

(3-4) Step A (S) step in the present invention (s), a material obtained by the shape of the mixture or powder of the above, a step of storing in a low oxygen atmosphere.

[0094] Here, the "Save in low-oxygen atmosphere", for example, packaged using a barrier packaging material, by using the inert gas replacement method, and Z or other deoxidizing materials as required It refers to a process to store the powder oxygen absorber in a state of low oxygen concentration atmosphere. Here, the low oxygen concentration is that the oxygen concentration is less than 20%, preferably less than 5%, further preferred properly is less than 1%. This step (S) has the effect of shortening the induction period of powdery oxygen-absorbing material preferably.

[0095] period to be saved, storage temperature, due to the ingredients and manufacturing methods that make up the powdery oxygen-absorbing material connexion come also different, but in general one day to several years, preferably from 3 days to 6 months , more preferably from 1 week to 3 months. Induction period is not so much reduced in the process in less than one day, also more than a few years when powdery oxygen-absorbing material attachment between, there is a high possibility that such decrease in productivity due to stock holding period is longer occurs Become. An example of a preferred storage period, for example when the thermoplastic polymer (A) is a styrene / butadiene copolymer was 20 days, the length of this is the same as inventory storage period during distribution powdery oxygen-absorbing material since the extent of the length, particularly preferred will be inventory storage during flow through also serves the role of step (S).

[0096] Temperature during storage is generally a 0 ° C~100 ° C, preferably 5 ° C~80 ° C, more preferably 10 ° C~60 ° C. 0 ° induction period in the process in less than C is not less shortened, also more than 100 ° C (212 ° F) when the productivity between the oxygen-absorbing material is fused is more likely to decrease.

[0097] Among the combinations of these processes, the thermoplastic polymer (A) and the step of melt-mixing in a heated molten state oxidation promoting component (B) (X), a step of grinding the molten mixture (Y), the molten mixtures or exposing the ground product to a 2 kiloGray or more gamma ray (Z), the molten blend compound or pulverized comprising the step of storing in a low oxygen atmosphere (S), the production method of powdery oxygen-absorbing material are particularly preferred it is an example.

[0098] powdered oxygen absorbent of the present invention may then, for example, small pieces mixed or used as a deoxidizer in a form placed in a breathable pouch remains powdery, the compression molded pieces and thermoplastic resin the or used as a deoxidizer in a form placed in a pouch, label, card, or used as a deoxidizer in the form states, such as packing, a de-oxygen packaging material such as film or sheet by mixing the thermoplastic resin, it is possible such as by or used in various forms in a part or all of the packaging bag or packaging container.

[0099] If you deoxidizer which takes into breathable pouch, polyethylene, copolymer of propylene and Orefin, ethylene one Bulle monomer copolymer, polypropylene, polystyrene, copolymers of scan styrene and Orefuin, oxygen permeation amount and high polymers such as polyester, paper, nonwoven, woven, microporous membranes or be an oxygen absorber in a state encapsulated in a sachet in consisting of multi-layer body, and the like. Also in the pouch, from the viewpoint of breathability, perforations may be subjected.

[0100] In the case of film or sheet, yo be one that is composed of only the layer (L1) containing powdery oxygen absorber les, but at least more (L2) or more layers of other materials good record, be a laminated film, which is composed of. The material constituting the L2, thermoplastic polyester resins, thermoplastic polyurethane resins, thermoplastic polyolefin resin (LDPE (low density polyethylene ethylene), VLDPE (very low density polyethylene), LLDPE (linear low density polyethylene), HDPE (high density polyethylene), propylene-based resins, butene - 1 resins), polyamide resins, Porishio Ihibiniru, styrene resin, an ethylene acetate Bulle copolymer, ethylene (meth) acrylate copolymers, ethylene (meth ), and acrylic acid copolymer and ethylene (meth) acrylic acid ionomer and the like.

[0101] In addition, laminated film layer having an oxygen barrier property powdery oxygen-absorbing material-containing layer (L1) (L3) are stacked is preferable embodiment. L1 is than L3, the configuration is located in the packaged articles side. The L3, EVOH (ethylene one Biel alcohol copolymer), PVDC (Po Ribiniridenku port ride), PET (polyethylene terephthalate), PBT (polybutylene terephthalate tallates), PTT (polytetramethylene terephthalate), PEN (polyethylene naphthalate ), PVA (poly Bulle alcohol), PAN (polyacrylonitrile), PA (polyamide) and child will be exemplified copolymers such as, or may be, for example, a resin composition containing an inorganic layered compound such as clay. Moreover, and barrier organic material on the surface of the film or the intermediate layer, § alumina, silica, inorganic materials such as amorphous carbon may be coated.

[0102] powdered oxygen absorbent of the present invention is also outside of food, medicine, test kits, medical devices, iron pipes, capacitors, packaging such batteries, also, bottle cap seal, Ru can be applied also to a label or the like.

Example

[0103] The present invention will be further described in detail by way of Examples.

First, the measurement methods and evaluation methods used in the present invention are summarized below.

<-Time one hundred twenty-one viscosity>

Arm one hundred twenty-one viscosity powdery oxygen-absorbing material of the present invention (ML1 + 4Z100 ° C) is a powdered oxygen absorbent 30g of the present invention is dissolved by adding toluene 250 g, and remove unnecessary components in the glass filter Chancellor after, 35 ° C this solution methanol lOOOg separated mosquitoes 卩 Ete powdery oxygen intake Osamuzai of a thermoplastic resin by reprecipitation (a), the Yamato scientific Co. vacuum drier DP63 (trade name) in, a material obtained by vacuum-dried for 48 hours, Ueshima Seisakusho Co., Ltd. arm one hundred twenty-one viscometer MVR - 1130 (trade name) with a preheating time of 1 minute in conformity with JIS K6300, the rotation time of 4 minutes of the rotor, It was measured under conditions of test temperature 100 ° C.

<Crystal melting peak (melting point) and crystal melting energy>

Crystal melting peak powdery oxygen-absorbing material of the present invention (melting point) is a powdered oxygen absorbent 30g of the present invention were dissolved by adding toluene 250 g, after removing the unnecessary components with a glass filter first class, methanol to the solution lOOOg separating Netsuka plastic resin (a) from the powdery oxygen-absorbing material by mosquito 卩 Ete reprecipitate a, at 35 ° C by Yamato scientific Co. vacuum drier DP63 (trade name), vacuum dried for 48 hours the ones using a Perkin Elmer Co. differential run 查熱 amount analyzer "PYRI S DIAMOND DSC" (trade name), in compliance with JIS K7121, between 200 ° C a sample of about 10mg from _ 50 ° C heated in a 10 ° C / min rate, retained after 200 ° C, 4, and 5 min - 50 ° was cooled in a 10 ° C / min rate among and C, further _ 50 ° C was held for 5 minutes from 200 ° crystal thaw peak temperature of the obtained DSC curve 10 ° CZ minutes at a rate of temperature increase was 2 time of Atsushi Nobori between C was used.

[0104] Further, according to JIS K7122, and the energy per unit weight of the area surrounded by the linear baseline drawn between the DSC curve to the melting completion temperature from the melting start temperature and crystal melting Sumi军 Enenoregi scratch.

<Specific surface area>

The specific surface area of ​​the powdery oxygen-absorbing material of the present invention, using a Shimadzu Corporation pore distribution / specific surface area measuring apparatus ASAP- 2010 (trade name), a powdered oxygen absorbent of the present invention, taken in a standard cell, in sample pretreatment unit of the apparatus, about 6 hours at a temperature 35 ° C, and degassed by Kr gas adsorption method, it was measured by using a BET approximation.

<Average particle diameter>

The average particle size is at JEOL Co. run 查型 electron microscope i¾JSM_ 5600LV (trade name), using the result of observation of the secondary electrons in high vacuum mode, select the 50 particles at random

, The diameter of a circle having the same area as each grains account in photographs was determined and with their simple average.

[0105] The average particle being asked as diameter, an average particle diameter of primary particles is flat particle size of Nag agglomerated particles.

Ku saturation oxygen absorption amount (Vos)>

A sample of about 0. lg of powdered oxygen absorbent, the wall thickness is oxygen permeation amount 30 cm 3 / at 80 xm (m 2 'day' MPa) less than a is polyvinylidene chloride made barrier with the volume of 200 cm 3 placed in a container, the oxygen volume 21% through the vessel was sealed and purged with nitrogen 79 volume% of the mixed gas. Then, we put these pot temperature 23 ° C, RH for humidity 17%, using PBI manufactured gas concentration measuring apparatus Dansensor CheckMate9900 (trade name), monitoring the change with time of the oxygen concentration in the container It was calculated oxygen absorption amount. The amount of oxygen absorbed per oxygen absorber lg at the time the oxygen concentration has reached the saturation, the saturated oxygen absorption amount (Vos, the unit is cc / g) was defined as.

<Maximum oxygen absorption rate (Ros), the induction period>

The vertical axis of the oxygen absorption amount obtained in the oxygen absorption amount measuring method, in was convex elapsed time on the horizontal axis curve (oxygen absorption curve), the maximum magnitude of slope the maximum oxygen absorption rate (Ros, unit It was defined as ccZ (g 'hr)).

[0106] Further, in the oxygen absorption amount measurement method, a period from the start of measurement until the oxygen concentration in the container is 20. Less than 6% (in hr or day) was defined as the induction period.

<Method of quantifying antioxidant>

An antioxidant sample of about 3g of powdered oxygen absorbent with standard addition, and Kurorohonoremu / methanol reprecipitation was concentrated dried and solidified The filtrate was created Sanpunore was filled up to 10ml with methanol. The sample Waters Corp. liquid chromatograph device 600 (trade name), micro-Bondapak C18 as column, methanol as liquid feed conditions: water = 80: 20 (start), a linear gradient (0-5 min), methanol: water = 100: 0 (5-20 minutes), flow rate lml / min, injection volume 30 mu 1, the condition of Waters Corp. UV detector 996 as the detector (trade name) (detection wavelength 28 5 nm) Te, a standard addition method was measured by a liquid chromatography measurement.

[Example 1]

Manufactured by Asahi Kasei Chemicals Corporation polybutadiene rubber having a Mooney viscosity of 55. (Hereinafter abbreviated as BR.) Jen 55AE (trade name) to 3g, and well stirred toluene 25g as the good solvent, and dissolved completely. Then added with stirring well with methanol 250g as a poor solvent to precipitate the polymer mass, using filter paper was removed the supernatant liquid to obtain precipitate this operation 3 times repetitive manner. The BR obtained by the dissolution reprecipitation method as the thermoplastic resin (A) was dissolved in toluene 12 g, 0 as manufactured by Wako Pure Chemical Industries, Ltd. naphthenate cobalt 0 · 05G (cobalt atom as oxidation promoting component (B) - what was stirring well with the addition of 1 wt 0/0), placed in a glass petri dish with a diameter of 8.5 cm, by Ri at 35 ° C in Yamato scientific Co., Ltd. of vacuum dryer DP63 (trade name), 48 to obtain a sheet of transparent thickness of about 300 mu m by the time vacuum drying. Next, using a SPEX Co. freezer mill SPEX6700 (trade name), after cooling for 10 minutes with liquid nitrogen was placed in crushed tube filled with nitrogen gas the sheet lg, by performing freeze powder crushed for 5 minutes to obtain a powdery oxygen-absorbing material. Powdery oxygen-absorbing material is a white solid powder, be returned to the normal temperature without adhere was base had a manageable form. Also the powder oxygen intake Osamuzai was observed with a scanning electron microscope, it has been a structure in which grain terminal of size of several mu m to about 1000 mu m are mixed. Further, when the particles further expand, how the primary particles of about 0. 5 / im ~ about 5 mu m is mutually aggregation was observed. Such large and small particles are mixed, such a structure that fine particles are mutually aggregated, to prevent adhesion of the powder to each other while maintained large area of ​​contact with oxygen, it contributes to excellent oxygen absorbing performance it is considered that. The specific surface area of the powder-like oxygen-absorbing material 2, 920cm 2 / g, average particle size was 0. 95 mm. Was the DSC measurement of the powder-like oxygen-absorbing material, the crystal melting peak did not have. Incidentally, the powder-like oxygen-absorbing material in 1 day after toluene immersion, to the extent that do not have their original will completely dissolve, did not substantially crosslinked. [0108] For powder oxygen absorbing material were evaluated by the above method, Vos = 230 cc / g, a Ros = 38cc / (g 'hr), shows excellent oxygen absorption amount and the oxygen absorption rate It was.

[0109] The powder oxygen absorbing material lg and Japan Enbai port Chemicals Inc. activated carbon granular Shirasagi GAAx

(Trade name) 0. 5 g Gurley tester method (IIS _p_ 8117) in which the air permeability in conformity is filled into sachets of 8, 000 seconds the bag material (hereinafter referred to as pouch sample), the volume 2L Omi Odoea one service manufactured by sampling bag. is Rere to flex sampler F (trade name), the air is oxygen absorption in a state where the seal is filled with, smelled the air in the bag after one day between the roller, unpleasant odor was not felt. Further, by using a Riken Keiki Co., Ltd. formaldehyde detector FP_ 30 (trade name), it was measured air formaldehyde in a bag, was below the detection limit (0. Olppm).

[0110] Further, the Dorayaki and the sachet samples weighing approximately 80g were sealed in bag above sampling, where smelling one day after the oxygen concentration measurement and air odor in the bag of the barrier bag , oxygen concentration is 0.1% and the pouch Sanpunore is not felt oxygen absorbing and and unpleasant odor, and good fragrant Dorayaki. Further, sealed and Dorayaki and sachet samples barrier bag in consisting of PP / PA / EVOH / LL DPE, and one day left to measure the oxygen concentration in the barrier bag (0.1%), followed the place smelling the air of odor in the bag after heating in a microwave oven, unpleasant odor is not felt, was a good smell of Dorayaki.

[Comparative Example 1]

Following the method of Example 1 of Patent Document 1, molecular weight 10, arm 000 one hundred twenty-one viscosity 5 polybutadiene 0. 5 g of less than the liquid, manufactured by Wako Pure Chemical Industries, Ltd. soybean oil 0. 5 g, net Wako the mixture Chemical Industries Co., Ltd. cobalt naphthenate consists 0. 2 g, was impregnated into Wako Pure Chemical Industries, Ltd. activated carbon 5 g, sprinkled hydrated lime 0. 5 g on the surface of the activated carbon is impregnated, powdered oxygen absorption It created the wood.

[0111] For powder oxygen absorbing material were evaluated by the above method, as shown in FIG. 1, Vos = 41cc / g, and Ros = lccZ (g 'hr), powdery oxygen present invention It was inferior compared to the absorption material. Thus Yore lower component than Mooney viscosity Mooney viscosity of less than 5 and the present invention to oxygen absorption reaction and Ru, and because apt powder to each other and reattached to each other, oxygen, such as carrying body because when the absorption reaction containing as a main component unrelated components oxygen absorber total amount per Rino oxygen absorbing performance is relatively low, the oxygen absorption amount by the like, the oxygen absorption speed is the invention It was lower than that of the oxygen-absorbing material.

[Comparative Example 2]

In the mixing step of Example 1, was further added to the cobalt naphthenate 0. 05G Nippon Yushi Co., Ltd. Organic peroxide Di - 2 _t_ butyl peroxide O carboxymethyl isopropylbenzene (trade name perbutyl P) 0. 3 g of 60 ° outside mixed with C to create a mixture in the same way, and cooling after heating 10 minutes at 180 ° C in a vessel equipped with nitrogen substitution and the mixture. This was triturated in the same manner as the more grinding E of Example 1 to prepare a powdery oxygen-absorbing material. Arm one hundred twenty-one viscosity of the powdery oxygen-absorbing material could not be measured beyond 400. It was completely dissolved in toluene. The specific surface area of the powder-like oxygen-absorbing material 2, 850cm 2 Zg, average particle size was 0. 82mm.

[0112] For powder-like oxygen-absorbing material, was evaluated by the above method, was Vos = 132cc / g, Ros = 14ccZ (g 'hr). Thus, you can reduce the double bond required by Ri oxygen absorption reaction to powdery oxygen-absorbing material is crosslinked, because, for example the molecular motion or I is limited, the oxygen absorption amount , the oxygen absorption rate was low compared to the oxygen-absorbing material of the present invention.

[Comparative Example 3]

Following the method of Example 1 of Patent Document 3, cobalt naphthenate salts 0. 8 mmol, tri E chill aluminum 2. 4 mmol, butadiene 240ml and carbon disulfide 1 · 6 mmol, was prepared powdery oxygen-absorbing material. Powder oxygen absorbing material is a spherical diameter 200 μ ΐη, a melting point of 147 ° C, Mooney viscosity could not be measured beyond 400.

[0113] For powder oxygen absorbing material were evaluated by the above method, Vos at 18 cc / g, Ros was substantially zero.

[0114] Thus, in the high powdery oxygen intake Osamuzai than the melting point of the powdered oxygen absorbent having a melting point of 147 ° C and the invention, for reasons such as that the molecular motion is restricted, the oxygen absorption amount , the oxygen absorption rate was low compared to the oxygen-absorbing material of the present invention.

[Comparative Example 4]

About Mitsubishi Gas Chemical Co., Ltd. Steel based oxygen absorber AGELESS ZP- 50 (trade name), was evaluated in the above-described how, Vos = 68cc / g, was Ros = 18cc / (g'hr). [Example 2]

In Example 1, in place of cobalt naphthenate 0. 05G, manufactured by Wako Pure Chemical Industries, Ltd. silver oxide (1) outside using 0. 03G (1.0 wt% as silver atoms) of oxygen-absorbing materials in exactly the same way Created. The specific surface area of the powder-like oxygen-absorbing material 9, 450cm 2 Zg, average particle diameter ivy 3 0. 78 mm.

[0115] For powder oxygen absorbing material were evaluated by the above method, a Vos = 153cc / g, Ros = 19ccZ (g * hr), exhibited excellent oxygen absorption amount and the oxygen absorption rate .

[Example 3]

In the mixing step of Example 1, dissolved to BR obtained by re-precipitation method, Ciba 'scan Bae Shariti' Chemicals Inc. Fuwenoru antioxidant · IRGANOX 1076 (trade name) as an antioxidant (C) (Okutadeshiru one 3- (3, 5-di one t- butyl one 4-hydroxyphenyl) the added Caro amount of propylene signage Bok), 260 ppm, 650 ppm, 1300 ppm, those that have been added while changing the 1800 ppm, also manufactured by Sumitomo chemical Co., Ltd. Iou system added Caro amount 100ppm antioxidant 'Sumilizer TPS (product name) (Jisutearinorechi old dipropylene Saisai ヽー Bok), 250 ppm, at 500ppm, 180 Oppm and varied in example 1 in exactly the same way as for those of the added you create a powdery oxygen-absorbing material. The specific surface area and average particle size of which such were substantially equivalent to those of the first embodiment.

[0116] For powder oxygen absorbing material were evaluated by the above method, all samples Vos is approximately 230 cc / g, Ros was approximately 38cc / (g -hr).

[0117] Here, the induction period of the pulverulent oxygen absorber are summarized in Figure 2, between the induction period will be described can be controlled by the antioxidant (C).

[0118] Figure 2 is the vertical axis the induction period of the powdery oxygen-absorbing material, the horizontal axis is a diagram was convex to 添Ka 卩量 antioxidant (C). Figure "♦" mark Rre in case of adding phenol antioxidant Te, "mouth" mark Ru les, show Te Nirre, when adding Iou antioxidant.

[0119] In FIG. 2, the force I force can be controlled induction time by the addition of an antioxidant (C), Ru.

In the case of [0120] Particularly in the drawing "♦" mark of the phenolic antioxidants, linear relationship between the induction period and the amount of phenolic antioxidant was seen, be controlled to a desired induction time it can be seen that it is easy. In the case of phenol-based antioxidant, the addition amount 50: 1, the induction period in the case of OOOppm of about 3 hours to about three days.

[Example 4]

倣Re ,, 1 Preparation of SB rubber latex of Example 2 of JP-A-05- 017507, 3-butadiene E down 18.0 parts by weight, Atari Roni Turin les 2.0 parts by weight, t-dodecyl mercaptan 0.1 parts, potassium salt 0.067 parts by weight of disproportionated rosin acid, tallow Ken fossil Ken 0.033 parts by weight of sodium persulfate 0.075 parts by weight, sodium hydroxide 0.03 parts by weight, sodium bicarbonate 0.10 parts by weight, de the ionized water 60.0 parts by weight, were charged into the autoclave was degassed inside was evacuated and polymerized by emulsion polymerization at 65 ° C.

[0121] In addition, over the polymerization initiator 2.5 hours force 5 hours, 1, 70.0 parts by weight of 3_ butadiene, styrene 10.0 parts, 0.3 parts by weight of t- dodecylmercaptan, disproportionation rosin acid strength potassium salt 0.67 part by weight, 0.33 parts by weight of beef tallow Ken fossil Ken, 1 part by weight of 0.1 sodium persulfate, 0.05 part by weight of sodium hydroxide, 0.15 parts by weight of sodium bicarbonate, oxide Nihon Kagaku Sangyo Co., Ltd. of zinc naphthenate as a promoter component (B) (trade name Nafutekkusu Zn8% T) of 0.5 by weight section (nitrous ii, 0. 04 parts by weight atom), 50.0 weight of deionized water a Department polymerized while continuously added to the autoclave, to produce a powdered oxygen absorbent.

[0122] The average particle size of the powder-like oxygen-absorbing material 3. 5 / im, the specific surface area is 19, 500cm 2 / g, the melting point had no. Further, arm one hundred twenty-one viscosity of powder oxygen absorbing material was 80. For dried powder oxygen absorbing material were evaluated by the above method, Vos = 140 cc / g, a Ros = 26cc / (g 'hr), shows excellent oxygen absorption amount and the oxygen absorption rate It was.

[Example 5]

Manufactured by Asahi Kasei Chemicals Corporation, styrene / butadiene copolymer Mooney viscosity 190 'Asa Puren T420 manufactured by Wako Pure Chemical Industries, Ltd. cobalt naphthenate 1.67% by weight relative to the (trade name) (0.1 wt% as cobalt atoms ) after mixing until uniform in a blender one was kneaded at 215 ° C using these mixture Ikegai Tekko Co. biaxial extruder PCM_45 (trade name). The strand-like resin composition emerging from the die and cooled with water, followed by post-cutting dried pellets using a win Seisakusho water cooled pelletizer one KN- 150 (trade name), put in an oxygen barrier property bag and sealed storage. Then, the pellets were ground using a Nishimura Machinery Co., Ltd. disc grinder grinder GPC_ 140 (trade name) Creates a powdery oxygen-absorbing material. Powdery oxygen-absorbing material, a pale blue solid powder, be returned to the normal temperature without adhere was base had a manageable form. Also was hand observation of the powdery oxygen-absorbing material to a scanning electron microscope, has been a structure in which the size of the particles of about 20 mu m to about lmm are mixed. Moreover, when further expanding the particles, how the primary particles of about 0. 5 zm~ about 20 zm are mutually aggregated was observed. The average particle size of the powder oxygen absorbing material 0. 78mm, a specific surface area of 2, 400cm 2 Zg. Further, the content of the antioxidant in the powder oxygen absorbing material was analyzed by the method described above, was 410 ppm. Was the DSC measurement of the powder-like oxygen-absorbing material, the crystal melting peak did not have.

[0123] The powder oxygen absorbing material, degassed packaged in a bag of the oxygen barrier property made EV_〇_H / Ny, and 240kGy irradiated the edge Noreto -60 gamma. It was 165 The measured beam one hundred twenty-one viscosity of powder oxygen absorbing material after irradiation.

[0124] For powder oxygen absorbing material were evaluated by the above method, Vos = 102cc / g, Ros = 20cc / (g 'hr), the induction period is 4 hours, excellent oxygen absorption amount and it showed the oxygen absorption speed.

[0125] Note that powder oxygen absorbing material to 25 ° C, after standing for 4 hours in the atmosphere of RH 20% RH were evaluated by the above method, the oxygen absorption amount and the oxygen absorption rate is changed Nakatsu was.

[Example 6]

Te embodiment Nobi Rere, gamma, line f, a morphism f fountain amount, 30 kGy, 120 kGy, also outside of changing ί or 500kGyi This created the oxygen-absorbing material in exactly the same manner as in Example 5. Incidentally, each arm one hundred twenty-one viscosity of each powdered oxygen intake Osamuzai were 135, 150, 180. It was evaluated with the powder-like oxygen-absorbing material by the above method, Vos of the oxygen-absorbing material which such substantially 102cc / g, Ros affect the dose of gamma radiation at approximately 20cc / (g -hr) It had been such a force.

[0126] On the other hand the induction period, the irradiation amount is 30, 120, 240, 500 of the gamma ray, 24-hour induction period, respectively, 8 hours, 4 hours, 0.5 hours, the dose of gamma rays, It was found to be controlled easily induction period.

[Example 7]

Example 5 of the powdered oxygen absorbent, and further Mitsubishi Gas degassed Chemical Co. deoxidizer Ageless ZP 200 (trade name) with EVOH / Ny made of oxygen barrier properties in the bag packaging, 40 ° C in 10 days, 20 days, 30 days, was stored for 60 days. For powdered oxygen absorbent after storage were evaluated by the above method, Vos is approximately 102cc / g, Ros is such affected by the substantially 20cc / (g 'hr) in the low oxygen atmosphere storage period force It was.

[0127] On the other hand, a low-oxygen atmosphere storage period and try to focus on the induction period 0 days, 10 days, 20 days, 30 days, with respect to 60 days, respectively induction period 4 hours, 2 hours, 1 hour, 1 hour, Ri 1 hour der, the induction period as a low-oxygen atmosphere storage period becomes longer became almost constant Eru Yue snow 20 days Te summer short.

Industrial Applicability

[0128] powdered oxygen absorbent of the present invention, metal products, food, pharmaceutical, photographic film, manuscripts, painting, can be suitably used in the fields of storage, such as electronic products.

Claims

The scope of the claims
[1] Mooney viscosity of 10 to 400, and differential run 查熱 meter no crystalline melting peak when measured by a differential scanning calorimeter (DSC) or melting point is below 75 ° C, Ariru hydrogen and Z or tertiary carbon thermoplastic polymer (a) and an oxidation promoting component comprises (B), powdered oxygen absorbent, wherein the specific surface area of 60cm 2 / g or more with a bonded hydrogen in the molecule and.
[2], wherein the beam one hundred twenty-one viscosity of the thermoplastic polymer (A) is between 20 and 150, pulverulent oxygen absorbing material according to claim 1.
[3], wherein the thermoplastic polymer (A) is a polymer or copolymer containing butadiene units 50 wt% or more, powdery oxygen-absorbing material according to claim 1 or 2.
[4] Thermoplastic polymer (A) is a butadiene unit and 50-99% by weight: ~ of 50 wt% of the scan styrene units, characterized in that it is a copolymer block or random structure, according powdery oxygen-absorbing material according to any of claim 1-3.
[5] 50 in a thermoplastic polymer (A):!, Characterized in that it contains an antioxidant (C) of OOOppm, powdery oxygen-absorbing material according to claim 1.
[6] The thermoplastic polymer (A), and also contains the oxidation promoting component (B), and a thermoplastic polymer (A) to hardly adhere to each other but having adhesion of the fine particles (D), the average particle size in the 10 zm~5 mm, and is characterized in that located on the surface of at least part of (a) and (B) a force comprising powder of the fine particles (D), any of claims 1 to 5 powdered oxygen absorbent crab according.
[7] The following powdery manufacturing method of the oxygen-absorbing material made of steps.
Step (X): a beam one hundred twenty-one viscosity 10 to 400, Ariru hydrogen and a and differential run 查熱 meter no crystalline melting peak or a melting point as measured by a differential scanning calorimeter (DSC) is less than 75 ° C thermoplastic polymer Z or is having a hydrogen bound to tertiary carbon in the molecule (a) and the step of melt-mixing in a heated molten state oxidation promoting component (B)
Step (Y): step a step of pulverizing the resulting melt mixture (X)
Step (Z): step (X) with resulting melt mixture or exposing the step (Y) obtained pulverized material into 2 Kirogu ray or radiation
Step (S): a step of storing the molten mixture or flour 碎物 hypoxic atmosphere
PCT/JP2006/304044 2005-03-07 2006-03-03 Powdery oxygen absorbent material and process for producing the same WO2006095640A1 (en)

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JP2008073628A (en) * 2006-09-22 2008-04-03 Asahi Kasei Chemicals Corp Oxygen absorbing composition and manufacturing method thereof
JP2009298889A (en) * 2008-06-11 2009-12-24 Kyoraku Co Ltd Oxygen-absorbing polyamide-based resin composition and method for producing the same
WO2014038659A1 (en) * 2012-09-07 2014-03-13 三菱瓦斯化学株式会社 Oxygen-absorbing resin composition and oxygen-absorbing multilayer body using same
JP2017039900A (en) * 2015-08-21 2017-02-23 横浜ゴム株式会社 Production method of modified polymer, modified polymer, rubber composition and pneumatic tire

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