TW200536488A - Oxygen absorbent, method for producing the same, and oxygen absorbing composition and packaging material using the same - Google Patents

Abstract

Disclosed is the oxygen absorbent containing an inorganic particle, an unsaturated organic compound chemically adsorbed on the inorganic particle, and an oxygen absorption accelerator. Such oxygen absorbent can be produced by a manufacturing process comprising a step to have an unsaturated organic compound chemically adsorbed on an inorganic particle, and a resin composition having a high oxygen-absorbing power is obtained from this oxygen absorbent. Also disclosed are an oxygen-absorbing resin composition and packaging material using this oxygen absorbent.

Description

^ 200536488 IX. Description of the invention: [Technical field to which Mao Ming belongs] Oxygen absorption using the present invention The present invention relates to an oxygen absorbent, a method for manufacturing the same, a recyclable composition, and a packaging material. [Prior art] Items that are easily deteriorated by oxygen, such as food, are important to be stored in a low-oxygen environment for stable storage. To be able to do so,

Various oxygen absorbers have been proposed. As such oxygen absorbents, there have been proposed oxygen absorbents in which organic compounds are supported by inorganic substances (for example, Japanese Patent Laid-Open Publication No. Hei. 2, Japanese Patent Laid-Open No. 2_, Japanese Patent Laid-Open No. 2 and Japanese Patent Laid-Open No. 2 _ Gazette No. 15 and JP-320917). The use of the oxygen absorber that has been proposed in the past, the% performance in dispersion in the resin will be greatly reduced, which is the problem. [Summary of the Invention] In view of this situation, one of the objects of the present invention is to provide an oxygen absorbent capable of constituting a resin composition capable of absorbing oxygen, and a method for producing the same, and a resin composition using the same. And packaging materials. In order to achieve the above object, the oxygen absorbent of the present invention contains organic compounds (organic compounds and oxygen absorption promoters) that are inorganicized and adsorbed on the inorganic particles. The organic compounds are described in the above-mentioned oxygen absorbent of the present invention. It is an organic 200536488 compound formed by reacting at least one organic compound (A) in the group consisting of carboxyl, aldehyde, alkoxysilane derivative, and amine with the inorganic particles. In the above-mentioned oxygen of the present invention In the absorbent towel, the organic compound may also be a saturated organic compound. In the oxygen absorbent of the present invention, the organic compound may also contain a structure represented by the following formula (1): CH2 \ R1 /

… ⑴ [wherein Ri A R2 is independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group,- I of COOR3, -OCOR3, cyano and _ atom; ^ is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, aralkyl, substituted aralkyl 1 of them]. The above-mentioned oxygen absorbent of the present invention may also contain a structure represented by the following formula (2); R \ / R5 0 ~ 〇 ^… —CH ^ factory [where R4 and R5 are independently selected from a hydrogen atom and an alkane One of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted alkyl group, -COOR3, -OCOR3, an aryl group, and an _ atom; One of a sulfanyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group]. In the oxygen absorbent of the present invention described above, the organic compound may have an unsaturated alicyclic structure. ^ 200536488 In the above-mentioned oxygen absorbent of the present invention, the organic amount may be 3,000 or less. The initial chemical formula is the one consisting of the inorganic substance in the oxygen absorbent of the present invention. In the above-mentioned oxygen-absorbing property of the present invention, the inorganic particles may be those on the surface. In this case, the inorganic particles may be particles of hydrotalcite. In the oxygen absorbing agent of the present invention, the oxygen absorption promoter may be at least one selected from a transition metal salt, a radical generator, and a photocatalyst. ',', And the manufacturing method of the present invention is used for manufacturing an oxygen absorbent containing an inorganic substance particle and a milk absorption promoter; and includes a process of chemically adsorbing an organic compound to the inorganic substance particle. In the above-mentioned manufacturing method of the present invention, the organic compound may be an unsaturated organic compound. In the manufacturing method of the present invention, the inorganic particles may have a base on the surface, and the organic compound may have a functional group capable of reacting with amidine. In the production method of the present invention, the organic compound may be at least one member selected from the group consisting of a transcript, an ester, an aldehyde, an alkoxysilane derivative, and an amine. The above-mentioned manufacturer & of the present invention may also include the following processes: preparing a process containing the organic compound, the inorganic particle, and a mixture of organic solvents; and (ii) removing the organic solvent from the mixture Process. This field eight

It may also include a process in which the mixture is heated at the temperature of the Buddha's point of water at a temperature of 1 after the process of (11). 1. The above-mentioned manufacturing method of the present invention may also include the following process: a process of adjusting a mixture containing the organic compound and the inorganic particle; and (^) • 200536488 The organic compound is heated by heating the worry-free compound A process for chemically adsorbing compounds onto the inorganic particles. In this case, the process of (H) may include a process of heating the mixture at a temperature higher than the boiling point of water. Li Guang = In the above-mentioned production method of the present invention, the mixture may be heated in a nitrogen atmosphere or under reduced pressure. In the manufacturing method of the present invention, the inorganic particles may be composed of a layered inorganic compound. X 'The other oxygen absorbent of the present invention is an oxygen absorbent produced by the above-mentioned production method of the present invention. ▲ The oxygen-absorbing composition of the present invention includes a resin and an oxygen-absorbing agent dispersed in the resin; the oxygen-absorbing agent may be a polymer in which the oxygen of the present invention is absorbed in the oxygen-absorbing composition. This resin contains an ethylene-vinyl alcohol copolymer and the packaging material of the present invention, and contains a portion composed of the oxygen-absorbing composition of the present invention described above.

The oxygen absorber of this month is in particulate form, so it can be easily and uniformly dispersed in the resin. x, the oxygen absorbent of the present invention 'because of the oxidized organic: compound chemically adsorbed on the inorganic particles, it can exert high oxygen absorption energy, and organic compounds can easily obtain the An oxygen absorber formed by chemical adsorption on inorganic particles. In addition, the oxygen-absorbing composition of the present invention can exhibit a high oxygen-absorbing ability by using the oxygen of the present invention, and can suppress the occurrence of exudation. 8 -200536488 In addition, it can prevent the oxidized organic compound from volatilizing from the mouth when the oxygen absorbent is mixed with the resin. In addition, even when the oxygen absorbent is mixed with the tree = before the oxygen: and the receiver are washed, the organic combination of oxidation can be prevented / removed. By using such a resin composition, the oxygen absorbency can be obtained. The processability is excellent, and each mouth ^ 4 丄 "Genkou mouth is born with high-safe packaging materials. Also,: Using such packaging materials' can reduce the oxygen inside the packaging formed by using Baoxiang materials. [ [Embodiment] The present invention will be described as "an embodiment of the present invention." The following i-items < compounds capable of exerting a specific role " are exemplified by specific examples: However, the present invention is not limited to this. The exemplified materials may be used alone or in combination unless otherwise specified. (Embodiment 1) = In the embodiment 1, the oxygen absorbent of the present invention will be described. This hair: and the receiver 'Contains inorganic particles, chemically adsorbed on the inorganic particles: organic compounds (organic groups), and oxygen absorption promoters. This organic compound is used for transition metal salts or free radical generators as oxygen absorption promoters: Carbon-carbon double bond In this case, the unsupported methylenyl group is preferably unsubstituted. A high oxygen absorption capacity can be found by the structure of ′, and the organic compounds can be suppressed. Oxygen contains low-molecular-weight compounds. As such a structure, for example, a structure represented by the following formula (1) or (2) may be used.

-CH f2 \-• (1) ^ 200536488 [In the formula, R1 and R2 are each independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, a substituted alkyl group, an aryl group, and a substituted group. One of aryl, aralkyl, substituted aralkyl, -COOR3, -OCOR3, cyano, and halogen atom; R3 is selected from alkyl, substituted alkyl, aryl, substituted One of aryl, aryl, and substituted aryl]. R \ R5 c = cx… ⑵ —GH ^ \ 〇Η2— [wherein R4 and R5 are each independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, One of aralkyl, substituted aralkyl, -COOR3, -OCOR3, cyano, and halogen atom; 113 is selected from alkyl, substituted alkyl, aryl, and substituted aromatic One of an aralkyl group, an aralkyl group, and a substituted aralkyl group]. When R1, R2, R3, R4, and R5 are substituted alkyl groups, substituted square groups, and substituted aryl groups, the substituents are preferably those that can improve the affinity with the resin. For example, an organic compound having a hydroxyl group and a carbon number of} to 10 can be chemically adsorbed on an inorganic particle, and an organic compound containing a functional group capable of reacting with the surface of the inorganic particle can be used (hereinafter also referred to as a Qianhua a compound). (A)) Formed by reacting with the surface of the inorganic particle. The ratio of the organic compound (A) to which inorganic particles are adsorbed and the absorption of oxygen is not particularly limited. Depending on the materials used and the purpose of use, 100 parts by weight of inorganic particles may be adsorbed on The organic compound thereon is preferably in the range of i parts by weight to 100 parts by weight, and more preferably 1 part by weight to 50 parts by weight. In the case of using a transition metal salt as an oxygen-200536488 absorption accelerator, the amount of the metal salt can be set to 10-4 weight " what? " Read, transitional gold ό ^ ^ parts by weight. In the case of using a chemocatalyst as an oxygen absorption accelerator, the amount of organic oxygen accelerant can be…… the average particle size of the organic particles is equal to _. ^ 4 上 " ,,, and the limit疋, to 100Onm to 仏 马 仏 'and to 500nm or below ^^

Below is better. The reason is to flatten the inorganic particles :: ... 00nm or less' can increase the surface area of the organic substance to more effectively chemisorb. Further, it is possible to improve the dispersion of the polymer, and to impart transparency. Inorganic particles are preferably functional groups having reactivity on the surface, and particularly preferably having a warp group on the surface. χ, inorganic particles, to be inorganicized by layer: Do not constitute 4 gui. As the layered compound, for example, a layered clay mineral such as a layered clay mineral such as hydrotalcite, montmorillonite, or kaolinite, such as a layered clay mineral, such as kanemite, can be cited. Pieces of big metal schrotite, thorium, copper oxide, etc. By making particles composed of a layered compound into an oxygen-absorbing composition with high gas barrier properties and packaging, the surface area can be increased by layer separation, and highly reactive functional groups can be effectively used. The organic compound (A) is caused to adsorb more. Among them, the fire / moonstone has a large number of warp groups on its surface, so by using hydrotalcite as the inorganic particles, the amount of the organic compound (A) adsorbed thereon can be 3: Zeng Likou 0 and ' Since the hydrotalcite is a neutral compound at both ends of the acid and the test, even when it is dispersed in various resins, it does not erode the resin and can form a composition stably. Therefore, hydrotalcite can also exhibit stable oxygen absorption when it is used in the composition of oxygen absorption 11 200536488. ^ Organic compound (A), which contains an agent capable of reacting with the surface of inorganic particles ^ When hydroxyl groups are contained on the surface of non-mechanical particles, it contains

, '土 反 二' s g '. Examples of the functional group having high reactivity with a hydroxyl group include a carboxyl group, an ester group, an aldehyde group, a oxysilyl group, and an amino group. That is, as the organic compound, for example, a compound selected from at least one selected from the group consisting of acid, vinegar, vinegar, plate, stalk, sporewood, and amines. By reacting these compounds with tritium on the surface of the inorganic particle, an organic compound having a compound adsorbed on the surface of the inorganic particle can be formed. In part 4, a part of the organic compound (A) (for example, a hydrogen atom or a hydroxyl group) reacts with the surface of the inorganic substance particle to form water to be detached. For example, the functional group that undergoes the reaction is a Wei group, an acyl group, or a% of an acid group, and will be bonded to the inorganic particle with a portion such as & In addition, when the functional group for reaction is an alkoxysilyl group, it is bound to the inorganic particles with its ^ 71 part ... When the functional group for reaction is an amine group, it is bonded to its nitrogen part, etc. Inorganic particles are bonded. The organic compound (A) and the organically-formed person chemically adsorbed on the inorganic particles may be selected from the group consisting of osmic acid, ester, aldehyde, oxanite derivative, and amine containing a structure represented by the above formula (1). At least one compound in the group. Further, the organic compound (A) and the organic compound chemically adsorbed on the inorganic particles may be selected from the group consisting of carboxylic acid, g, end, and pyroxenite derivatives containing a structure represented by the above formula (2), and One compound in the group consisting of amines to 7 Wang Xi 0 organic compounds (A), and organic compounds chemisorbed on inorganic particles 12 200536488 It is also an alicyclic structure with a 5-membered ring to a 10-membered ring Since Junxi Yue, at least i kinds of chelating substances in the group consisting of acid, mahogany and amine derivatives and amines. In addition, the use of a compound having an unsaturated alicyclic structure can suppress the production of low-molecular compounds due to the oxidation of organic compounds when absorbing oxygen, and "hunting this" can suppress the generation of odors accompanying oxygen absorption. The hydrogen bonded to the carbon constituting the cyclic structure may be substituted by another substituent. When plural substituents are present, they may be the same or different. Examples of the substituent include a hydrogen atom, fluorene (with or without a substituent), alkoxy group (with or without a substituent), an atom, a cyclic substituent containing a methyl group, and an oxymethylene group. Cyclic substituent. Examples of representative carboxylic acids suitable for use as the organic compound (A) include palmitic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, docosahexaenoic acid, eicosapentaenoic acid, Dimer acid, linseed oil fatty acid, soybean oil fatty acid, stalk oil fatty acid, sugar oil fatty acid, flax oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, fish oil fatty acid, tall oil, etc. unsaturated fatty acids such as fatty acids . Among these, especially linolenic acid, since there are three double bonds in the molecule, the molecular oxygen absorption amount is high, and an oxygen absorbent having a high oxygen absorption capacity can be obtained. When photocatalyst is used as an oxygen absorption accelerator, in addition to the above unsaturated acids, for example, saturated aliphatic monotarctic acids such as formic acid, acetic acid, propionic acid, butyric acid, stearic acid, etc .; oxalic acid, malonic acid, etc. Saturated aliphatic dicarboxylic acids such as acids, succinic acid, glutaric acid, adipic acid, and sebacic acid; aromatic aromatic acids such as benzoic acid, phthalic acid, and terephthalic acid. In addition, as a representative brew used as the organic compound (A), the g purpose of the carboxylic acid described in 13 • 200536488 is mentioned. k is used as a representative aldehyde of the organic compound (A), and examples thereof include dibutenal, senelite, pentenal, hexenal, 7-octenal, nonane red, and 5 · norbornene _2 Zun, acrylic, methacrylate, etc. When the catalyst is used as an oxygen absorption accelerator, in addition to the above-mentioned unsaturated, for example, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, hexanal, and octaldehyde Saturated fatty acid aldehydes, such as nonanal, decanal, and azelal.

In addition, a typical alkoxysilane derivative that is suitable as the organic compound (A), that is, a compound having an alkoxysilyl group, and examples thereof include compounds containing a trimethoxysilyl group or a diethoxysilyl group. Outside of alkoxysilyl hydrazone. The p component is not particularly limited, and may contain, for example, halogen, an alkyl group (which may have a substituent), an alkenyl group (which may have a substituent), an alkynyl group (which may have a substituent), and an aryl group (which has a substituent). (Also), aralkyl (with substituents), alkoxy, carboxyl, alkynyl, cyano and other atomic groups. Also, the representative amines suitable for use as the organic compound (A) include, for example, female hydrazine, oleylamine, N-methyl propylamine, dimethylamine, N, N, -diethyl 2-butane Ene · ι, 4-diamine, N-di-propylcyclopentylamine, di-propylcyclohexylamine, 2- (h-cyclohexene) ethylamine, and the like. When a photocatalyst is used as an oxygen absorption accelerator, in addition to the unsaturated amines described above, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, second butylamine, and third butylamine can be used. Amine, pentylamine, isoamylamine, tertiary pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, Dipentylamine, dihexylamine, dioctylamine, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, diaminobutane, 1,5-diaminopentane , Ι, 6-diaminohexane, ι, 7-14 200536488 based nonane, 1,10. Diaminoheptane, 1,8-diaminooctane, diaminodecane, etc. Saturated aliphatic amine. Among these compounds, You J: Prefectural Bismuth Office, You /, Carboxyl S, are preferred because they can be strongly adsorbed on the surface of inorganic particles. Although the molecular weight of the total organic compound is not particularly limited, the amount of the chemical compound of the organic compound adsorbed to the precatalyst particles is set to be equal to or less than the side (for example, equal to or less than 5,000), so that it can be easily dispersed in the resin. Therefore, the molecular weight of the organic compound (A) is preferably 3,000 to τ < J (for example, 500 or less). 〃Oxygen absorption promoter is an additive used to promote the absorption of oxygen. The milk absorption enhancer can promote the oxidation of the organic compound (A) which is chemically unstacked particles, and as a result, the oxygen of the breast of the corpse can be eliminated. Since the oxygen and collector of the present invention contain an oxygen absorption accelerator, the inorganic particles do not require a photocatalytic action. Oxygen absorption enhancers can _eg, _ contact with auto-oxidation at least! Species. As the oxidation catalyst in the group consisting of a radical generator and a photocatalyst, a transition metal salt can be used. Examples of the transition metal constituting the salt include iron, nickel, and copper, cobalt, germanium, titanium, chromium, palladium, and ruthenium. + Iron, nickel, copper, manganese and cobalt are preferred. Examples of the anion constituting the transition gold sol include anion derived from an organic acid or a gaseous substance. Examples of the organic acid include acetic acid, stearic acid, dimethyldithiocarbamic acid, and palmitic acid. , 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, oleic acid, resin acid, capric acid, and naphthoic acid. Typical representative salts' include, for example, a 2-ethylhexanoic acid chain, neodecanoate, naphthoate, and phosphonium stearate. As a transition metal, an ionomer 15 • 200536488 (ionomer) can also be used as the radical generator, and examples thereof include N-hydroxysuccinic acid imine and N-. Cis-butenedioic acid amidine Amine, n, n, _dihydroxycyclohexanetetracarboxylic acid diimine, N-hydroxyphthalimide, imine, N-hydroxytetrachlorobenzenedicarboxylic acid imine, N-hydroxytetrabromobenzenediamine Ammonium oxalate, imine N-hydroxyhexahydrophthalate, ammonium 3-sulfohydroxyphthalate, ammonium imine 3-methoxycarboxy-N-hydroxybenzenediacetate, 3_ Methyl hydrazone-hydroxybenzoic acid sulfonium imine, 3-hydroxyhydroxy phthalic acid sulfonium imine, 4_nitro_N_hydroxybenzene difluorene owing & imine, 4-gas hydroxy phthalic acid fluorene Imine, 4_methoxy_N_ = phenyliminoimide, imine, cardiac dimethylamino_n_hydroxyphthalimide, imine, 4-carboxyhydroxyhexahydrophthalate, imine , * • methyl • hydroxyhexahydrophthalic acid imine, fluorenyl hytrate sulfonium imine, norbornene-2,3-dicarboxylic acid sulfonium imine, glacial hydroxytrimellitic acid sulfonium imine, n, n_ Dimeryl pyromellitic acid and the like. Among these, particularly preferred are: N-mercaptosuccinate, N-hydroxycis-butanedioic acid, imine, hydroxyhexahydrophthalic acid, imine, N, N , Dicyclohexyl tetrahexane diammonium diimide, N ·: phthalimide diimide, N, dimethyl tetraimide, imidyl tetrachlorophthalimide. Examples of the photocatalyst include zinc, titanium oxide, tungsten oxide, oxide, selenium oxide, thallium titanate, and potassium niobate. For this calculation, s ^ is in use. Among these, the photocatalyst t powder type has the highest catalyst effect and is recognized as food. , Agent, safe and waste scales W Fugugen Mouth type is better, and titanium dioxide is better. Titanium dioxide is preferably anatase and more than 30% by weight of titanium dioxide powder (50 weight is more preferred for cutting) is the best type titanium dioxide = heavy! ^ ^ Anatase type 16.200536488 titanium dioxide particles can be used to obtain high photocatalyst effect. The oxygen absorption accelerator may be simply mixed with the inorganic particles or may be adsorbed on the inorganic particles. Also, in the dispersion medium. —The particles are dispersed in fluorene and the like: It is important that the organic compound (A) is chemically adsorbed (chemically bonded) to the surface of the inorganic particles in the oxygen absorbent of the fluorene-type 1 only. Such chemical adsorption can be achieved by, for example, the method of the second embodiment. Hair moon oxygen absorbent can be used in powder form, so it can be easily and uniformly dispersed in resin. Therefore, a uniform oxygen-absorbing composition can be easily obtained. Moreover, in the oxygen absorbent of the present invention, since the organic compounds are adsorbed on the surface of the inorganic particles, compared with the conventional oxygen absorbents which do not chemically adsorb the organic compounds on the inorganic particles, can the following be obtained? Effect: By using chemical adsorption ', a higher oxygen absorption capacity can be obtained than in the case of physical adsorption. (2) Different from the case of physical adsorption, it is not easy to produce β-shaped clearing. (3) When kneaded with resin, it can prevent the swelling of organic compounds ⑷ air vents | '⑷ In order to suppress the free organic compounds when kneaded with resin For decomposition, it is better to wash the oxygen absorber before kneading, but it is different from the case of physical adsorption, 'the organic compound can be prevented from falling off the surface of the inorganic particles during cleaning;' the resin composition obtained Unlike the case of physical adsorption, the situation of dissolving in a solvent can be suppressed. (Embodiment 2) In Embodiment 2, the method of the present invention for producing an oxygen absorbent will be described. The oxygen absorbent produced by the method of the second embodiment is one of the oxygen absorbents of the present invention. Θ 17 -200536488 The manufacturing method of the present invention White #S is a process for chemically adsorbing unsaturated organic compounds onto inorganic particles. Unsaturated organic compounds and inorganic particles are applicable to the organic compounds (A) and inorganic particles of the fins and sun rays of the first embodiment. It is also used in the form of "inorganic particles". "I use the powder of the aggregate of non-mechanical particles below, in the case of inorganic particles having a radical on the surface and organically presenting a functional group capable of reacting with a hydroxyl group " J Zhuo σ, the spear king, two examples Explanation: In the i-th method, first, a mixture of an organic compound (⑷) with inorganic particles and an organic agent (process la) is prepared. As long as the organic solvent allows the organic compound and the inorganic particles to be uniformly separated, the knife is cut or the solution is broken. Both can be used. Examples of such an organic solvent include toluene, xylene, diisoamidine, tetrahydrofuran (THF), dichloromethane, chloroform, methyl acetate, ethyl acetate, and the like. Its hexane and Toluene is preferred because it can be removed by azeotropic dehydration of the organic compound hydrazone and the water produced on the surface of the inorganic particles with hydrazone-based materials. Then, the organic solvent is removed from the above mixture. The method for removing the agent is not particularly limited, and for example, at least one of a method such as sacrifice, reduction of U, and heating can be used. The organic compound ⑷ can be selected by selecting the type of the inorganic particles and the organic solvent. A part of the organic compound (A) is chemically adsorbed on the inorganic particles by the process h. Hug: In the second method, a mixture containing the organic compound ⑷ and inorganic particles is first prepared (process lb). The organic compound (A) is chemically adsorbed on the inorganic particles by heating the compound. In the method of the present invention, in the process 2a and the process 2b, the product produced by the reaction of the official group 18 200536488 energy group and the base group is generated. It is particularly preferable to remove water. By removing the organic compound (A), the reaction between the functional group of the organic compound (A) and the surface of the inorganic particles = hydroxyl groups can increase the ratio of the organic compound (A) that is chemisorbed. 7 This is in the process 2a In the case of heating in process 2b, it is better to perform the process in a ^ = tender environment atmosphere (such as under a nitrogen atmosphere such as a nitrogen stream or under reduced pressure). Similarly, 'process 2a and process holes, containing The process of heating the mixture at a temperature above the boiling point of water is preferred. It is also preferable to add 埶 at a temperature below the decomposition temperature of the organic compound ⑷. When water is removed at the process port, an organic solvent can be separated from water. Removal ^^ Simultaneous removal. For example, 'the organic solvent can be removed, and then the mixture with the organic solvent removed at a temperature above the boiling point of water can be subjected to chemical adsorption (chemical bonding) by the above-mentioned process. Inorganic particles of organic compounds (A). Fi &, the oxygen absorption promoter described in M yoke 1 can also be used in the above, +, +, t, reverse /, organic compounds (A)- It can also be adsorbed on the inorganic particles after the above process. In addition, ... make the inorganic particles and the oxygen absorbent dry-kneaded in the above-mentioned equipment & The inorganic particles and the oxygen absorbent y obtained in step I are dispersed in a dispersion medium such as a resin. In this way, the oxygen absorbent described in Embodiment 1 can be obtained. In addition, the irritations of Implementation Forms 1 and 2 can be used alone or dispersed in resin. (Embodiment 3) Among Embodiment 3 and Embodiment 3, the oxygen-absorbing composition of the present invention will be described. A recoverable composition containing a resin (polymer compound), the oxygen absorbent described in 19 «200536488 and the oxygen absorbent 2 dispersed in the resin. The amount of the oxygen absorbent in the embodiment or the application form is not particularly limited, and can be adjusted according to the purpose. A A] on the composition of Tongdandan X as an example, the amount of oxygen absorbent is 100 parts by weight to the resin and 树脂 is, for example, 1 part by weight to 30 parts by weight, and is set to 1 part by weight to 1G by weight The range of servings is better. The resin can be selected according to the use of the composition. As a representative resin,

: List of examples " Synthetic resins such as vinyl alcohol resins, polyamide resins, and polypropylene nitrile resins. Since these resins have high oxygen barrier properties, it is possible to obtain a composition suitable as a packaging material for articles which may be deteriorated by oxygen. As other resins other than the above, polyolefins such as polyethylene, polypropylene, poly4-methyl-pentene, and poly-1-τene can also be used. Further, an ethylene-propylene copolymer, polyvinylidene chloride, polyvinyl chloride, polystyrene, polycarbonate, or polyacrylate can also be used. Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate can also be used. A copolymer of ethylene or propylene with other monomers may also be used. Examples of other monomers include α-olefins such as butene, isobutylene, 4-methylpentene, ^ hexene, and 1-octene; itaconic acid, fluoracrylic acid, acrylic acid, and cis-butene Unsaturated carboxylic acids such as oxalic anhydride, their salts, their partial or complete esters, their nitriles, their amines, and their anhydrides; vinyl formate, vinyl acetate, propylene ethyl acetate, ethyl butyrate , Ethyl octanoate, vinyl dodecanoate, vinyl stearate, vinyl arachidate, etc .; vinyl carboxylates such as ethylene trioxosilane; unsaturated sulfonic acid or its Salt; 20 200536488 oligoceryl alcohols, ethylene D than ketones. τ Ethyl alcohol resin can be used for homopolymerization of vinyl esters or copolymers of vinyl esters and / or other monomers (especially copolymers of vinyl esters and ethylene) with alkali catalysts for I ^ β ^ , t and serve. Examples of vinyl esters include vinyl acetate

Vinegar, or other fatty acid vinyl esters (vinyl propionate, vinyl trimethyl acetate, etc.).

The degree of saponification of the vinyl ester component of the water vinyl alcohol resin is preferably 90 mol% or more (for example, 95 mol% or more). By setting the degree of saponification to 90 mol% or more, Y can suppress gas barrier properties under high humidity. In addition, two or more of the same polyvinyl alcohol-based resins may be saponified. The degree of saponification of the polyvinyl alcohol resin can be determined by a nuclear magnetic resonance (NMR) method. . The preferred melt flow rate (MFR) of polyvinyl alcohol resin (measured in accordance with JIS K7210 under a load of 2160 =, 2160g) is preferably divided into 0.5 to 50 g / l, divided by 0.5 to 50 g / l0. Good, especially Yibu, 10 points is better. : When the melt flow rate deviates from the range of 0.1 g to 100 g / 10 minutes, the workability at the time of performing the blow molding is often deteriorated. "In the pinene alcohol-based resins, in particular, ethylene-vinyl alcohol copolymers (hereinafter, also referred to as EVOH) have the characteristics of being melt-meltable and forming and having good gas barrier properties under high humidity. The structure of EV () H The proportion of the ethylene unit in the unit is preferably, for example, 5 to 60 mole% (in the range of 10 to 55 mole%. By suppressing the ratio of the ethylene unit M to 5 mole% or more, the ratio can be suppressed. Decrease in gas barrier properties under south humidity. Also, by setting the proportion of ethylene units to 60 mol% or less, high gas barrier properties can be obtained. The proportion of ethylene units can be determined by nuclear magnetic resonance (NMR) method. It can also be used as a mixture of at least 2 kinds of ethylene 21 * 200536488 olefin units with different ratios.

As long as the effects of the present invention can be obtained, EVOH may also contain other monomers as a kappa mouth knife. Examples of such monomers include, for example, propylene, butylene, isobutylene, 4-methylpentene, α-olefins such as "hex, Greek, 1-octene, etc .; itaconic acid, methacrylic acid Unsaturated acid and its derivatives such as acrylic acid, acrylic acid, cis-T-dicarboxylic acid needles, etc .; Ethylene trimethoxy stone ethene ethylene triethoxy stone cyanide, ethylene tri (3_methoxy_ethoxy) stone XI r Methacryloxypropyltrimethoxysilane and other ethylene silane-based compounds such as unsaturated stone yin, acids or their salts; alkyl mercaptans; ethylene pyrrolidone. VOH 3 has ethylene as a copolymerization component. In the case of a silane-based compound / 002. 2 mol%, 'co-extrusion molding or co-injection can be used to form a homogeneous molded product when molding is performed. As an ethylene sintered compound, it is easier The best ones can use ethylene trimethoxyl, ethylene triethylene, or boron compounds in EVOH. This makes it easy to manufacture in the case of forming by co- ^ L forming 幵 y or co-injection molding. Shaped product of homogeneous shell. Examples of the boron compound include boric acids (for example, ortho-I acid) , Borate, borate, boron hydride. Also, EVOH: Alkali metal salts (for example, sodium acetate, potassium acetate, sodium phosphate). By this, = high-level indirect contact and compatibility In addition, it is also possible to add sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, phosphorus = dipotassium phosphate to the paste. This can improve the thermal stability of EV0H. Adding stone δ EVOH, which is an additive such as alkali metal salt and phosphorus compound, can be produced by a known method. 22 • 200536488 ♦ The type of the resin is not particularly limited, and examples thereof include polyamine (nylon-6), polyundacan Aliphatic polymerization of amines (nylon-11), polylauryl acetic acid (nylon) to hexamethylenediamine diamine (nylon-6,6), polyhexamethylene decanediamine n (edge 6,12), etc. Homopolymer of fermented amines; caprolactam / lauryl «copolymer (nylon_6 / 12), caprolactam / aminodeca-acid copolymer (ni-6 / U), caprolactam / ω · Aminononanoic acid copolymer (nylon_6 / 9), caprolactone into the moon: / Liujialou hexamethylene diamine copolymer (nylon_6 / 6,6), caprolactam / hexamethylene Perylene diamine copolymer / hexamethylene sebacic acid Copolymers (nylon_ 6 / 6'6 / 6,1〇) and other aliphatic polyamidoamine copolymers; polym-xylylene adipazolium (MX-Nibon), hexamethylene terephthalate / Hexamethylene isoxylylene fefe copolymer (nylon_6T / 6I), etc. Aromatic polyamines, etc. These polyisocyanates can be used alone or in combination of two or more Among them, polyhexamide (nylon-6) and polyhexamethylene adipamide (nylon · 66) are particularly preferable. '' As the polyacrylonitrile resin, acrylonitrile may be mentioned A copolymer of a dilute monomer and acrylonitrile. As long as the composition of the third aspect of the present invention can obtain the effect of the present invention, it may also contain an oxidation inhibitor, a plasticizer, a heat stabilizer (melt stabilizer), Photoinitiator, deodorant, ultraviolet absorber, antistatic agent, lubricant, colorant, filler, pigment, dye, processing aid, fire retardant, anti-fog and desiccant . Examples of the deodorant include zinc compounds, aluminum compounds, compounds, iron (II) compounds, and organic acids. The composition of the present invention can be formed by mixing components of an oxygen absorbent (that is, an inorganic particle having an organic compound adsorbed thereon and an oxygen absorption promoter), a resin, and an additive. The method of mixing the ingredients and the order of mixing are not particularly limited. For example, all ingredients can be mixed simultaneously. It is also possible to mix the oxygen absorbent with the additive and then the resin, or the oxygen absorber and the resin and then the additive. Alternatively, the additives may be mixed with a resin and then mixed with an oxygen absorbent. In these cases, the inorganic particles to which the organic compound is adsorbed and the oxygen absorption promoter may be mixed in advance, or may be mixed with other components separately at other stages. Specific methods of mixing include, for example, a method of dissolving each component in a heart preparation to prepare a plurality of solutions, mixing these solutions, and then evaporating the solvent; a method of adding other components to the molten resin and kneading the mixture. . The kneading can be performed, for example, with a ribbon blender, a high speed mixer, a kneader, a mixing roller, an extruder, or an in-mixer. The composition of the present invention can be formed into various forms, such as a film, a sheet, a container, and the like. These shaped articles' τ are used as packaging materials or deoxidizers. In addition, the composition of the present invention may be formed into pellets and then formed, or the components of the composition may be dry-mixed and then directly formed. (Embodiment 4) In Embodiment 4, the packaging material of this invention is demonstrated. The packaging material of the present invention contains a portion composed of the oxygen-absorbing composition described in the third embodiment. This portion 'may have various shapes, such as a layered, bottle-shaped, or cap-shaped shape. This packaging material can be formed by processing the group 24 200536488 of Embodiment 3 into various shapes. The composition of Form 3 can also be applied to the shape of a film, a sheet, or an official body by Mu .. It can also be shaped by injection molding. Also, you can also use Zhong Yun # // / for the valley. Mouth is medium ... Shaped into a hollow container such as a bottle. Operation :: 2 can be used for extrusion hollow molding and injection hollow molding. " The packaging material of the wide shape sad 4 'may be a layer composed of the composition of the embodiment 3 (hereinafter, also referred to as a layer (A to, a layer composed of materials (herein, also referred to as "the two" and other The layered product can be further improved into a layered product. By making properties such as mechanical properties, water vapor insulation, gas insulation, etc., the material and number of layers (B) can be selected. The structure of the laminated material required for the clothing material is not particularly limited. Between the layer ⑷ and the layer ⑼, an accessor resin (hereinafter, also referred to as (〇) ) ° The structure of the laminates includes, for example, layer ⑷ / layer (B), / (^ layer ⑷ / layer ⑻), layer (A) / layer (c) / layer (B), layer (β) / layer ( c) / layer ⑻, layer ⑻ / layer ㈧ / layer ⑻ / layer ㈧ / layer ⑻, and layer (b) / (j ⑷ / layer ⑹ / layer ⑻ / layer (c) / layer ㈧ / layer (c) / Layer ⑻. In the case of plural layers (B) of i, 1 thing has the thickness of each layer, and it can be the same or different. The layer of the thing ..., the limit of the temple. The thickness of the set layer (A) is relatively In the range of 2 to 20% of the total thickness, Yu Cheng The layer (B) can be formed of, for example, a thermoplastic resin or a metal. Examples of the family that can be used for the layer () include steel or aluminum. The resin that can be used for the layer (B) is not particularly limited, Ketian / For example, the resin exemplified for layer (A). For example, 25 * 200536488 Polyethylene such as polyethylene, polypropylene, poly · 4-methyl-pentene, poly-butene, and the like can be used. Also, an ethylene-propylene copolymer, polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylic acid, and ethylene-vinyl alcohol copolymer can be used. Also, polyparaphenylene terephthalate can be used. Polyesters of polyethylene formate, polybutylene terephthalate, polyethylene naphthalate, etc. In addition, polyhexamethyleneamine, hexamethylene adipamide diamine, polym-xylene Polyamines such as hexamethylene diamine. Copolymers of ethylene or propylene with other monomers can also be used. Examples of other monomers include: butene, isobutene, and 4-methylpentene , 1-hexane, 1-octane, etc .; itaconic acid, methacrylic acid, acrylic acid, cis-Tene, etc. Saturated m acid, its salt, its mouth I5 knife or 70 kings, its nitrile, its amidine, its anhydride; vinyl formate, ethyl acetate seller, vinyl propionate, vinyl butyrate, caprylic acid Vinyl carboxylates, such as vinyl esters, vinyl dodecanoate, vinyl stearate, vinyl arachidate, etc .; Ethylene diene-based compounds such as ethylene trimethoxyethene; unsaturated continuous acids or their salts; silk Thiols; second class money leftovers. Layers (A) and (B) can also be unstretched, uniaxially stretched, biaxially stretched, or calendered. Can be used for layers The adhesive resin of (C) is not particularly limited as long as it can be used for bonding between layers. For example, polyurethane- 0, poly-I or a two-liquid type hardening adhesive can be used. Unsaturated acetic acid or its acid needles (cis-succinic acid needles, etc.) are copolymerized or advanced with dilute hydrocarbon polymers: graft-modified ones (polyacrylic resins modified by several acids). In the case of layer ⑷ and layer ⑻ "in the case of polyalkylene resins", the south adhesion can be achieved by using a polyalkylene resin modified by a slow acid. As "modified polyenes", for example 26 • 200536488: · Polyethylene, polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylate copolymer are polymers obtained by carboxylic acid modification. A deodorant may be added to at least one of the layers constituting the laminate. As the deodorant, for example, the deodorant exemplified in Embodiment 3 can be used. There is no particular limitation on the manufacturing method of the laminate of the yoke-shaped evil 4, and it can be formed by a known method, for example. For example, methods such as extrusion lamination & dry lamination method 'solvent flow molding method, co-injection molding method, co-extrusion waste molding method, and the like can be used. As the co-extrusion molding method, a co-extrusion lamination molding method, a co-extrusion sheet forming method, a co-extrusion expansion molding method, and a co-extrusion blow molding method can be applied. : When the packaging material of this hair month is a container with a multi-layer structure, the layer composed of the grouped filaments of Embodiment 3 is arranged close to the container: the inner layer (for example, the innermost layer) can quickly absorb the container Oxygen inside. Among the multi-layered containers, the present invention is preferably used in a multi-layered multilayer container. The thickness of the entire layer is a multi-layer container under the core U, which is a container 4 'composed of a multi-layer film ′ and a relatively thin multi-layer structure. It is soft, easy to manufacture, and has a gas-separating effect of ::::, which is very useful for its high sensitivity to oxygen and easy deterioration. By forming the thickness of the entire layer as follows, high flexibility can be obtained. By making #m n m + and 7 as the predecessor, 250 ≤ or less, especially 200 core or less, and considering the mechanical strength, the thickness of the whole layer is equal to 2 = softness. It is better to go above, and 27 • 200536488 is better than 20 # m. In order to make such a multi-layered container a dense surface layer, at least one of the resins that can be used can be exemplified by: poly, B :, and the like. As such contents, olefins such as dipropylene are processed into bags. By going to multiple containers. , Xi s / # film and then heat-sealed, you can get + n = surface ’multi-layer volume cry made by ㈣ blow molding method, usually used in the form of bottles, etc ...

Here, we can see that the ancient surname is clean, productive, and has excellent gas barrier properties ... and has a sustained oxygen absorption effect. The packaging of deteriorated products is extremely useful. Nowadays, the container of the ampoule-shaped container is still standing β + + 赔, and the degree of the mouth knife is generally in the range of 100 to 2000 P. It can be selected according to the application. In this case, the thickness of the layer composed of the composition of the second embodiment can be set in a range of 2 to 2 called @, for example. The packaging material of the present invention may also be a padding material for a container, and a padding material for the container. In this case, a cushion material can be formed from the composition of the third embodiment. Hereinafter, the present invention will be described in more detail with reference to the following examples. [Example 1] Fang; Example 1 shows the evaluation results of the oxygen absorption capacity of the oxygen absorbent of the present invention. In the production of the following samples, Kyowado-500 manufactured by Kyowa Chemical Industry Co., Ltd. was used as the powder of the hydrotalcite. (Sample 1) 4.00 g of linolenic acid was dissolved in deaerated hexane i500 nL, and 16.0 g of hydrotalcite powder was added, and the bath temperature was 80 ° C under a nitrogen atmosphere. 〇, into 28 • 200536488 remainder division. Then, in a nitrogen atmosphere, the bath temperature was 11 ℃, and the powder was heated for 3 hours while mixing the powder ink. Then, the powder was dried under reduced pressure to obtain a powder of hydrotalcite chemically adsorbed with linolenic acid (Sample 1). (Sample 2) 9.78 g of the oxygen absorbent of the above-mentioned sample 1 was added with degassed hexane (100 mL) and stirred at room temperature for 2 hours, followed by suction filtration. In this way, a powder of sample 1 which was washed with hexane (sample 2) was obtained. (Sample 3) 2.00 g of linolenic acid was dissolved in 100 mL of hexane, and 8.00 g of hydrotalcite powder was added thereto, followed by stirring at room temperature for 2 hours. Then, the mixed liquid was subjected to suction filtration, and the obtained powder was dried under reduced pressure. In this way, a powder of hydrotalcite with linolenic acid adsorbed (Sample 3) was obtained. (Comparative Sample 1) 2.00 g of linolenic acid was dissolved in 100 mL of hexane, activated carbon (manufactured by Kuratian Chemical Co., Ltd., BP_2) 800 g was added, and the mixture was stirred at room temperature for 2 hours. The liquid after the dagger was suction-filtered, and the obtained powder was dried under reduced pressure. In this way, a powder of hydrotalcite physically adsorbed with linolenic acid was obtained (production and evaluation of the lice absorbent of comparative sample 1). About 10 times the weight of the four types of powders and the hydrotalcite cobalt of comparative sample 2 were added. The degassed hexane is added, and the naphthoic acid f is added (the amount is equal to the amount called ㈣) and mixed. Since the mixed liquid was cut squarely, the solvent was removed 'and the powder was dried. For the 4 types of oxygen absorbers that have been previously transmitted, 0.5§ to 23 respectively. . , 29 • 200536488 50% RH (relative humidity) is put into a bottle with a capacity of 260cc and the bottle is sealed. This bottle was stored at 23 C, and the oxygen concentration in the bottle after a certain period of time was measured to determine the oxygen absorption rate of the oxygen absorbent. The evaluation results are shown in Fig. 10. The vertical axis of Fig. 1 represents the oxygen absorption amount per 1 g of the oxygen absorbent. As shown in FIG. 1, Samples 1 to 3 showed higher oxygen absorption capacity than Comparative Sample 1 in which linolenic acid was physically adsorbed on activated carbon. However, sample 3 has a lower oxygen absorption capacity than samples 1 and 2. The sample 2 obtained by washing the heat-treated sample 1 did not significantly reduce the characteristics compared to the sample 丨. For the reason that the decrease in the oxygen absorption capacity of sample 2 caused by washing is small, I think that it is because a large amount of linolenic acid is chemically adsorbed to the hydrotalcite of the sample. On the other hand, Comparative Sample 2 showed almost no absorption of oxygen. Although the reasons for the differences in the oxygen absorption capacity and the infrared absorption spectrum of samples 1 to 3 have not yet been elucidated, I believe that the adsorption amount and adsorption state of linolenic acid are different due to different processing methods. [Example 2] In Example 2 of the present invention, another example of producing and evaluating the oxygen absorbent of the present invention will be described. (Sample 4) First, 2,000 g of linolenic acid in a sintered solution of cobalt naphthalate was added to 2000 g of linolenic acid under a nitrogen atmosphere (concentration of naphthalate was 0.8 mg / mL in terms of c), and stirred for 4 to No. 1 Luoye. On the other hand, 8 mL 'of hydrotalcite powder was added to OOmL of hexane] and stirred to obtain a solution. Then, under a nitrogen atmosphere ’ The solution was dropped into the second solution and mixed. 30 • 200536488 The obtained liquid was heated at a bath temperature of 80 t, the hexane was distilled off, and then heated in an oil bath at 120 ° C. for 2 hours and allowed to cool. The obtained powder was dried under reduced pressure to obtain a powder of hydrotalcite chemically adsorbed with linolenic acid (Sample 4). 0.5 g of the oxygen absorbent thus obtained was put into a 260 cc bottle in a room at 23 ° C 50% RH, and the bottle was sealed. Then, by storing the bottle at 23 ° C ', the oxygen concentration in the bottle after a certain period of time was measured, and the oxygen absorption rate of the oxygen absorbent was determined. The evaluation results are shown in Fig. 3. As shown in FIG. 3, sample 4 showed an oxygen absorption capacity equal to or more than that of sample 3. [Example 3] In Example 3, another example of producing and evaluating the oxygen absorbent of the present invention will be described. (Sample 5) 4.00 g of linolenic acid was dissolved in 150 mL of degassed hexane, and 160 g of a powder of synthetic mica-based somacif ME (manufactured by Popular Science Co., Ltd.) was added. Under a nitrogen atmosphere, Hexane was distilled off at a bath temperature of 80 ° C. Then, the powder obtained by distilling away the own house was heated under a nitrogen atmosphere at a bath temperature of 11 ° C for 3 hours with stirring. Then, the powder was dried under reduced pressure to obtain a chemically adsorbed linolenic acid. Massif ME powder (Sample 5). (Production and Evaluation of Oxygen Absorbent) Add about 5 to Sample 5! Degassed hexane by weight, and then add naphthalene-cobalt (to convert to 800 ppm cobalt) From the mixed liquid, the solvent was distilled off under reduced pressure, and the obtained powder was dried. 0.5 g of the oxygen absorbent thus obtained was taken into a 260cc bottle in a 23 ° C, 50% RH room. The bottle was sealed. The bottle was stored in 231, and the oxygen concentration in the bottle after a certain period of 31.200536488 was measured to determine the oxygen absorption rate of the oxygen absorbent. The evaluation results are shown in Figure 4. [Example 4] In Example 4, other examples of making and evaluating the oxygen absorbent of the present invention will be described. (Sample 6)

Dissolve 4.00 g of ethyl eicosapentaenoate in 15 mL of degassed hexane, add hydrotalcite powder 16.0§, and distill off the hexane under a nitrogen atmosphere at a bath temperature of 80 ° C. . Then, the powder obtained by distilling off hexane was heated under a nitrogen ring atmosphere at a bath temperature of 110 ° C for 3 hours with stirring. Then, the powder was dried under reduced pressure to obtain a powder of hydrotalcite chemically adsorbed on eicosapentaenoic acid (sample 6). (Production and Evaluation of Oxygen Absorbent) About 10 times the weight of degassed hexane was added to Sample 6 and then cobalt naphthalate (the amount converted to cobalt was 800 ppm) was mixed. The solvent was distilled off from the mixed liquid under reduced pressure, and the obtained powder was dried. 0.5g of the oxygen absorbent thus obtained was placed in a room at 23 ° C and 50% RH, and was placed in the center of a 2660cc capacity to seal the bottle. Force 231 kept this bottle, measured the oxygen concentration in the bottle after a certain period of time, and determined the oxygen absorption rate of the oxygen absorbent. The evaluation results are shown in Fig. 5. [Embodiment 5] In the present embodiment, an example of producing a laminated film composed of an oxygen-absorbing composition will be described. (Sample 7) 32.200536488 First, the dagger and the attached flaxseed hydrotalcite powder (Sample 1) described in Example 1 were prepared. To the sample, add 10 times the weight of gently degassed hexane, and then add cobalt naphthalate (to make the conversion, the amount of dioxin, palladium is 800 ppm) and mix a. From the mixed liquid, the solvent was distilled off under reduced pressure, and the obtained powder was dried to obtain an oxygen absorbent. ㈣ 'The weight of the thus obtained agent H) was mixed with 90 parts by weight, and the mixture was kneaded for 5 minutes. .Kneading is performed in a nitrogen atmosphere. J After heating, it will be obtained in this way.

The mixture was molded with a compression molding machine to a thickness of about 100 #m to form a compression film (sample 7). & Put 0.5 g of sample 7 in a 23 ° C 50% RH room and put it in a bottle with a capacity of "a" to seal the bottle. Store this bottle at 2rc and check the oxygen concentration in the bottle after a certain period of time. The measurement is performed to determine the oxygen absorption rate of the oxygen absorber. The evaluation result is shown in Fig. 6. The above is an example of the embodiment of the present invention. However, the present invention is not limited to the above embodiment and can be applied. In other embodiments based on the technical idea of the present invention. (Industrial Applicability) The present invention is applicable to an oxygen absorbent, an oxygen absorbent composition, and a packaging material using the same. It is particularly suitable for use with oxygen. Packaging materials for items that have a significant impact on deterioration (for example, food, medicine, medical equipment, machinery parts, clothing, etc.) [Simplified illustration of the drawing] Figure 1 shows the oxygen absorption capacity of the oxygen absorbent of the present invention and the comparative example. An example of a graph. 33.200536488 FIG. 2 is a graph showing an example of the infrared absorption spectrum of the oxygen absorbent of the present invention. FIG. 3 is a graph showing an example of the oxygen absorption capacity of the oxygen absorbent of the present invention. 4 is a graph showing another example of the oxygen absorption capacity of the oxygen absorbent of the present invention. FIG. 5 is a graph showing another example of the oxygen absorption capacity of the oxygen absorbent of the present invention. A graph showing an example of the oxygen absorption capacity of other examples of the laminated film composed of the composition. [Description of the main component symbols]

34

Claims (1)

.200536488 10. Scope of patent application: Inorganic particles, chemical conversion, and oxygen absorption promotion • The oxygen absorber is characterized by containing: "organic compounds" adsorbed on the inorganic particles. Price absorbent, which includes at least 1 # + alkane silane derivatives and amine conformers in the organic group. One of the organic compound formers vh, δ, and inorganic particles reacts: Γ applies for an oxygen absorbent according to item 1, wherein the organic compound is an unsaturated organic compound. 4. As the oxygen absorbent according to item 3 of the application, the organic compound contains the following formula (1 ): —CH2 \, c = c,… ⑴ R〆 \ ch2— [wherein R1 and R2 are each independently selected from hydrogen atom, alkyl group, substituted alkyl group, aryl group, substituted group Aryl, aralkyl, substituted aralkyl, -COOR3, -OCOR3, cyano, and halogen atoms; are selected from the group consisting of alkyl, substituted alkyl, aryl, and Substituted aryl, aralkyl, substituted One of the bases]. 5 · The oxygen absorbent according to item 3 of the patent application scope, wherein the organic compound contains the structure represented by the following formula (2); R \ .R5… ⑵ —CH ^ XCH2— [Formula In the formula, R4 and R5 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl group having a substituent 35 200536488, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, -COOR3, _ 〇C〇R3, i type of cyano and halogen atom; r3 is selected from the group consisting of alkyl, substituted alkyl'aryl, substituted aryl, aromatic alkyl, substituted aromatic alkyl One of them]. 6. If the oxygen absorbent according to item 3 of the patent application, wherein the organic compound has an unsaturated alicyclic structure. 7. If the oxygen absorbent according to item 丨 of the patent application, wherein The amount of the chemical formula of the organic compound is 3,000 or less. 8. For example, the oxygen absorbent of the item i in the patent application range, wherein the inorganic particles are composed of a layered inorganic compound. The oxygen absorbent of the item, wherein the inorganic particles have a hydroxyl group on the surface. 10. If the ninth scope of the patent application, the organic particles are particles of hydrotalcite. 11 • If the jth absorption promoter in the scope of the patent application is at least one selected from transition metal salts. The oxygen absorbent according to the item, wherein the oxygen absorbent without the item, wherein the manufacturing method of 1 absorbs plutonium in the oxygen, the free radical generator and the photocatalyst, is used for manufacturing the product containing helmet particles and an oxygen absorption promoter. Oxygen absorber; characterized in that: chemical adsorption of organic compounds on the inorganic 13 · as in the scope of application for patent No. 12 / where the organic compound is not ... the right milk absorbent manufacturing method Compounds. 14. As in β ^^ of the scope of application for patent, wherein the inorganic particle has a method for producing a milk absorbent on the surface, the square and the surface have warp groups, and the organic compound has a functional group that can react with a hydroxyl group. κ The method for manufacturing an oxygen absorbent according to item 14 of the application, wherein the organic compound is at least one selected from the group consisting of carboxylic acid, ester, aldehyde, alkoxysilane, and amine. Fan Hesheng 1 6. The manufacturer of the oxygen absorbent of item 14 in the scope of Shenyan Patent includes the following processes: '' Wei Wei contains a mixture of the organic compound and the inorganic particles; and Valley (11) from the mixture The organic solvent was removed. I7. The method for manufacturing an oxygen absorbent according to item 16 of the scope of patent application, which is a process of heating the mixture at a temperature above the boiling point of water after the process of (ii). / JnL 18 · The manufacturing method of the oxygen absorbent according to item 14 of the patent, which includes the following processes: ⑴ preparing a mixture containing the organic compound and the inorganic particle and ⑴) heating the mixture to make the organic Compound chemical absorption particles. … The manufacturing method of the oxygen absorbent as set forth in the patent claim No. 18,-The clothing of Λ (11) includes a process of heating the mixture at a temperature above the boiling point of water. For example, the scope of the patent application: 17J member of the oxygen absorber manufacturing method, /, this & system is heated in a nitrogen atmosphere or under reduced pressure. 21 · The method for manufacturing an oxygen absorbent according to item 13 of the scope of patent application, 37 200536488, wherein 'the inorganic particle is composed of a layered inorganic compound. 22 ·: An oxygen absorbent characterized by being manufactured by a method for manufacturing an oxygen absorbent according to the scope of patent. 23. A milk absorbent composition, which contains a resin and a milk absorbent dispersed in the tree, which is characterized in that the oxygen absorbent is an oxygen absorbent of the first patent in the dry patent. 24. The oxygen-absorbing composition according to claim 23, wherein the resin contains an ethylene-vinyl alcohol copolymer. —25. — A packaging material characterized in that it contains a part composed of an oxygen-absorbing composition in the scope of patent application No. 23. XI. Schematic ... 38