CN101346434A - Oxygen-absorbing resin compositions, oxygen-absorbing film, and oxygen-absorbing multilayer structure - Google Patents

Abstract

The invention provides an oxygen absorption resin composition with the advantages of excellent oxygen absorption function, less metal content and less smell while absorbing oxygen under the room temperature. The oxygen absorption resin composition comprises an oxygen absorption film of the oxygen absorption resin composition and an oxygen absorption multiple layer structure containing the oxygen absorption resin composition. One oxygen absorption resin composition comprises a resin (A1) having a C-H bond with dissociation energy below 3.70eV and a resin (B1) having a C-H bond with dissociation energy between 3.70eV and 4.20eV. The other oxygen absorption resin composition comprises a resin (A2) having a C-H bond capable of generating the carbon free radical whose reaction energy with oxygen below 10.0cal/mol and a resin (B2) having a C-H bond capable of generating the carbon free radical whose reaction energy with oxygen beteeen 10.0cal/mol and 22.0cal/mol.

Description

Oxygen-absorbing resin composition, oxygen-absorbing film and oxygen-absorbing multilayer structure

Technical field

The present invention relates to the oxygen uptake excellence oxygen-absorbing resin composition, comprise the oxygen-absorbing film of this oxygen-absorbing resin composition and comprise the oxygen-absorbing multilayer structure of the oxygen uptake layer that comprises this oxygen-absorbing resin composition.More specifically, relate to the oxygen-absorbing resin composition that stink is few after oxygen absorbed and oxygen absorption rate excellence under the room temperature, the oxygen uptake, the oxygen-absorbing multilayer structure that comprises the oxygen-absorbing film of this oxygen-absorbing resin composition and comprise the oxygen uptake layer that comprises this oxygen-absorbing resin composition.

Background technology

Food, beverage, medicine etc. are because of quality badness takes place in oxygen, therefore need preserve under the few condition of anaerobic or oxygen.

Therefore, also carry out in the container of preserved food products, beverage, medicine etc. or packing and fill nitrogen, but have following problem: for example, cost increases during manufacturing; In case break a seal then air flow into from the outside, can't prevent later quality badness.So having carried out various absorption of residual, someone stays container or the interior oxygen of packing, in system, to remove the research of deoxidation.

In the past, as the method for oxygen of removing in container or the packing, extensively adopted configuration discrete inside to be equipped with to be the method for pouch of the oxygen absorbent of main component with the iron powder.Though but this method cost is low, oxygen absorption rate is also fast, when using metal detector or be with packing to have disadvantage when being directly used in microwave oven in order to detect foreign matter.

Therefore, aspect resin container or wrapping material, make container or wrapping material itself have the research of oxygen uptake.

For example, people's motion has been arranged and used the oxygen absorbent (patent documentation 1) of transition metal salts such as the new cobalt decanoate comprise poly-(α-Pai Xi), poly-(beta-pinene), poly-(limonene) polyterpene of etc.ing and to bring into play the oxygen uptake catalyst action, cobalt oleate.

In addition, people's motion having been arranged uses and to comprise polyisoprene, 1, the oxygen absorbent of 2-polyhutadiene equiconjugate diene polymer and transition metal salt (patent documentation 2).

Somebody's motion use and to comprise the multipolymer of ethene and cyclopentenes and the oxygen absorbent of transition metal salt (patent documentation 3).

But there is following problem in disclosed each composition of above-mentioned patent documentation: the oxygen uptake performance is insufficient, and the residual stink of thinking the uniqueness that produced by the by product of oxygen catching reaction in the packaging vessel.In addition, above-mentioned each composition all contains transition metal, therefore along with the polymer deterioratoin that carries out of oxygen uptake reaction, the physical strength that wrapping material might occur significantly reduces, the problem of painted even transition metal salt stripping, and above-mentioned composition is difficult to use in some purposes.

Patent documentation 1: Japanese Unexamined Patent Application Publication 2001-507045 communique (the international brochure that discloses No. 98/06779)

Patent documentation 2: TOHKEMY 2003-71992 communique

Patent documentation 3: Japanese Unexamined Patent Application Publication 2003-504042 communique (the international brochure that discloses No. 01/013521)

Summary of the invention

Invent problem to be solved

Therefore, the object of the present invention is to provide oxygen absorbed and oxygen absorption rate excellence under the room temperature, the oxygen-absorbing resin composition that stink is few when need not to contain metal, oxygen uptake, the oxygen-absorbing multilayer structure that comprises the oxygen-absorbing film of this oxygen-absorbing resin composition and comprise the oxygen uptake layer that comprises this oxygen-absorbing resin composition.

The inventor etc. further investigate in order to solve above-mentioned problem, even found that not adding transition metal salt with cyclized product of conjugated diene polymer as the oxygen absorbent of effective constituent also shows high oxygen uptake as catalyzer, and still keep high mechanical strength after the oxygen uptake, thus motion with the oxygen absorbent (TOHKEMY 2005-186060 communique) of cyclized product of conjugated diene polymer as effective constituent.

The inventor etc. study oxygen absorbent, discovery by will constituting oxygen absorbent cyclized product of conjugated diene polymer and have the resin combination of ad hoc structure, can further improve oxygen uptake (oxygen absorbed and oxygen absorption rate), stink after the oxygen uptake also further reduces, improve the physical strength of resin combination, expect containing respectively the combination of two kinds of resins of C-H of the specific dissociation energy of tool and the combination that can produce two kinds of resins of free radical that can be in specified range with the reaction of oxygen respectively based on this discovery, go forward side by side one the step study, thereby finished the present invention.

Solve the method for problem

According to the present invention, first oxygen-absorbing resin composition is provided, said composition comprises that to have bond dissociation energy be the resin (A1) of the following c h bond of 3.70eV and have bond dissociation energy greater than 3.70eV and be the resin (B1) of the c h bond below the 4.20eV.

In first oxygen-absorbing resin composition of the present invention, the resin (A1) that has bond dissociation energy and be a following c h bond of 3.70eV with have bond dissociation energy and be preferably 3/97～50/50 in weight ratio greater than 3.70eV and for the ratio of the resin (B1) of the c h bond below the 4.20eV.

In first oxygen-absorbing resin composition of the present invention, the number that has bond dissociation energy and be bond dissociation energy in the resin (A1) of the following c h bond of 3.70eV and be the following c h bond of 3.70eV is preferably in each repeating unit that constitutes resin (A1) to be had at least more than one.

In first oxygen-absorbing resin composition of the present invention, the resin (A1) that has bond dissociation energy and be the following c h bond of 3.70eV is preferably cyclized product of conjugated diene polymer.

In first oxygen-absorbing resin composition of the present invention, have bond dissociation energy and be preferably cyclic olefin resin greater than 3.70eV and for the resin (B1) of c h bond below the 4.20eV.

In first oxygen-absorbing resin composition of the present invention, cyclic olefin resin is preferably ethene-cyclic olefin copolymer.

According to the present invention, second oxygen-absorbing resin composition also is provided, said composition comprise have can generate with the reaction of oxygen can be for the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol and have and can generate with the reaction of oxygen and can and be the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol greater than 10.0kcal/mol.

In second oxygen-absorbing resin composition of the present invention, have can generate with the reaction of oxygen can for the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol with have can generate with the reaction of oxygen can greater than 10.0kcal/mol and for the content of the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol than being preferably 3/97～50/50 in weight ratio.

In second oxygen-absorbing resin composition of the present invention, have and to generate with the reaction of oxygen and can have at least more than one for generating in the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol can be preferably in each repeating unit that constitutes resin (A2) for the number of the c h bond of the carbon radicals below the 10.0kcal/mol with the reaction of oxygen.

In second oxygen-absorbing resin composition of the present invention, have and to generate with the reaction of oxygen and can be preferably cyclized product of conjugated diene polymer for the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol.

In second oxygen-absorbing resin composition of the present invention, have and to generate with the reaction of oxygen and can be preferably polystyrene or cyclic olefin resin greater than 10.0kcal/mol and for the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol.

Be used for oxygen-absorbing resin composition of the present invention (below, when only address is when " oxygen-absorbing resin composition of the present invention ", the meaning of this speech is meant " first oxygen-absorbing resin composition of the present invention " and " second oxygen-absorbing resin composition of the present invention ") cyclized product of conjugated diene polymer preferably have unsaturated link(age) decrement below 60%.

In addition, the cyclized product of conjugated diene polymer that uses in the oxygen-absorbing resin composition of the present invention is preferably the cyclisation thing of polyisoprene rubber or the cyclisation thing of styrene-isoprene block copolymer.

According to the present invention, provide the oxygen-absorbing film that comprises above-mentioned oxygen-absorbing resin composition.

According to the present invention, also provide the oxygen-absorbing multilayer structure that comprises the oxygen uptake layer that comprises above-mentioned oxygen-absorbing resin composition.

Above-mentioned oxygen-absorbing multilayer structure preferably at least also comprises the gas barrier material layer.

The invention effect

The oxygen absorbent that oxygen-absorbing resin composition of the present invention is different from the past, it need not to contain the metallic compound as the oxygen uptake catalyst for reaction.Good oxygen uptakes such as oxygen-absorbing resin composition of the present invention need not that above-mentioned catalyzer can bring into play that the oxygen absorbed of every film weight is big, the oxygen absorption rate of time per unit and film unit surface is big.

And oxygen-absorbing resin composition of the present invention can be in the stink amount after the minimizing oxygen uptake under the situation that does not reduce oxygen absorbed owing to its oxygen uptake mechanism.

The oxygen-absorbing film of the present invention and the oxygen-absorbing multilayer structure that use this oxygen-absorbing resin composition to obtain, its oxygen uptake excellence at room temperature, the problem of residual stink can not take place, and is suitable as the wrapping material of various food, chemical, medicine, makeup etc.

The best mode that carries out an invention

First oxygen-absorbing resin composition of the present invention comprises that to have bond dissociation energy be the resin (A1) of the following c h bond of 3.70eV and have bond dissociation energy greater than 3.70eV and be the resin (B1) of the c h bond below the 4.20eV.

Among the present invention, " having bond dissociation energy is the resin of the following c h bond of 3.70eV " meaning is meant " in the bond dissociation energy of all c h bonds that this resin had, minimum bond dissociation energy is that 3.70eV is following ".

The bond dissociation energy of a certain c h bond can followingly calculate in the resin: suppose that this resin is made of the repeating unit that contains this c h bond, the model that is combined with methyl for two ends at this repeating unit uses following formula to calculate.

Bond dissociation energy=E (R)+E (H)-E (R-H)

Wherein, E (R), E (H) and E (R-H) represent the electron energy of the R-H key before the electron energy of electron energy, hydroperoxyl radical of the free radical after key dissociates and key dissociate respectively.

Adopt the DMol3 module in density functional method (with reference to following [1] and [2]) the program Accelrys corporate system MS Modeling v3.2 in the calculating, functional uses HCTH (with reference to following [3]), and basis funciton uses DND (with reference to following [4]).

[1]Hohenberg，P.；Kohn，W.，Phys.Rev.B，136，864-871(1964).

[2]Kohn，W.；Sham，L.J.，Phys.Rev.A，140，1133-1138(1965).

[3]Boese，A.D.，Handy，N.C.，J.Chem.Phys.，114，5497(2001).

[4]Delley，B.J.，Chem.Phys.，92，508(1990).

The bond dissociation energy of c h bond (allyl group position carbon-hydrogen) is 3.70eV in the ring that shows with thick word in the formula that tried to achieve by aforesaid method, cyclized product of conjugated diene polymer (1).

Try to achieve by aforesaid method, 1, the bond dissociation energy of the c h bond that shows with thick word in the hydride of 4-polyisoprene polymkeric substance and the ethylene-norbornene copolymer is respectively suc as formula shown in (2) and the formula (3).

[Chemical formula 1]

[Chemical formula 2]

[chemical formula 3]

In the resin (A1), bond dissociation energy is that the number of the following c h bond of 3.70eV is not particularly limited, and has at least more than one but be preferably in each repeating unit that constitutes resin (A1).

Resin (A1) is not particularly limited, but is preferably cyclized product of conjugated diene polymer so long as have the resin that bond dissociation energy is the following c h bond of 3.70eV.

Second oxygen-absorbing resin composition of the present invention comprise have can generate with the reaction of oxygen can be for the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol and have and can generate with the reaction of oxygen and can and be the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol greater than 10.0kcal/mol.

Among the present invention, " have the reaction that can generate and to be the resin of the c h bond of the carbon radicals of (greater than 10.0kcal/mol) below the 10.0kcal/mol " meaning and be meant " in the reaction energy of all carbon radicals that the c h bond that this resin had can generate and oxygen, minimum response can be (greater than 10.0kcal/mol) below the 10.0kcal/mol " with oxygen.

The carbon radicals that a certain c h bond can generate in the resin and the reaction of oxygen can be able to followingly be calculated: suppose that this resin is made of the repeating unit that contains this c h bond, for the model that is combined with methyl at two ends of this repeating unit, use following formula to calculate.

Reaction energy=the E (R-O-O) of carbon radicals and oxygen-{ E (R)+E (O ₂)

Wherein, E (R-O-O), E (R) and E (O ₂) respectively expression and the electron energy of the reacted free radical of oxygen, with the oxygen reaction before the electron energy of free radical and the electron energy of oxygen molecule.

Use the DMol3 module in the above-mentioned density functional method program Accelrys corporate system MS Modelingv3.2 in the calculating, functional uses HCTH, and basis funciton uses DND (with reference to above-mentioned [1]～[4]).

The free radical in the ring that shows with thick word in the formula (4) of the cyclized product of conjugated diene polymer of being tried to achieve by aforesaid method on the carbon atom of allyl group position and the reaction of oxygen can be 10.0kcal/mol.

By this method try to achieve 1, the carbon atom that shows with thick word in hydride, polystyrene and the ethylene-norbornene copolymer of 4-polyisoprene polymkeric substance and the reaction of oxygen can be 23.3kcal/mol, 13.9kcal/mol and 19.7kcal/mol respectively suc as formula shown in (5), (6) and (7).

Owing on carbon radicals (R), have free radical (R-O-O) instability of oxygen, therefore with the reaction of oxygen can value more little, show that unsettled degree is more little.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

In the resin (A2), can generate with the reaction of oxygen and can be not particularly limited, have at least more than one but be preferably in each repeating unit that constitutes resin (A2) for the number of the c h bond of the following carbon radicals of 10.0kcal/mol.

Resin (A2) so long as have can generate with the reaction of oxygen and can be not particularly limited, but be preferably cyclized product of conjugated diene polymer for the resin of the c h bond of the following carbon radicals of 10.0kcal/mol.

Among the present invention, be suitable as that to have bond dissociation energy be that the resin (A1) of the following c h bond of 3.70eV and having can generate with the reaction of oxygen and can obtain by making conjugated diolefin polymer carry out cyclization in the presence of acid catalyst for the cyclized product of conjugated diene polymer of the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol.

As conjugated diolefin polymer, can use the homopolymer of conjugate diene monomer and multipolymer and conjugate diene monomer and can with the monomeric multipolymer of its copolymerization.

Conjugate diene monomer is not particularly limited, its object lesson has: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-divinyl, 2-phenyl-1,3-divinyl, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene etc.

Above-mentioned monomer can use separately, also can be used in combination of two or more.

Can and other monomers of conjugate diene monomer copolymerization for example have: vinylbenzene, o-methyl styrene, p-methylstyrene, a vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, to t-butyl styrene, alpha-methyl styrene, Alpha-Methyl-p-methylstyrene, chloro styrene, m-chlorostyrene, to chloro-styrene, to bromstyrol, 2, aromatic vinyl monomers such as 4-Dowspray 9, vinyl naphthalene; Chain olefinic monomers such as ethene, propylene, 1-butylene; Cyclic olefin monomers such as cyclopentenes, 2-norbornylene; 1,5-hexadiene, 1,6-heptadiene, 1, non-conjugated diene monomers such as 7-octadiene, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate; Other (methyl) acrylic acid derivatives such as (methyl) vinyl cyanide, (methyl) acrylamide etc.

Above-mentioned monomer can use separately, also can be used in combination of two or more.

The object lesson of conjugated diolefin polymer has: the independent or multipolymer of natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), butadiene isoprene copolymer rubber (BIR) equiconjugate diene; Aromatic vinyl-conjugated diene block copolymer equiconjugate diene such as styrene butadiene rubbers (SBR), isoprene-isobutylene copolymers rubber (IIR), ethylene-propylene-dienes copolymer rubber (EPDM), styrene-isoprene block copolymer and can with the monomeric multipolymer of its copolymerization.Wherein preferred polyisoprene rubber, polybutadiene rubber and styrene-isoprene block copolymer, more preferably polyisoprene rubber and styrene-isoprene block copolymer.

Conjugated diolefine and can with the monomeric multipolymer of its copolymerization in, the content of conjugated diene monomeric unit is suitably selected in the scope that does not undermine effect of the present invention, but be generally more than 10% mole, be preferably more than 50% mole, more preferably more than 70% mole.The multipolymer that wherein preferably in fact only comprises conjugated diene monomeric unit.If the content of conjugated diene monomeric unit very little, then might be difficult to obtain the unsaturated link(age) decrement of proper range.

When cyclized product of conjugated diene polymer is the cyclisation thing of aromatic vinyl-conjugated diene block copolymer, aromatic vinyl monomer unit content is not particularly limited in the cyclisation thing, but be generally 1～90% weight, be preferably 5～50% weight, more preferably 10～30% weight.If this content very little, then the initial stage physical strength of oxygen-absorbing resin composition has a declining tendency, and the decline of the physical strength after the oxygen uptake has the trend that becomes big.Otherwise if aromatic vinyl monomer unit content is too many, then the ratio of cyclized product of conjugated diene polymer block descends relatively, exists oxygen absorbed to reduce or the oxygen absorption rate downward trend.

The polymerization process of conjugated diolefin polymer can carry out according to ordinary method, for example use and contain the suitable catalyzer such as Ziegler class polymerizing catalyst, lithium alkylide polymerizing catalyst or catalysts for radical polymerization as catalyst component such as titanium, undertaken by solution polymerization or letex polymerization.

The cyclized product of conjugated diene polymer that uses among the present invention obtains by making above-mentioned conjugated diolefin polymer carry out cyclization in the presence of acid catalyst.

The acid catalyst that is used for cyclization can use known material.Its object lesson has: sulfuric acid; Organic sulfonic acid compounds such as fluorine methylsulfonic acid, Difluore methane-sulfonic acid, tosic acid, xylene monosulfonic acid, acid anhydrides and alkyl ester with the alkyl benzene sulphonate (ABS) that carbonatoms is 2～18 alkyl, above-mentioned acid; Boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, monochlor(in)ate diethyl aluminum; Lewis acids such as dichloride ethyl ammonium, aluminum bromide, antimony pentachloride, tungsten hexachloride, iron(ic) chloride etc.Above-mentioned acid catalyst can use separately, also can be used in combination two or more.Wherein preferred organic sulfoacid compound, more preferably tosic acid or xylene monosulfonic acid.

In per 100 parts by weight of conjugated diene polymkeric substance, the consumption of acid catalyst is generally 0.05～10 weight part, is preferably 0.1～5 weight part, more preferably 0.3～2 weight part.

Cyclization normally is dissolved in conjugated diolefin polymer in the hydrocarbon solvent and carries out.

As hydrocarbon solvent, only otherwise hinder cyclization, be not particularly limited, aromatic hydrocarbons such as benzene,toluene,xylene, ethylbenzene are for example arranged; Aliphatic hydrocarbons such as Skellysolve A, normal hexane, normal heptane, octane; Clicyclic hydrocarbon such as pentamethylene, hexanaphthene etc.The boiling point of above-mentioned hydrocarbon solvent is preferably more than 70 ℃.

The solvent that is used for the polyreaction of conjugated diolefin polymer can be identical with the solvent that is used for cyclization.In this case, can add the acid catalyst that is used for cyclization in the polymerization liquid after polyreaction finishes, then polyreaction is carried out cyclization.

The consumption of varsol is generally the scope that the solids content that makes conjugated diolefin polymer is 5～60% weight, preferred 20～40% weight.

Cyclization can carry out under any pressure such as pressurization, decompression and normal atmosphere, considers from the simplicity aspect of operation, wishes under atmospheric pressure to carry out.When under the environment of drying air stream, particularly dry nitrogen or dry argon, carrying out cyclization, can suppress the caused side reaction of moisture.

Temperature of reaction in the cyclization and reaction times are not particularly limited.Temperature of reaction is generally 50～150 ℃, is preferably 70～110 ℃; Reaction times is generally 0.5～10 hour, is preferably 2～5 hours.

Carry out making the acid catalyst inactivation according to ordinary method after the cyclization, remove the acid catalyst residue, then remove varsol, can obtain the cyclized product of conjugated diene polymer of solid state.

Among the present invention, the unsaturated link(age) decrement of cyclized product of conjugated diene polymer is preferably below 60%, and more preferably 55～40%.

By using the unsaturated link(age) decrement is cyclized product of conjugated diene polymer, the oxygen absorbed of oxygen-absorbing resin composition of the present invention and oxygen absorption rate excellence below 60%.

Wherein, the unsaturated link(age) decrement is the index of the degree that unsaturated link(age) reduces because of cyclization in the conjugated diene monomeric unit part that is illustrated in the conjugated diolefin polymer, can following calculating and try to achieve.That is, analyze to obtain respectively before and after the cyclization by proton N MR and directly be combined in the ratio of the peak area of the proton on two keys in the conjugated diene monomeric unit part in the conjugated diolefin polymer, calculate its decrement with respect to the peak area of total proton.

In the conjugated diene monomeric unit part in conjugated diolefin polymer, when the peak area that the total proton peak area after the peak area that is SBT with the total proton peak area before the cyclization, directly is combined in the proton on two keys is SBU, cyclization is SAT, directly be combined in the proton on two keys was SAU, the peak area ratio (SB) that then directly is combined in the proton on two keys before the cyclization was:

SB＝SBU/SBT

The peak area ratio (SA) that directly is combined in the proton on two keys behind the cyclization is:

SA＝SAU/SAT

Therefore, the unsaturated link(age) decrement is tried to achieve by following formula:

Unsaturated link(age) decrement (%)=100 * (SB-SA)/SB

The unsaturated link(age) decrement of cyclized product of conjugated diene polymer can suitably be selected amount, temperature of reaction and the reaction times of acid catalyst in the cyclization to wait to regulate.

In order to obtain having the cyclized product of conjugated diene polymer of required unsaturated link(age) decrement, can make the typical curve in acid catalysis dosage, temperature of reaction and reaction times etc. in the cyclization in advance respectively, adopt the method for carrying out cyclization etc. according to typical curve.

The weight-average molecular weight of the cyclized product of conjugated diene polymer that uses among the present invention (A) is preferably 10,000～1,000 in the polystyrene standard scaled value of gel permeation chromatography, 000, more preferably 20,000～700,000, more preferably 30,000～500,000.

When cyclized product of conjugated diene polymer was the cyclisation thing of aromatic vinyl-conjugated diene block copolymer, the weight-average molecular weight of aromatic vinyl polymer block was preferably 1,000～500,000, more preferably 3,000～300,000, more preferably 5,000～100,000, be preferably 8 especially, 000～50,000.If above-mentioned weight-average molecular weight is too low, then the initial stage physical strength of oxygen-absorbing resin composition has a declining tendency, and the decline of the physical strength after the oxygen uptake has the trend that becomes big in addition.Otherwise if weight-average molecular weight is too high, then the ratio of cyclized product of conjugated diene polymer block descends relatively, and oxygen absorbed is tending towards descending.

The weight-average molecular weight of cyclized product of conjugated diene polymer can suitably be selected to supply with the weight-average molecular weight of the conjugated diolefin polymer of cyclisation and regulate.

If the weight-average molecular weight of cyclized product of conjugated diene polymer is too low, then might be difficult to form film, physical strength step-down.If the weight-average molecular weight of cyclized product of conjugated diene polymer is too high, then soltion viscosity raises and is difficult to operation during cyclization, and the processibility during extrusion molding might reduce simultaneously.

The gel of cyclized product of conjugated diene polymer (toluene insoluble composition) amount is generally below 10% weight, is preferably below 5% weight, but the preferred especially cyclisation thing that does not contain gel in fact.If gel content is many, might undermine its smoothness when then forming film.

In the present invention, adding the thermostability in man-hour, can in cyclized product of conjugated diene polymer, add oxidation inhibitor in order to ensure cyclized product of conjugated diene polymer.Amount to oxidation inhibitor is not particularly limited, and with respect to the weight of cyclized product of conjugated diene polymer, is generally 10～5, and 000ppm is preferably 30～3,000ppm, more preferably 50～2, the scope of 000ppm.

In addition, the amount of oxidation inhibitor is generally 10～3 in the oxygen-absorbing resin composition of the present invention, and 000ppm is preferably 30～2,000ppm, more preferably 50～1, the scope of 000ppm.But therefore oxygen uptake decline when the addition of oxidation inhibitor is too many consider that oxygen-absorbing resin composition adds the stability in man-hour, and it is most important suitably to regulate addition simultaneously.

Oxidation inhibitor so long as in resin material or the field of rubber materials normally used oxidation inhibitor get final product, be not particularly limited.The typical example of this oxidation inhibitor has: the oxidation inhibitor of Hinered phenols, Phosphorus and lactone.Above-mentioned oxidation inhibitor can also be used in combination of two or more.Especially preferably phenolic antioxidant and Phosphorus oxidation inhibitor are used in combination.Can also add Photostabilised dose of amine (HALS).

The object lesson of Hinered phenols antioxidant has: 2, the 6-ditertbutylparacresol, [3-(3 for tetramethylolmethane four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], the sulfo-divinyl is two, and [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, N, N '-oneself is-1 years old, 6-two bases are two, and [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide], diethyl [[3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxyphenyl] methyl] phosphoric acid ester, 3,3 '; 3 " 5,5 '; 5 "-six tertiary butyls-a, a ', a "-(sym-trimethylbenzene-2,4; 6-three bases) three p-cresol; two [3-(3; the 5-di-t-butyl)-4-hydroxyphenyl] propionic esters of hexa-methylene; four [methylene radical-3-(3,5-di-t-butyl-4-hydroxypropyl) propionic ester] methane; Octadecane base-3-(4 '-hydroxyl-3,5 '-tert-butyl-phenyl) propionic ester, 1,3,5-three (3,5-di-t-butyl-4-acrinyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, 2, two (positive hot the sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3 of 4-, the 5-triazine, three (3,5-di-t-butyl-4-acrinyl) chlorinated isocyanurates, the 2-tertiary butyl-6-(3 '-tertiary butyl-2 '-hydroxyl-5 '-methyl-benzyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-di-t-butyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate etc.

The example of Phosphorus oxidation inhibitor has: 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, phosphorous acid two [2, two (1, the 1-the dimethyl ethyl)-6-aminomethyl phenyls of 4-] ethyl ester, four (2, the 4-di-tert-butyl-phenyl) [1,1-biphenyl]-4,4 '-two basic diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol phosphite etc.

The example of lactone oxidation inhibitor has: 5, and the reaction product of 7-di-t-butyl-3-(3, the 4-3,5-dimethylphenyl)-3H-benzofuran-2-ones etc. and o-Xylol.

In addition, can in cyclized product of conjugated diene polymer, mix the common all cpds that adds as required.Above-claimed cpd for example has: weighting agents such as lime carbonate, aluminum oxide, titanium oxide; Binding property imparting agent (hydrogenated petroleum resin, hydrogenated terpene resin, castor oil derivative, sorbitan high-grade aliphatic ester, lower molecular weight polybutene); Plasticizer (phthalic ester, glycol ester); Tensio-active agent; Flow agent; UV light absorber; Photostabilizer; Dewatering agent; Extension of validity agent (methyl ethyl diketone, methyl alcohol, ortho-acetic acid methyl esters etc.); Shrink activator etc.

Among the present invention, can in cyclized product of conjugated diene polymer, be used in combination the alpha-olefin resin as required.Thus, can be under the situation of oxygen absorption rate that does not influence oxygen-absorbing resin composition and oxygen absorbed, and improve physical strength before and after the oxygen uptake.

The poly-alpha olefins resin can be any of the multipolymer of the homopolymer of alpha-olefin, two or more alpha-olefin or alpha-olefin and the monomeric multipolymer except that alpha-olefin, can also be the modifier of above-mentioned (being total to) polymkeric substance.

The object lesson of poly-alpha olefins resin has: the homopolymer of alpha-olefins such as ethene, propylene or multipolymer, for example alpha-olefin homos such as polyethylene, polypropylene, metallocenes polypropylene, polymethylpentene, polybutene such as straight chain shape new LDPE (film grade) (LLDPE), new LDPE (film grade) (LDPE), medium-density polyethylene (MDPE), high density polyethylene(HDPE) (HDPE), metallocene polyethylene; The multipolymer of ethene and other alpha-olefins, for example ethylene-propylene random copolymer, Ethylene-Propylene Block Copolymer, ethylene-propylene-polybutene-1 multipolymer etc.; Based on the multipolymer of the alpha-olefin of alpha-olefin and carboxylic acid unsaturated alcohol and saponified, for example vinyl-vinyl-acetic ester multipolymer, ethylene-vinyl alcohol copolymer etc.; Alpha-olefin and α based on alpha-olefin, beta-unsaturated carboxylic acid ester or α, the multipolymer of beta-unsaturated carboxylic acid etc., ethene-α for example, beta-unsaturated carboxylic acid ester copolymer (ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer etc.), ethene-α, beta-unsaturated carboxylic acid multipolymer (ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer etc.) etc.; With alpha-olefin (being total to) polymkeric substance of polyethylene or polypropylene etc. with unsaturated carboxylic acid-modified sour modification poly-alpha olefins resins such as vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acids; Make the ionomer resin of the effects such as multipolymer of Na ion or Zn ion and ethene and methacrylic acid; The mixture of above-mentioned resin etc.

The poly-alpha olefins resin can be used alone, and also can be used in combination two or more.With respect to the cyclized product of conjugated diene polymer and the polyolefin resin that amount to 100 weight parts, the consumption of poly-alpha olefins resin is preferably 0～90% weight, 10～80% weight more preferably, more preferably 15～70% weight are preferably 20～50% weight especially.When the consumption of poly-alpha olefins resin was above-mentioned scope, the equilibrium of the oxygen absorption rate of oxygen-absorbing resin composition, oxygen absorbed and physical strength was well kept, and the ratio of cyclized product of conjugated diene polymer is high more, and oxygen absorption rate and oxygen absorbed are good more.

To another of first oxygen-absorbing resin composition of the present invention must composition-have bond dissociation energy to be not particularly limited greater than 3.70eV and for the resin (B1) of the c h bond below the 4.20eV.The bond dissociation energy of preferred resin (B1) is greater than 3.70eV and for below the 4.17eV.

Having bond dissociation energy has greater than 3.70eV and for the object lesson of the resin (B1) of c h bond below the 4.20eV: cyclic olefin resin.

To another of second oxygen-absorbing resin composition of the present invention must composition-have and can generate with the reaction of oxygen and can be not particularly limited greater than 10.0kcal/mol and for the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol.Preferred resin (B2) can be for below the 20.0kcal/mol with the reaction of oxygen.

Have and to generate with the reaction of oxygen and can have: polystyrene and cyclic olefin resin greater than 10.0kcal/mol and for the object lesson of the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol.

Among the present invention, the cyclic olefin resin that is used as resin (B1) or resin (B2) can be the ring-opening polymerization polymer of cyclic olefin, also can be the addition polymer of cyclic olefin.Except that the homopolymer and multipolymer of ring-type alkene, can also be cyclic olefin and can with the multipolymer of other alkene of its copolymerization.And cyclic olefin resin can carry out polymer modification or hydrogenant products such as toxilic acid addition, cyclopentadiene addition after cyclic olefin (being total to) polymerization.

Among the present invention, resin (B1) and resin (B2) can be the resins that is obtained by the monomer beyond the cyclic olefin, this resin by polymerization after the processing of (hydrogenation etc.) etc. can reach with cyclic olefin resin and have equal structure.

Weight-average molecular weight to the cyclic olefin resin that uses among the present invention is not particularly limited, polystyrene standard scaled value to be measured by gel permeation chromatography (GPC) in toluene or cyclohexane solvent is generally 1,000～1,000,000, be preferably 10,000～500,000,20,000～100,000 scope more preferably.If weight-average molecular weight is too little, then use the physical strength of the oxygen-absorbing resin composition that this resin obtains poor; Otherwise,, then be difficult to sometimes be shaped if weight-average molecular weight is too big.

The example of cyclic olefin resin has: open loop (being total to) polymkeric substance of the cyclic olefin of being put down in writing as Japanese kokai publication hei 7-231928 communique, the addition copolymer of addition (being total to) polymkeric substance, cyclic olefin and the alpha-olefin etc. of cyclic olefin and their hydride etc.

Cyclic olefin can be that cycloolefin also can be a polycyclic olefin, can also have the condensed ring part with aromatic ring etc., and its typical example has: two ring [2.2.1] hept-2-ene" class and Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-norbornene compound monomers such as 4-alkene class.

The monomeric object lesson of norbornene compound has: norbornylene, 5-methyl-2-norbornylene, 5, norbornene compounds such as the alkyl of norbornylenes such as 5-dimethyl-2-norbornylene, 5-ethyl-2-norbornylene, 5-butyl-2-norbornylene, 5-ethylidene-2-norbornene or alkylidene group substituent; The polar group of norbornene compound (halogen atom, cyano group, pyridyl, methoxyl group etc.) substituent; Dicyclopentadiene (DCPD), 2, Dicyclopentadiene (DCPD) classes such as 3-dihydro Dicyclopentadiene (DCPD); The affixture of cyclopentadiene and tetrahydroindene etc.; 4,9:5,8-two endo-methylene groups-3a, 4,4a, 5,8,8a, 9,9a-octahydro-1H-benzindene, 4,11:5,10:6,9-three endo-methylene groups-3a, 4,4a, 5,5a, 6,9,9a, 10,10a, 11,11a-ten dihydros-1H-encircles three～tetramer of cyclopentadiene such as penta anthracene; The 6-methyl isophthalic acid, 4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8,8a-octahydro naphthalene, 6-ethyl-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8,8a-octahydro naphthalene, 6-ethylidene-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8, two endo-methylene group octahydro naphthalene classes such as 8a-octahydro naphthalene; 6-chloro-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8,8a-octahydro naphthalene, 6-cyano group-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8,8a-octahydro naphthalene, 6-pyridyl-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8,8a-octahydro naphthalene, 6-methoxycarbonyl-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8, the two endo-methylene group octahydro naphthalene classes that 8a-octahydro naphthalene isopolarity group replaces etc.

Can have with the monomeric example of norbornene compound monomer copolymerization: alpha-olefins such as ethene, propylene; Monocycle shape alkene such as cyclopentenes; Styrenics such as vinylbenzene etc.

The polymerization of above-mentioned cyclic olefin resin and hydrogenation thereof can be carried out according to ordinary method.

In the present invention, optimal ethylene-norbornene copolymer, ethene-ethene-cyclic olefin copolymers such as Fourth Ring dodecane multipolymer in the above-mentioned cyclic olefin resin.

In first oxygen-absorbing resin composition of the present invention, the resin (A1) that has bond dissociation energy and be a following c h bond of 3.70eV with have bond dissociation energy greater than 3.70eV and for the content of the resin (B1) of the c h bond below the 4.20eV than being preferably 3/97～50/50 in weight ratio.The resin (A1) that has bond dissociation energy and be a following c h bond of 3.70eV with have bond dissociation energy greater than 3.70eV and for the content of the resin (B1) of the c h bond below the 4.20eV than in above-mentioned scope the time, can obtain the oxygen absorption rate under the room temperature and oxygen absorbed is excellent especially, stink is especially less and the oxygen-absorbing resin composition of physical strength excellence during oxygen uptake.

First oxygen-absorbing resin composition of the present invention at room temperature oxygen absorption rate and oxygen absorbed is excellent especially and the reason that do not produce stink during oxygen uptake does not limit the present invention, but think as follows.

One of composition of first oxygen-absorbing resin composition of the present invention-have bond dissociation energy is the resin (A1) of the following c h bond of 3.70eV, and it utilizes heat or light to be easy to generate＞the C free radical.This moment is if oxygen-absorbing resin composition and oxygen meet, then should＞the C free radical immediately with oxygen reaction, easy generation＞COO free radical.If have the low free radical aceeptor of bond dissociation energy in the oxygen-absorbing resin composition, then from this free radical aceeptor, obtain hydrogen, generation＞COOH, it decomposes generation＞CO free radical or HO free radical, therefore total system can be carried out autoxidation, its result, oxygen is consumed by free radical, and the result is that the oxygen absorption is carried out.In this case, if free radical aceeptor has alicyclic structure, even hydrogen is removed the decomposition that also is unlikely to take place molecule integral body, the generation of stink reduces as a result.Promptly, in first oxygen-absorbing resin composition of the present invention, the bond dissociation energy that has as free radical aceeptor has the resin (A1) that bond dissociation energy is the following c h bond of 3.70eV greater than existing in 3.70eV and the matrix for the resin (B1) of c h bond below the 4.20eV, this resin (A1) causes the oxygen uptake reaction, this oxygen uptake reaction causes the oxygen uptake reaction of the resin (B1) that constitutes matrix, oxygen is absorbed carried out.If this matrix resin (B1) has alicyclic structure, then can not decompose because of oxygen uptake (key dissociates), its result, the stink that is produced by resolvent also reduces.

Like this, if the ratio height of matrix resin (B1), therefore the decomposition of little that is caused by this oxygen uptake then all can obtain the oxygen-absorbing resin composition of physical strength excellence before and after oxygen uptake.

In second oxygen-absorbing resin composition of the present invention, have can generate with the reaction of oxygen can for the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol with have can generate with the reaction of oxygen can greater than 10.0kcal/mol and for the content of the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol than being preferably 3/97～50/50 in weight ratio.Have can generate with the reaction of oxygen can for the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol with have can generate with the reaction of oxygen can greater than 10.0kcal/mol and for the content of the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol than in above-mentioned scope the time, can obtain the oxygen absorption rate under the room temperature and oxygen absorbed is excellent especially, the stink during oxygen uptake especially less and the oxygen-absorbing resin composition of physical strength excellence.

Second oxygen-absorbing resin composition of the present invention at room temperature oxygen absorption rate and oxygen absorbed is excellent especially and the reason that do not produce stink during oxygen uptake does not limit the present invention, but think as follows.

One of composition of second oxygen-absorbing resin composition of the present invention-have can generate with the reaction of oxygen can be the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol, and it utilizes heat or light to be easy to generate＞the C free radical.This moment is if oxygen-absorbing resin composition and oxygen meet, then should＞the C free radical immediately with oxygen reaction, easy generation＞COO free radical.If have the low free radical aceeptor of bond dissociation energy in the oxygen-absorbing resin composition, then from this free radical aceeptor, obtain hydrogen, generation＞COOH, it decomposes generation＞CO free radical or HO free radical, therefore total system can be carried out autoxidation, its result, oxygen is consumed by free radical, and the result is that the oxygen absorption is carried out.In this case, if free radical aceeptor has alicyclic structure, even hydrogen is removed the decomposition that also is unlikely to take place molecule integral body, the generation of stink reduces as a result.Promptly, in second oxygen-absorbing resin composition of the present invention, can generate with the reaction of oxygen and can be the resin (A2) of the c h bond of the carbon radicals below the 10.0kcal/mol as having of free radical aceeptor greater than existing in 10.0kcal/mol and the matrix to have to generate with the reaction of oxygen for the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol, this resin (A2) causes the oxygen uptake reaction, this oxygen uptake reaction causes the oxygen uptake reaction of the resin (B2) that constitutes matrix, oxygen is absorbed carried out.This moment then can be because of oxygen uptake (key dissociates) be decomposed if matrix resin (B2) has alicyclic structure, its result, and the stink that is produced by resolvent also reduces.

Like this, if the ratio height of matrix resin (B2), therefore the decomposition of little that is caused by this oxygen uptake then all can obtain the oxygen-absorbing resin composition of physical strength excellence before and after oxygen uptake.

As long as the preparation method of first oxygen-absorbing resin composition of the present invention can be with resin (A1) and resin (B1) uniform mixing, be not particularly limited, can adopt known method, for example: the solution casting, promptly, resin (A1) and resin (B1) are dissolved in the solvent, afterwards that solution coat is also dry on the face of general planar; And with (A) with (B) carry out method of melting mixing etc. with mixing rolls such as forcing machine, kneader and/or Banbury mixeies.

Resin (A1) can be changed into resin (A2), change resin (B1) into resin (B2), prepare second oxygen-absorbing resin composition of the present invention according to preparation method same as described above.

The oxygen absorbent that oxygen-absorbing resin composition of the present invention is different from the past, it need not to contain the metallic compound as the oxygen uptake catalyst for reaction.Good oxygen uptakes such as oxygen-absorbing resin composition of the present invention does not need that above-mentioned catalyzer can bring into play that the oxygen absorbed of every film weight is big, the oxygen absorption rate of time per unit and film unit surface is big.

Oxygen-absorbing film of the present invention comprises oxygen-absorbing resin composition of the present invention.

Need to prove that unless otherwise specified, then the notion of film had both comprised that film also comprised thin slice, both can strictly distinguish by thickness.

The method of oxygen-absorbing resin composition of the present invention being made film is not particularly limited, and can adopt known method in the past.For example utilize the solution casting to obtain film, that is, oxygen-absorbing resin composition of the present invention is dissolved in the solvent, afterwards that solution coat is also dry on the face of general planar.In addition, for example with resin combination etc. behind the forcing machine melting mixing, be extruded into predetermined shape by the T-shape of the mouth as one speaks, the circular shape of the mouth as one speaks (the annular shape of the mouth as one speaks) etc., obtain T-die method film, blown film etc.Forcing machine can use mixing rolls such as single screw extrusion machine, twin screw extruder, Banbury mixer.By forming biaxially oriented film with T shape of the mouth as one speaks film is biaxial stretch-formed.

Oxygen-absorbing multilayer structure of the present invention has the oxygen uptake layer that comprises oxygen-absorbing resin composition of the present invention at least.

In the oxygen-absorbing multilayer structure of the present invention, only otherwise undermine under the prerequisite of effect of the present invention, the oxygen uptake layer can contain the known oxygen uptake composition except that oxygen-absorbing resin composition of the present invention.Total amount (total amount of oxygen-absorbing resin composition of the present invention and the oxygen uptake composition except that oxygen-absorbing resin composition of the present invention) with respect to the oxygen uptake composition, the amount of the oxygen uptake composition except that oxygen-absorbing resin composition of the present invention is less than 50% weight, be preferably less than 40% weight, more preferably less than 30% weight.

Formation according to multilayered structure, the oxygen uptake layer of oxygen-absorbing multilayer structure of the present invention absorbs the oxygen that sees through the gas barrier material layer from the outside, in addition, for example use comprise have sealing material layer-when the wrapping material configuration example of the oxygen-absorbing multilayer structure of the formation of oxygen uptake layer-gas barrier material layer such as bag shape packaging vessel, above-mentioned oxygen uptake layer becomes and has the layer of function that absorbs the oxygen of wrapping material inside via sealing material layer.

Oxygen-absorbing multilayer structure of the present invention preferably has the gas barrier material layer at least except having the oxygen uptake layer.

The structure of oxygen-absorbing multilayer structure of the present invention is not particularly limited, and can be film, thin slice, perhaps can have structure in addition.

Oxygen-absorbing multilayer structure of the present invention can further have sealing material layer, support base material layer, deodorizing composition layer, surface resin layer or protective layer.

In oxygen-absorbing multilayer structure of the present invention, the laminated order that constitutes each layer of this multilayered structure is not particularly limited, and is generally sealing material layer/oxygen uptake layer/gas barrier material layer/deodorizing composition layer/surface resin layer/protective layer.Required layer can be set in above-mentioned each layer as required.

The gas barrier material layer is to be used to stop the layer that is provided with from the gas permeation of outside.During for example by oxygen-absorbing multilayer structure structure pouch wrapping material, the gas barrier material layer becomes skin.As long as processibility and cost allow, then preferably reduce the oxygen flow degree of gas barrier material layer as far as possible, oxygen flow degree and its thickness are irrelevant, and the oxygen flow degree of the film that 20 μ m are thick in 25 ℃ of environment with relative humidity 65% must be 100cc/m ²It normal atmosphere is following [to be denoted by " 100cc/m in the present invention ²It normal atmosphere following (20 μ m) ", need to prove, when changing envrionment conditions, enclose this], 50cc/m more preferably ²It normal atmosphere following (20 μ m).

Be used to constitute the material of gas barrier material layer, be not particularly limited, can use metal, inorganic materials, resin etc. so long as the low material of gas-premeables such as oxygen, water vapour gets final product.

As metal, use the low aluminium of ventilation property usually.Metal can be used as paper tinsel and is laminated on resin film etc., also can thin metal film be formed on resin film etc. by evaporation.

Inorganic materials is used metal oxides such as silicon-dioxide or aluminum oxide, and these metal oxides can separately or be used in combination, also can evaporation use on resin film etc.

Though resin less than metal and inorganic materials, has multiple choices on mechanical properties, thermal properties, chemical proofing, optical property and preparation method aspect gas barrier property, consider from above-mentioned advantage, be preferably used as the gas barrier material layer.The employed resin of gas barrier material layer of the present invention is not particularly limited, and gets final product so long as have the resin of good gas-barrier properties, can use any, can not produce obnoxious flavour during burning disposal when using not chloride resin, and be therefore preferred.

In the above-mentioned film, preferably use on resin film evaporation that the transparent evaporated film of inorganic oxide is arranged.

The object lesson that is used as the resin of gas barrier material layer has: polyvinyl alcohol resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer; Vibrin such as polyethylene terephthalate, polybutylene terephthalate; Nylon 6, nylon 66, NYLON610, Ni Long11, nylon 12, MXD nylon (poly hexamethylene adipamide metaphenylene dimethylamine) and their polyamide resins such as multipolymer; The polyaramide resin; Polycarbonate resin; Polystyrene resin; Polyacetal resin; Fluoro-resin; Polyethers, adipic acid ester class, caprolactone class, thermoplastic polyurethane such as polycarbonate-based; Ethylene halide such as polyvinylidene dichloride, polyvinyl chloride base resin; Polyacrylonitrile; The multipolymer of alpha-olefin and vinyl-acetic ester, acrylate, methacrylic ester etc., for example vinyl-vinyl-acetic ester multipolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer; With unsaturated carboxylic acid-modified sour modification poly-alpha olefins resins such as alpha-olefins such as polyethylene or polypropylene (being total to) polymkeric substance vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acids; Make the ionomer resin of the effects such as multipolymer of Na ion or Zn ion and ethene and methacrylic acid; The mixture of above-mentioned resin etc.Can also on the said gas-blocking material layer, carry out the evaporation of inorganic oxides such as aluminum oxide or silicon oxide.

Above-mentioned resin can consider mechanical characteristicies such as gas barrier property, intensity or toughness or rigidity, thermotolerance, printing, the transparency, binding property etc. required require characteristic, according to suitably selecting as the purpose of multilayered structure.Above-mentioned resin can be used alone, and also can be used in combination two or more.

Can in being used as the resin of gas barrier material layer, mix following material: heat-resisting stabilizing agent; UV light absorber; Oxidation inhibitor; Tinting material; Pigment; Neutralizing agent; Plasticizer such as phthalic ester, glycol ester; Weighting agent; Tensio-active agent; Flow agent; Photostabilizer; Dewatering agents such as alkaline earth metal oxide; Deodorizing composition such as activated carbon or zeolite; Binding property imparting agent (castor oil derivative, sorbitan high-grade aliphatic ester, lower molecular weight polybutene); Extension of validity agent (methyl ethyl diketone, methyl alcohol, ortho-acetic acid methyl esters etc.); Shrink activator; Other resins (poly-alpha olefins etc.) etc.

Can also add antiblocking agent, antifogging agent, weathering resistance stablizer, slip(ping)agent, antistatic agent, strengthening agent, fire retardant, coupling agent, whipping agent, releasing agent etc. as required.

Can also be on the gas barrier material layer implement for example required print patterns such as literal, figure, mark, pattern, decorative pattern of positive printing or back face printing according to common printing process.

In order to give thermotolerance etc., can form protective layer in the outside of gas barrier material layer.

The resin that is used for protective layer for example has: ethene polymerss such as high density polyethylene(HDPE); Alfon; Propene polymers such as propylene-ethylene random copolymers, propylene-ethylene block copolymer; Polymeric amide such as nylon 6, nylon 66; Polyester such as polyethylene terephthalate etc.Wherein preferred polyamide and polyester.

Need to prove that when the film that uses polyester film, polyamide layer, inorganic oxide evaporated film, vinylidene chloride to coat etc. during as the gas barrier material layer, the said gas-blocking material layer is also brought into play the function of protective layer simultaneously.

In oxygen-absorbing multilayer structure of the present invention, the sealing material layer that can be provided with is a layer as described below as required, promptly this layer is because of heat fusion and bonding mutually (heat-sealing), in packaging vessel, form and the outside isolated spatial function of packaging vessel thereby have, and prevent that in packaging vessel inside the oxygen uptake layer from directly contacting with packed article, oxygen is seen through and absorbed by the oxygen uptake layer.

The object lesson that is used to form the heat sealability resin of sealing material layer has: the homopolymer of alpha-olefin; The multipolymer of ethene and alpha-olefin; Multipolymer based on the alpha-olefin of alpha-olefin and vinyl-acetic ester, acrylate, methacrylic ester etc.; With alpha-olefin (being total to) polymkeric substance with unsaturated carboxylic acid-modified sour modification poly-alpha olefins resin; Ionomer resin; The mixture of above-mentioned resin etc.

Oxygen flow degree and the number of plies, thickness or the constituent material of sealing material layer under 25 ℃ is irrelevant, is preferably 200cc/m ²More than the normal atmosphere sky (20 μ m), be preferably 400cc/m especially ²More than the normal atmosphere sky (20 μ m).

Need to prove that permeability is represented with the gas volume of unit test film by unit surface in the following unit time of partial pressure difference, can measure according to the method for defined among the JIS K7126 " the Gas permeability test method of plastics film and thin slice ".

Oxygen-absorbing multilayer structure of the present invention can have the deodorizing composition layer that contains the deodorization composition.

The deodorization composition can use known material.The deodorization composition can be the sorbent material of catching the stink composition by adsorption, also can be the deodorizing composition with deodorization functions that the stink composition is become the odorless composition by chemical reaction etc.It can also be the material that has adsorption and deodorization functions concurrently.

Sorbent material can be organic adsorbents such as soyflour, vibrin, acrylic resin, can be inorganic adsorbents such as clay mineral such as natural zeolite, synthetic zeolite, silica dioxide gel, activated carbon, impregnated activated carbon, atlapulgite, activated alumina, clay, diatomite, kaolin, talcum powder, wilkinite, magnesium oxide, ferric oxide, aluminium hydroxide, magnesium hydroxide, ironic hydroxide, Magnesium Silicate q-agent, pure aluminium silicate, synthetic hydrotalcite, silicon-dioxide, sepiolite, mica also, but consider preferred inorganic adsorbent from stable on heating angle.

Among the present invention, the preferred basic cpd of deodorizing composition.This be because, think that in the present invention the oxygen uptake effect of effective constituent-cyclized product of conjugated diene polymer of oxygen uptake choke resin layer undertaken by following circulative metabolism: at first, the active hydrogen of cyclized product of conjugated diene polymer is removed the generation free radical, then, this radical-scavenging oxygen molecule forms peroxy, this peroxy obtains hydrogen atom, and above-mentioned circulation repeats.Its result produces acidic components such as aldehyde or acid.

Basic cpd for example has: the oxyhydroxide of basic metal or alkaline-earth metal; Other oxyhydroxide such as ironic hydroxide; The carbonate of basic metal or alkaline-earth metal, supercarbonate; Ammonia; The compound that contains amino or imino-; The compound of amide-containing or imide; The organic basic compounds such as compound that contain the urea key.

In oxygen-absorbing multilayer structure of the present invention, can be in the arranged outside surface resin layer of gas barrier material layer.

The resin that is used to form surface resin layer preferably merges by the heating melting and heat sealability resin that can extrusion molding mutually.

In addition, when the oxygen uptake multilayered tube is used as various container,, preferably utilize photogravure or offset printing etc. to print in order to indicate content etc.

The thickness of surface resin layer and constituent material are irrelevant, are preferably the scope of 5～150 μ m, more preferably the scope of 10～100 μ m.The thickness of surface resin layer can be given full play to ability to take oxygen in above-mentioned scope the time.

Oxygen-absorbing multilayer structure of the present invention can have the support base material layer as required.The material that constitutes the support base material layer uses: the poly-alpha olefins resin; Polyethylene terephthalate vibrin such as (PET); Polyamide 6 or polyamide 6-polyamide resins such as polyamide 66 multipolymer; Natural fiber; Synthon; The paper that mentioned component papermaking is obtained.

The support base material layer can be arranged between oxygen uptake layer and the gas barrier material layer, also can be according to the order setting of oxygen uptake layer/gas barrier material layer/support base material layer.

In addition, can be formed for the binder layer of bonding each layer.Can use the film or the thin slice of the resin that fusion also can be merged mutually by heat in the binder layer.The object lesson of above-mentioned resin has: the homopolymer of alpha-olefin or multipolymer; Acid modification poly-alpha olefins resin; Ionomer resin; The mixture of above-mentioned resin etc.

In oxygen-absorbing multilayer structure of the present invention, the protective layer that is provided with, sealing material layer, deodorizing composition layer, surface resin layer, support base material layer, binder layer etc. as required equally with the gas barrier material layer can add various additives.

Manufacture method to oxygen-absorbing multilayer structure of the present invention is not particularly limited, and can obtain constituting the single thin film of each layer of multilayered structure earlier, and is again that they are laminated, also can directly form multilayered structure.

Single thin film can obtain according to the method identical with the method for oxygen-absorbing resin composition of the present invention being made film.

Utilize the single thin film as above operate and to obtain, by extrusion coated method, lamination, dry type is laminated can make multilayered structure.

In the manufacturing of multilayered structure, can adopt known coextrusion shaping method, for example,, can carry out extrusion molding with above-mentioned same operation except using with the forcing machine of resin kind similar number, using the multiple shape of the mouth as one speaks of multilayer.

Coextrusion shaping rule is if any the laminated method of coextrusion, co-extrusion film moulding method, coextrusion inflation moulding method etc.

For example, utilize water-cooled or air-cooled type inflation method, each resin that constitutes gas barrier material layer, oxygen uptake layer and each layer of sealing material layer is heated with the fusion of many forcing machines difference, for example under 190～210 ℃ extrusion temperature, from the multilayer ring-type shape of the mouth as one speaks, extrude, solidify with aqueous refrigeration agent quenchings such as water coolants immediately, can form the tubular resin laminated product.

When making multilayered structure, each layer of formation multilayered structure is preferably 160～250 ℃ with the temperature of resin.When temperature was lower than 160 ℃, the fracture of uneven thickness or multilayered structure appearred sometimes; If surpass 250 ℃, then cause the fracture of multilayered structure sometimes.More preferably 170～230 ℃.

Draw off rate when multilayered structure is made is generally 2～200m/ minute, is preferably 50～100m/ minute.Draw off rate is below 2m/ minute the time, and production efficiency might variation; During greater than 200m/ minute, fully the cooling multiplayer structure merges when curling sometimes.

Multilayered structure comprises stretchable material, is improved by its characteristic that stretches, and as polyamide resin, vibrin, polypropylene etc., the multilayer film that coextrusion can be obtained under this situation further carry out single shaft or biaxial stretch-formed.Can further carry out thermal-setting as required.

Stretching ratio is not particularly limited, and vertically (MD) and horizontal (TD) respectively stretches 1～5 times usually, and being preferably in length and breadth, direction respectively stretches 2.5～4.5 times.

Stretching can be carried out according to known methods such as tentering stretching mode, inflation stretching mode, roller stretching modes.The stretching order can be vertically also can be earlier that earlier laterally preferably direction stretches simultaneously in length and breadth, can adopt tubular type biaxial stretch-formed method simultaneously.

Oxygen-absorbing multilayer structure of the present invention re-uses after can being shaped as the packaging vessel of different shape.

Packaging vessel can have various forms according to its purpose, purposes etc., for example has the liquid packing container of shapes such as chevron (gable top), brick shape, cubes, positive tetrahedron, other tower trays or cup-like container, bag-like container etc.

The manufacturing process that is used to obtain above-mentioned packaging vessel is not particularly limited, with oxygen-absorbing multilayer structure reheat under the temperature below the fusing point of the resin that constitutes it, carry out single shaft or biaxial stretch-formed according to method for hot forming such as tractive shaping, vacuum forming, pressure forming, press forming, roller stretching method, pantographic stretching method or inflation stretching method etc., can obtain the tensile molding.

The packaging vessel that is obtained by oxygen-absorbing multilayer structure of the present invention can hold: liquid drinks such as milk, fruit juice, japanese wine, whisky, liquor, coffee, tea, jelly beverage, healthy beverage for example; Seasonings such as sauce, sauce, soy sauce, sauce, liquid Normal juice soup, mayonnaise, bean flour sauce, ground spicy material; Pasty foods such as jam, cream, chocolate paste, yogurt, jelly; Liquid soup, boil the liquid type food of representatives such as liquid processed food such as product, pickles, stew; Perhaps life face such as buckwheat noodles, noodles, Chinese noodle soup and boil face; Husked rice goods classes such as rice class before the culinary arts such as polished rice, damping rice, disposable rice or the rice of having cooked, kedgeree, RED BEAN RICE, congee; The employed lunch box of high-moisture food, convenience store of representatives such as powder such as powder soup material, soup stock seasonings; Other agricultural chemicals or agrochemical solid state or liquid pharmaceutical chemicals; The medicine of liquid and pulpous state; Toiletry such as astringent, cosmetic cream, cosmetic emulsion, hair care agent, hair dye; Lotion classes such as shampoo, perfumed soap, lotion; Various article such as electronic material, recording medium.By the packaging vessel that oxygen-absorbing multilayer structure of the present invention obtains, the oxygen of internal tank is absorbed by the oxygen uptake layer, therefore can prevent the oxidation corrosion of article etc., can keep good quality for a long time.

Embodiment

Below, enumerate Production Example and embodiment and further specify the present invention.Need to prove that unless otherwise specified, then " part " in each example and " % " are quality criteria.

Various characteristics is estimated in accordance with the following methods.

[weight-average molecular weight of cyclized product of conjugated diene polymer (Mw)]

Adopt gel permeation chromatography, try to achieve as the polystyrene conversion molecular weight.

[the unsaturated link(age) decrement of cyclized product of conjugated diene polymer]

With reference to following document (i) and the (ii) middle method of putting down in writing, try to achieve by proton N MR mensuration.

(i) M.A.Golub and J.Heller, Can.J.Chem., the 41st volume, 937 (1963).

(ii) Y.Tanaka and H.Sato, J.Polym.Sci:Poly.Chem.Ed., the 17th volume, 3027 (1979).

In the conjugated diene monomeric unit part in conjugated diolefin polymer, when the peak area that the total proton peak area after the peak area that is SBT with the total proton peak area before the cyclization, directly is combined in the proton on two keys is SBU, cyclization is SAT, directly be combined in the proton on two keys was SAU, the peak area ratio (SB) that then directly is combined in the proton on two keys before the cyclization was:

SB＝SBU/SBT

The peak area ratio (SA) that directly is combined in the proton on two keys behind the cyclization is:

SA＝SAU/SAT

Therefore, the unsaturated link(age) decrement is tried to achieve by following formula:

Unsaturated link(age) decrement (%)=100 * (SB-SA)/SB

[oxygen concn] and [oxygen absorption rate]

The oxygen-absorbing resin composition film is cut into the size of 100mm * 100mm, put into the aluminium bag (Sakurai produce corporate system of 300mm * 400mm size, trade(brand)name " Hiretort AlumiALH-9 ") in, inner air is removed the back fully, and to enclose oxygen concn be 20.7% 100cc air, preserved 5 days down at 23 ℃, use oxymeter (U.S. Ceramatic corporate system, trade(brand)name " Food Checker HS-750 ") to measure afterwards.

Calculate oxygen absorption rate (cc/100cm by gained oxygen concn and the oxygen concn before on-test 20.7% ²My god) (20 μ m) [its meaning is meant that seeing through thickness every day is that 20 μ m, sectional area are 100cm ²The volume (cc) of oxygen of film].This numerical value is big more, shows that oxygen absorption rate is excellent more.

[oxygen absorbed]

Accurately take by weighing 0.2～0.3g oxygen-absorbing resin composition film, rest in the air circulating type baking oven that temperature is controlled at 60 ℃, follow the trail of its changes in weight (increase) in time.Think that the weight increase of oxygen-absorbing resin composition film all comes from the oxygen absorption, obtains the oxygen amount that 1g oxygen-absorbing resin composition film is absorbed.

This numerical value is big more, shows that oxygen absorbed is excellent more.

[stink after the oxygen uptake]

The oxygen-absorbing resin composition film is cut into the size of 100mm * 100mm, put into the aluminium bag (Sakurai produce corporate system of 300mm * 400mm size, trade(brand)name " Hiretort AlumiALH-9 ") in, inner air is removed the air that 100cc is enclosed in the back fully, Kaifeng after preserving 15 days under 25 ℃, by following standard evaluation stink, get the mean value of its scoring by 5 syndics.The little stink of marking is less.

Be destitute of smell fully ... scoring 0

Few stink ... scoring 1

A little stink ... scoring 2

Some stink ... scoring 4

Unusual intensive stink ... scoring 5

(reference example 1)

Be cut into the foursquare polyisoprene of 10mm (73% cis-1 with 300 parts, Unit 4,22% anti-form-1, Unit 4,5%3,4-unit, weight-average molecular weight are 154,000) and 700 parts of hexanaphthenes together pack into and possess in the voltage-resistant reactor of stirrer, thermometer, reflux condensing tube and nitrogen ingress pipe.Nitrogen displacement post-heating to 75 ℃ will be carried out in the reactor, stir and be dissolved in polyisoprene in the hexanaphthene fully down, add 2.19 parts of tosic acid (in toluene, carry out reflux dewatering make amount of moisture be product below the 150ppm) afterwards, make temperature be no more than 80 ℃, carry out cyclization.React after 7 hours, add 25% aqueous sodium carbonate that contains 0.84 part of yellow soda ash, stopped reaction.Remove by the azeotropic reflux dewatering under 80 ℃ anhydrate after, using the aperture is that the glass fibre filter of 2 μ m is removed the catalyst residue in the system, obtains the solution of cyclized product of conjugated diene polymer (A).The weight-average molecular weight of gained cyclized product of conjugated diene polymer (A) is 141,000, and the unsaturated link(age) decrement is 48.9%.

(embodiment 11)

Adding the oxidation inhibitor-sulfo-divinyl be equivalent to the amount of 100ppm with respect to cyclized product of conjugated diene polymer (A) in the solution of 300 parts of cyclized product of conjugated diene polymer (A) that above-mentioned reference example 1 obtains, pair [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] (Ciba SpecialtyChemicals corporate system, trade(brand)name " Irganox1010 ") and be equivalent to the Phosphorus oxidation inhibitor-2 of 200ppm, 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " Adekastab HP-10 ") and (B1-1) (Polyplastic corporate system of 700 parts of cyclic olefin resin-ethylene-norbornene copolymers (norbornylene/ethene ratio of components=65/35), trade(brand)name " TOPAS 8007X "), heat up in a steamer a part of hexanaphthene in the solution afterwards, carry out vacuum-drying again and remove toluene, obtain cyclized product of conjugated diene polymer (A)/ethylene-norbornene copolymer (B1-1) mixture of solid state.Mixture is pulverized, used minor axis mixing extruder (shape of the mouth as one speaks φ 3mm * 1 hole) to make ball, obtain the bead p11 of oxygen-absorbing resin composition of the present invention.

Need to prove that ethylene-norbornene copolymer (B1-1) has the structure shown in the formula (3), the bond dissociation energy of the c h bond in the formula shown in the arrow is 4.13eV.

(embodiment 12)

Except using 3, the hydride of 4-polyisoprene (25% cis-1,4-structure isoprene unit, 11% anti-form-1,4-structure isoprene unit, 63%3,4-structure isoprene unit, weight-average molecular weight are 252,000 hydride) (B1-2) replace ethylene-norbornene copolymer (B1-1) in addition, carry out same operation, obtain the bead p12 of oxygen-absorbing resin composition of the present invention with embodiment 1.

Need to prove, 3, the hydride of 4-polyisoprene (B1-2) has the structure shown in the formula (8), and the bond dissociation energy of the c h bond in the formula shown in the arrow is 4.17eV.

(comparative example 11)

Except using 1, hydride (86% cis-1 of 4-polyisoprene polymkeric substance, 4-structure isoprene unit, 12% anti-form-1,4-structure isoprene unit, 2%3,4-structure isoprene unit, weight-average molecular weight are 136,000 hydride) (C-1) replace ethylene-norbornene compound copolymer (B1-1) in addition, carry out same operation with embodiment 1, obtain the cyclized product of conjugated diene polymer (A)/1 of solid state, hydride (C-1) mixture of 4-polyisoprene polymkeric substance.Mixture is pulverized, used minor axis mixing extruder (shape of the mouth as one speaks φ 3mm * 1 hole) to make ball, obtain oxygen-absorbing resin composition bead pc11.

Need to prove, 1,4-polyisoprene hydride (C-1) has the structure shown in the formula (2), and the bond dissociation energy of the c h bond in the formula shown in the arrow is 4.24eV.

(comparative example 12)

Except using new LDPE (film grade) (MFR=4.0, bright dipping petroleum chemistry corporate system, trade(brand)name " Moretec 0438 ") (C-2) replaces ethylene-norbornene compound copolymer (B1-1) in addition, carry out same operation, obtain oxygen-absorbing resin composition bead pc12 with embodiment 1.

Need to prove that new LDPE (film grade) (C-2) has the structure shown in the formula (9), the bond dissociation energy of the c h bond in the formula shown in the arrow is 4.30eV.In the formula (9), R represents chain alkyl.

The composition of bead p11, p12, pc11 and pc12 etc. is summarised in the table 1.

[table 1]

(embodiment 13～14, comparative example 13～14)

(evaluation of the stink after oxygen concn, oxygen absorption rate and the oxygen uptake)

Each bead p11, the p12, pc11 and the pc12 that use embodiment 11～12 and comparative example 11～12 to make, on the Labo-Plastomill single screw extrusion machine, connect the T shape of the mouth as one speaks and biaxial stretch-formed testing apparatus (making society of institute system) by the smart mechanism of Japan, by extrusion molded, obtain film f11, f12, fc11 and the fc12 of wide 100mm, thick 20 μ m respectively.The size that above-mentioned film is cut into 100mm * 100mm is as test film, estimates the stink after oxygen absorbed, oxygen absorption rate and the oxygen uptake.The results are shown in Table 2.

[table 2]

	Embodiment 13	Embodiment 14	Comparative example 13	Comparative example 14
					Film	f11	f12	fc11	fc12
Oxygen absorbed (cc/g)	108	106	45	42
					Oxygen absorption rate (cc/100cm 2My god) (20 μ m)	1.63	0.76	0.10	0.00
Stink after the oxygen uptake	1.4	2.1	2.5	2.3

As shown in Table 2:

Has bond dissociation energy as the resin (A1) (being cyclized product of conjugated diene polymer) of the c h bond below the 3.70eV with to have bond dissociation energy (be ethylene-norbornene copolymer (B1-1 among the embodiment 11) or 3 greater than 3.70eV and as the resin (B1) of the c h bond below the 4.20eV using, the hydride of 4-polyisoprene (B1-2 among the embodiment 12)) among the embodiment 11～12, oxygen absorbed and oxygen absorption rate under the room temperature are big, when particularly using ethylene-norbornene copolymer (being B1-1), the stink after the oxygen uptake is few (embodiment 13) also.

With respect to this, when the resin that uses bond dissociation energy greater than 4.20eV (C-1 or C-2) replaces having bond dissociation energy greater than 3.70eV and as the resin (B1) of the c h bond below the 4.20eV (comparative example 11～12), oxygen absorbs and almost or fully not to carry out, and can also feel stink after the oxygen uptake.

Think this be because, have bond dissociation energy in embodiments of the present invention and accepted the free radical that produces by cyclized product of conjugated diene polymer greater than 3.70eV and for resin (B1) high-level efficiency of c h bond below the 4.20eV, improved the oxygen uptake performance under the room temperature, and particularly in embodiment 11, because resin (B1) has alicyclic structure, it also is not easy to decompose even c h bond dissociates, so the generation of stink is also few.

(embodiment 21)

Adding the oxidation inhibitor-sulfo-divinyl be equivalent to the amount of 100ppm with respect to cyclized product of conjugated diene polymer (A) in the solution of 300 parts of cyclized product of conjugated diene polymer (A) that above-mentioned reference example 1 obtains, pair [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] (Ciba SpecialtyChemicals corporate system, trade(brand)name " Irganox1010 ") and be equivalent to the Phosphorus oxidation inhibitor-2 of 200ppm, 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " Adekastab HP-10 ") and 700 parts of polystyrene (Japan Styrene corporate systems, trade(brand)name " Toyostyrol GP G200C ") (B2-1), heat up in a steamer a part of hexanaphthene in the solution afterwards, carry out vacuum-drying again and remove toluene, obtain cyclized product of conjugated diene polymer (A)/polystyrene (B2-1) mixture of solid state.Mixture is pulverized, used minor axis mixing extruder (shape of the mouth as one speaks φ 3mm * 1 hole) to make ball, obtain the bead p21 of oxygen-absorbing resin composition of the present invention.

Need to prove that polystyrene (B2-1) has the structure shown in the formula (6), the carbon radicals that can be generated by c h bond in the formula shown in the arrow and the reaction of oxygen can be 13.9kcal/mol.

(embodiment 22)

Except using 6-ethylidene-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8, the ring-opening polymerization polymer hydride of 8a-octahydro naphthalene (weight-average molecular weight is 40,000) (B2-2) replaces polystyrene (B2-1) in addition, carry out same operation with embodiment 1, obtain the bead p22 of oxygen-absorbing resin composition of the present invention.

Need to prove 6-ethylidene-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8, the ring-opening polymerization polymer hydride of 8a-octahydro naphthalene has the structure shown in the formula (10), and the carbon radicals that can be generated by c h bond in the formula shown in the arrow and the reaction of oxygen can be 21.8kcal/mol.

(comparative example 21)

(MFR 7.0 except using polypropylene, Japan Polypro corporate system, trade(brand)name " WintecWFX4T ") (C-3) replaces polystyrene (B2-1) in addition, carry out same operation, obtain cyclized product of conjugated diene polymer (A)/polypropylene (C-3) mixture of solid state with embodiment 1.Mixture is pulverized, used minor axis mixing extruder (shape of the mouth as one speaks φ 3mm * 1 hole) to make ball, obtain the bead pc21 of oxygen-absorbing resin composition.

Need to prove that polypropylene (C-3) has the structure shown in the formula (5), the carbon radicals that can be generated by c h bond in the formula shown in the arrow and the reaction of oxygen can be 28.4kcal/mol.

(comparative example 22)

Except using new LDPE (film grade) (MFR=4.0, bright dipping petroleum chemistry corporate system, trade(brand)name " Moretec 0438 ") (C-4) in addition, to carry out same operation, obtain the bead pc22 of oxygen-absorbing resin composition with embodiment 21.

Need to prove that new LDPE (film grade) (C-4) has the structure shown in the formula (11), the carbon radicals that can be generated by c h bond in the formula shown in the arrow and the reaction of oxygen can be 24.5kcal/mol.In the formula (11), R represents chain alkyl.

The composition of bead p21, p22, pc21 and pc22 etc. is summarised in the table 3.

[table 3]

^*The 1:C-H key dissociates and the carbon radicals that produces and the reaction energy of oxygen

^*2:6-ethylidene-1,4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8,8a-octahydro naphthalene

(embodiment 23～24, comparative example 23～24)

(oxygen concn after the oxygen uptake and the evaluation of stink)

Each the bead a～d that uses embodiment 21～22 and comparative example 21～22 to make, on the Labo-Plastomill single screw extrusion machine, connect the T shape of the mouth as one speaks and biaxial stretch-formed testing apparatus (making society of institute system) by the smart mechanism of Japan, by extrusion molded, obtain film f21, f22, fc21 and the fc22 of wide 100mm, thick 20 μ m respectively.The size that above-mentioned film is cut into 100mm * 100mm is as test film, estimates oxygen concn and stink after the oxygen uptake.The results are shown in Table 4.

[table 4]

	Embodiment 23	Embodiment 24	Comparative example 23	Comparative example 24
					Film	f21	f22	fc21	fc22
Oxygen absorption rate (cc/100cm 2My god) (20 μ m)	1.46	0.76	0.00	0.00
					Oxygen absorbed (cc/g)	105	106	45	42
Stink after the oxygen uptake	1.4	1.5	2.5	2.3

As shown in Table 4:

Use have generate with the reaction of oxygen can be as the resin (A2) (being cyclized product of conjugated diene polymer) of the c h bond of the carbon radicals below the 10.0kcal/mol and have and generate and the reaction of oxygen can and be resin (B2) (polystyrene (B2-1) or the 6-ethylidene-1 of the c h bond of the carbon radicals below the 22.0kcal/mol greater than 10.0kcal/mol, 4:5,8-two endo-methylene groups-1,4,4a, 5,6,7,8, the ring-opening polymerization polymer hydride of 8a-octahydro naphthalene (B2-2)) among the embodiment 21～22, oxygen absorbed is big, the stink after the oxygen uptake is also few.

With respect to this, generate and the reaction of oxygen can be greater than 10.0kcal/mol and as the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol time (comparative example 21～22) when using to have to generate to replace having greater than the resin (C-3 or C-4) of the c h bond of the carbon radicals of 22.0kcal/mol with the reaction of oxygen, almost or fully do not carry out oxygen and absorb, and can also feel stink after the oxygen uptake.

Think this be because, have in embodiments of the present invention and generate with the reaction of oxygen and can accept to generate the free radical that can produce for the resin (A) (being cyclized product of conjugated diene polymer) of the c h bond of the carbon radicals below the 10.0kcal/mol, improved the oxygen uptake performance under the room temperature greater than 10.0kcal/mol and for resin (B2) high-level efficiency of the c h bond of the carbon radicals below the 22.0kcal/mol with the reaction of oxygen by having.When resin (B2) when having alicyclic structure, even also be not easy to decompose with free radical reaction, so the generation of stink is also few.Reason is also uncertain when resin (B2) is polystyrene, think that main chain is difficult to cut off, so stink is few.

Claims (16)

1. oxygen-absorbing resin composition, said composition comprise that to have bond dissociation energy be the Resin A 1 of the following c h bond of 3.70eV and have bond dissociation energy greater than 3.70eV and be the resin B 1 of the c h bond below the 4.20eV.

2. the oxygen-absorbing resin composition of claim 1, the Resin A 1 that wherein has bond dissociation energy and be a following c h bond of 3.70eV with have bond dissociation energy and count 3/97～50/50 with weight ratio greater than 3.70eV and for the ratio of the resin B 1 of the c h bond below the 4.20eV.

3. each oxygen-absorbing resin composition in the claim 1～2, wherein, in having the Resin A 1 that bond dissociation energy is the c h bond below the 3.70eV, bond dissociation energy is that the number of the following c h bond of 3.70eV is at least more than one in each repeating unit that constitutes Resin A 1.

4. each oxygen-absorbing resin composition in the claim 1～3, the Resin A 1 that wherein has bond dissociation energy and be the following c h bond of 3.70eV is cyclized product of conjugated diene polymer.

5. each oxygen-absorbing resin composition in the claim 1～4 wherein has bond dissociation energy and is cyclic olefin resin greater than 3.70eV and for the resin B 1 of the c h bond below the 4.20eV.

6. the oxygen-absorbing resin composition of claim 5, wherein cyclic olefin resin is ethene-cyclic olefin copolymer.

7. oxygen-absorbing resin composition, said composition comprise have can generate with the reaction of oxygen can be for the Resin A 2 of the c h bond of the carbon radicals below the 10.0kcal/mol and have and can generate with the reaction of oxygen and can and be the resin (B2) of the c h bond of the carbon radicals below the 22.0kcal/mol greater than 10.0kcal/mol.

8. the oxygen-absorbing resin composition of claim 7, wherein have can generate with the reaction of oxygen can for the Resin A 2 of the c h bond of the carbon radicals below the 10.0kcal/mol with have can generate with the reaction of oxygen can greater than 10.0kcal/mol and for the content of the resin B 2 of the c h bond of the carbon radicals below the 22.0kcal/mol than counting 3/97～50/50 with weight ratio.

9. each oxygen-absorbing resin composition in the claim 7～8, wherein, have can generate with the reaction of oxygen can Resin A 2 for the c h bond of the carbon radicals below the 10.0kcal/mol in, can generate with the reaction of oxygen and can in each repeating unit that constitutes Resin A 2, be at least more than one for the number of the c h bond of the carbon radicals below the 10.0kcal/mol.

10. each oxygen-absorbing resin composition in the claim 7～9 wherein has and can generate with the reaction of oxygen and can be cyclized product of conjugated diene polymer for the Resin A 2 of the c h bond of the carbon radicals below the 10.0kcal/mol.

11. each oxygen-absorbing resin composition in the claim 7～10 wherein has and can generate with the reaction of oxygen and can be polystyrene or cyclic olefin resin greater than 10.0kcal/mol and for the resin B 2 of the c h bond of the carbon radicals below the 22.0kcal/mol.

12. each oxygen-absorbing resin composition in the claim 4～10, wherein cyclized product of conjugated diene polymer has the unsaturated link(age) decrement below 60%.

13. the oxygen-absorbing resin composition of claim 12, wherein cyclized product of conjugated diene polymer is the cyclisation thing of polyisoprene rubber or the cyclisation thing of styrene-isoprene block copolymer.

14. oxygen-absorbing film, this film comprise in the claim 1～13 each oxygen-absorbing resin composition.

15. oxygen-absorbing multilayer structure, this multilayered structure comprise the oxygen uptake layer that comprises each oxygen-absorbing resin composition in the claim 1～13.

16. the oxygen-absorbing multilayer structure of claim 15 wherein at least also comprises the gas barrier material layer.