CN1198874C

CN1198874C - Oxygen absorption resin compositions

Info

Publication number: CN1198874C
Application number: CNB001038494A
Authority: CN
Inventors: 田井伸二; 下浩幸; 中谷正和; 高松秀雄; 前田瑞穗
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 1999-03-03
Filing date: 2000-03-03
Publication date: 2005-04-27
Anticipated expiration: 2020-03-03
Also published as: KR100490710B1; CN100384931C; KR20000062720A; CN1266071A; CN1654536A

Abstract

The invention provides oxygen a thermoplastic resin (a) having carbon-carbon double bonds; a gas barrier resin (b) having an oxygen transmission rate of 500 ml.20 mum/m2.day.atm or less (20 DEG C. 65% RH); and a transition metal salt (c). This resin composition and molded articles formed using the resin composition effectively absorb and scavenge oxygen when used to package products susceptible to degradation by oxygen, such as foods and drinks.

Description

Oxygen absorption resin compositions

The present invention relates to be used for susceptibility height, easily the oxygen absorption resin and the resin combination of the wrapping material, container etc. of product, particularly food, beverage, pharmaceuticals, the makeup etc. of deterioration to oxygen.In addition, the invention still further relates to except above-mentioned oxygen absorption, also have the oxygen absorption resin compositions of good gas-barrier property, moisture resistance, fragrance protectiveness and smell shielding.And then, the invention still further relates to and use such composition or the molding of resin, for example wrapping material of food, beverage, pharmaceuticals, makeup etc., container etc.

As everyone knows, the goods to oxygen sensitivity height, easy deterioration can keep this Products Quality by avoiding it that oxygen is exposed, prolong storage life, promptly so-called " Shelf Life ".For example, the oxygen of deterioration food exposes by using wrapping material to suppress under the oxygen atmosphere easily, can keep this food quality, avoid rotting of food.This packing can keep the commodity value of goods more longways, and can reduce because necessary discarded and reprocess required expense.In the food product pack field, the means that several restriction oxygen expose had been developed already.Present normally used means have the atmosphere package of improvement (MAP), vacuum packaging and oxygen screened film packing.The above two are that the atmosphere gas that oxygen concn is low is used for packing, and the latter prevents that physically oxygen from entering pack environment.

Above-mentioned oxygen screened film packing is the most ancient use means, can use all gases shielding resin as mould material.

As such gas-barrier resin, can use vinyl-vinyl alcohol copolymer (below, be called for short EVOH), polymeric amide, polyvinyl chloride, polyacrylonitrile etc. widely.These resins are oxygen or carbonic acid gas shielding excellent material, and the melting shaping, and can be widely used in film for packaging, plate, bottle, container etc.Good thermoplastic resins, particularly polyolefin-based resins layer such as such resin and wet fastness, mechanical characteristics carry out lamination, can be suitable as the laminated plastics wrapping material.For example can bag, shapes such as bottle, cup, pouch are extensive use of in scopes such as food, makeup, medicochemistry medicine, the makeup of washing one's hands as the good container of oxygen shielding.

Though use the shielding of wrapping material oxygen, carbon dioxide etc. of such gas-barrier resin good, but can not be as the glass of purposes such as the metallic substance of purposes such as can or bottling, for the transit dose of gases such as oxygen ad infinitum near 0, but the gas permeation of the amount of can not be ignored in addition.Particularly, worry under the situation of prolonged preservation, because the content oxidation causes downgrade, so wish to improve the oxygen shielding consumingly for the wrapping material of food uses.In addition, also wish when the content of the easy oxidation of packing, by when content pack or filling the time remove the oxygen that is blended in content and the packaging vessel, prevent the content deterioration.For this reason, the Oxygen Scavenger of inclosure is arranged in pack environment or Oxygen Scavenger is blended in the gas-barrier resin, pay the motion of deoxidation function for gas-barrier resin.When particularly in for gas-barrier resin, paying the oxygen absorptive function, can obtain the homogeneous removal effect of whole package interior, and remove the oxygen that passes through the wrapping material wall by remover by remover.For this reason, can make by all oxygen levels of package interior and maintain minimum.

As above-mentioned Oxygen Scavenger, known have an all cpds, but, proposed to contain the motion (opening flat 5-115776 number) of the composition of transition-metal catalyst and ethene unsaturated compound (for example polyhutadiene, polyisoprene etc.) with reference to the spy as the Oxygen Scavenger of improvement.In this communique, can enumerate anti-form-1,4-polyisoprene and 1,2-polyhutadiene as the ethene unsaturated compound; Can enumerate cobalt compound as transition-metal catalyst., the deoxidation effect of this Oxygen Scavenger is not necessarily abundant, in addition, according to occasion, exists the elongated problem of property time lag that useful deoxidation begins (below, claim inductive phase).

As the method for in gas-barrier resin, paying oxygen absorptive function (removing function), following method is proposed: 1. by in EVOH, adding the oxide catalyst of transition metal etc., the easy oxidation of this EVOH, the oxygen that sees through and this EVOH are reacted, in EVOH, pay the method (spy opens flat 4-211444 number) of oxygen absorptive function thus; 2. by in polyvinyl chloride, adding the oxide catalyst of transition metal etc., the easy oxidation of this polyvinyl chloride, the oxygen that sees through and this polyvinyl chloride are reacted, in polyvinyl chloride, pay the method (spy opens flat 4-45144 number) of oxygen absorptive function thus; 3. oxygen that disperses in EVOH, sees through by the resin combination that polyolefine and oxide catalyst are formed and the polyolefine among the EVOH react, obtain having the oxygen absorptive function resin combination method (spy opens flat 05-156095 number) and 4. react by oxygen and the Polyolefin and EVOH that makes EVOH, Polyolefin and oxide catalyst cooperate, see through, obtain having the method (spy opens flat 05-170980 number) of the resin combination of oxygen absorptive function.

, the raising effect that the above-mentioned method that 1. reaches 2. exists the oxygen shielding is insufficient, and exists because volume is added the problem that oxide catalyst makes transparent variation.3. the method that reaches 4. also exists the problem that adds polyolefine and make the obvious variation of the transparency in gas-barrier resin.

The object of the present invention is to provide in packing the isochronous removal of goods, particularly food, beverage, pharmaceuticals, makeup of oxygen sensitivity height, easy deterioration or the good composition of effect of absorption oxygen.Another object of the present invention is to provide except removing or absorbing the above-mentioned oxygen effect, also has the oxygen absorption resin compositions of good gas-barrier property, the transparency, moisture resistance, fragrance protectiveness and smell shielding.Another purpose of the present invention is to provide the resin with above-mentioned character.A further object of the invention is to use above-mentioned composition or resin, and good moulding product such as above-mentioned oxygen absorption, gas-barrier property are provided.

The present invention relates to oxygen absorption resin compositions, it contains thermoplastic resin (a), the oxygen permeation rate 500ml20 μ m/m with carbon-to-carbon double bond ²Gas-barrier resin (b) and filtering metal salt (c) that dayatm (20 ℃, 65%RH) is following.

In the embodiment preferred, above-mentioned resin combination rate of oxygen absorption is 0.01ml/m ²More than the day.

The invention still further relates to oxygen absorption resin compositions, it is to contain thermoplastic resin (a), the oxygen permeation rate 500ml20 μ m/m with carbon-to-carbon double bond ²The oxygen absorption resin compositions of the gas-barrier resin (b) that dayatm (20 ℃, 65%RH) is following, its rate of oxygen absorption is 0.01ml/m ²More than the day.

In the embodiment preferred, the above-mentioned thermoplastic resin (a) in the above-mentioned 2 kinds oxygen absorption resin compositions contains the carbon-to-carbon double bond of the above ratio of 0.0001eq/g.

In the embodiment preferred, wherein above-mentioned thermoplastic resin (a) is the multipolymer of aromatic ethenyl compound and diolefin.

And then in the preferred embodiment, wherein above-mentioned thermoplastic resin (a) contains a kind of structural unit of useful structural formula (I) expression at least, and number-average molecular weight is 1000～500000 scope,

[in the formula, R ₁Be alkyl, aryl, alkylaryl or the alkoxyl group of carbonatoms 1～10, R ₂And R ₃Be respectively hydrogen atom, carbonatoms 1～10 alkyl, substituted aryl, non-substituted aryl ,-COOR ₄,-OCOR ₅, cyano group or halogen atom, R ₄And R ₅Be respectively alkyl, aryl, alkylaryl or the alkoxyl group of carbonatoms 1～10 independently].

In addition, in the embodiment preferred, wherein the specific refractory power of above-mentioned gas shielding resin (b) is 1.50～1.56.

In the preferred embodiment, wherein above-mentioned gas shielding resin (b) is select from polyvinyl alcohol resin, polymeric amide, polyvinyl chloride and polyacrylonitrile at least a.

In the embodiment preferred, wherein above-mentioned gas shielding resin (b) is 5～60 moles of % of ethylene content, the vinyl-vinyl alcohol copolymer of saponification deg more than 90%.

In the embodiment preferred, wherein above-mentioned transition metal salt (c) is select from molysite, nickel salt, mantoquita, manganese salt, cobalt salt at least a.

In the embodiment preferred, the above-mentioned transition metal salt (c) that wherein contains, being converted into metallic element is the ratio of 1～5000ppm.

In the embodiment preferred, the difference of the specific refractory power of wherein above-mentioned thermoplastic resin (a) and gas-barrier resin (b) is below 0.01.

And then in the embodiment preferred, the above-mentioned thermoplastic resin (a) that wherein contains is 0.1～30 weight %, and to contain above-mentioned gas shielding resin (b) be the ratio of 99.9～70 weight %.

In the embodiment preferred, wherein the particle that is made of above-mentioned thermoplastic resin (a) is dispersed in the matrix of above-mentioned gas shielding resin (b).

The present invention and then relate to oxygen absorption resin compositions, it is a kind of structural unit that 1000～500000 scopes and having are used structural formula (I) expression at least that said composition contains its number-average molecular weight, and the carbon-to-carbon double bond that is imported in the resin by this structural unit is thermoplastic resin (a) more than the 0.0001eq/g and the transition metal salt (c) that is converted into metallic element 1～10000ppm

In the embodiment preferred, its rate of oxygen absorption is 0.01ml/m ²More than the day.

In addition, in the embodiment preferred, in the said structure formula (I), R ₁Be methyl, R ₂And R ₃It is respectively hydrogen atom.

And then in the embodiment preferred, wherein above-mentioned thermoplastic resin (a) has the structural unit that is derived by aromatic ethenyl compound.

In the embodiment preferred, wherein above-mentioned thermoplastic resin (a) mainly is that the polyisoprene blocks and the polystyrene block that contain structural formula (I) constitute.

In addition, in the embodiment preferred, wherein above-mentioned thermoplastic resin (a) is the ternary block polymer that polyisoprene blocks-polystyrene block of polystyrene block-contain structural formula (I) constitutes.

In the embodiment preferred, and then still contain the resin combination of above-mentioned thermoplastic resin (a) thermoplastic resin in addition.

In the preferred embodiment, wherein above-mentioned thermoplastic resin (a) thermoplastic resin in addition is oxygen permeation rate 500ml20 μ m/m ²The gas-barrier resin (b) that dayatm (20 ℃, 65%RH) is following.

In the preferred embodiment, wherein the particle that is made of above-mentioned thermoplastic resin (a) is dispersed in the matrix of above-mentioned gas shielding resin (b).

The invention still further relates to the oxygen absorption thermoplastic resin, its number-average molecular weight is 1000～500000 scope, and have a kind of structural unit of using structural formula (I) expression at least, and the carbon-to-carbon double bond that imports in the resin with this structural unit is that 0.0001eq/g is above, rate of oxygen absorption is 0.01ml/m ²More than the day.

The invention still further relates to the moulding product that contain above-mentioned any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin.

The invention still further relates to multilayer structure making with the layer that contains above-mentioned any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin.

The invention still further relates to laminated vessel with the layer that contains above-mentioned any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin.

The invention still further relates to the layer that contains above-mentioned any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin formation, and holostrome thickness is the laminated vessel that the following multilayer film of 300 μ m constitutes.

The invention still further relates to and contain the laminated vessel that the layer that is made of above-mentioned any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin reaches the layer that is made of the thermoplastic polyester layer.

The present invention and then relate to the lid that the gasket seal that is made of above-mentioned any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin is installed.

In this manual, " removal " oxygen is meant from give the environment with oxygen absorption, oxygen consumed or its amount is reduced.

In the present invention, can use thermoplastic resin (a) with carbon-to-carbon double bond.Because thermoplastic resin (a) has carbon-to-carbon double bond at its intramolecularly, so can react efficiently with oxygen, obtains deoxidation function (oxygen absorptive function).Above-mentioned carbon-to-carbon double bond comprises conjugated double bond, but does not comprise the multiple bond that is contained on the aromatic nucleus.

This carbon-to-carbon double bond preferably is contained in the thermoplastic resin (a) with the ratio more than the 0.0001eq/g.This pair key is more preferably with more than the 0.0005eq/g and then preferably with more than the 0.001eq/g, and most preferably the above ratio of 0.002eq/g is contained in the thermoplastic resin (a).When carbon-to-carbon double bond contains quantity not sufficient 0.0001eq/g, the situation that has the deoxidation effect of inadequate situation of rate of oxygen absorption and composition of the present invention fully not improve.

The molecular weight of thermoplastic resin (a), as mentioned above, preferably 1000～500000.And then, if consider moulding, the processibility of resin combination, the mechanical properties of moulding product therefrom and to the dispersiveness of thermoplastic resin (a) thermoplastic resin in addition, preferably 10000～250000,40000～200000 scopes most preferably.

When the molecular weight less than 1000 of thermoplastic resin (a), the easiness of worrying moulding, processing or the use of resin combination significantly reduces and mechanical propertiess such as intensity when worrying as the moulding product and degree of drawing also reduce.And then, mixing with thermoplastic resin (a) thermoplastic resin (for example gas-barrier resin) in addition when using, the dispersed reduction, its result is because gas-barrier property has the problem of deoxidation performance reduction.Surpass at 500000 o'clock in number-average molecular weight, also have the moulding of resin combination, the problem that processibility reduces.And then, mix with thermoplastic resin (a) thermoplastic resin in addition when using, also exist dispersedly reduce, because gas-barrier property and problem that the deoxidation performance reduces.

The carbon-to-carbon double bond of thermoplastic resin (a) generally is from diolefin, but also is not limited thereto.As the example of the synthetic diolefin that is used for the used thermoplastic resin of the present invention (a), can enumerate isoprene, divinyl, 2-ethyl-divinyl, 2-butyl-divinyl etc.As diolefin, can only use 1 composition, also can use 2 compositions simultaneously, have no particular limits.

The carbon-to-carbon double bond of the thermoplastic resin (a) that the present invention is used can be contained on the main chain, also can be contained on the side chain, but be contained in the two strands amount of side chain many (that is, the base with carbon-to-carbon double bond is many on side chain), because rate of oxygen absorption is fast, so be ideal.For example as the synthesis material of thermoplastic resin (a), when using isoprene or divinyl, the ethylenic linkage content in the thermoplastic resin that obtains (a), preferably more than 10%, more preferably more than 20%, most preferably more than 30%.So-called ethylenic linkage content be meant in polymkeric substance, in the unit from all diene, form ethylenic linkage (CH ₂=CH-) the ratio of (1,2 addition polymerization).In addition, the two keys that exist after the polymerization, in the scope that does not hinder present composition performance, also it doesn't matter promptly to use its part of hydrogen reduction.

For the content with ethylenic linkage reaches more than 10%, when diolefins such as polymerization isoprene,, can use Lewis base as co-catalyst.Example as Lewis base, can enumerate glycol ethers, the N of the ethers, ethylene glycol diethyl ether, glycol dimethyl ether etc. of dme, diethyl ether, methyl ethyl ether, tetrahydrofuran (THF) etc., N, N ', contains the amine of ethers such as N-methylmorpholine, N-ethylmorpholine at the tertiary amines of N '-Tetramethyl Ethylene Diamine (TMEDA), Triethylene Diamine etc.The initiator described later of per 100 weight parts uses the Lewis base of 0.1～400 weight part.

As solvent, can use organic solvent inert.Particularly carbonatoms is 6～12 hydrocarbon, and for example hexane, heptane, octane, decane and their cyclic analogs are fit to.The solvent of fragrance family, for example toluene, benzene, dimethylbenzene etc. also are fit to.Polymerization is carried out under-20～80 ℃ temperature range, 1～50 hour scope usually.

The thermoplastic resin that obtains like this (a) is owing to be rich in two keys, so easily oxidation, oxygen absorption can be good on side chain.

As the thermoplastic resin (a) that is fit to, for example can enumerate and have with unitary at least a kind shown in the following structural formula (I), number-average molecular weight resin in 1000～500000 scopes.

In the definition of said structure formula (I), the carbonatoms of aryl is preferred 6～10, and the carbonatoms of alkylaryl is preferred 7～11, the carbonatoms of alkoxyl group preferred 1～10.Can enumerate conduct, the example of alkyl be methyl, ethyl, propyl group, butyl, and the example of aryl is a phenyl, and the example of alkylaryl is a benzyl, and the example of alkoxyl group is the example of methoxyl group, oxyethyl group, halogen atom, is the chlorine atom.

The structural formula (I) that thermoplastic resin (a) has is as R ₁(when particularly having the structural unit that isoprene, 2-ethyl divinyl, 2-butyl polymerizing butadiene are formed) when having the alkyl of carbonatoms 1～3, thermoplastic resin (a) are easily oxidized, are ideal as the oxygen absorption resin.Particularly, thermoplastic resin (a), as the structural unit with structural formula (I) expression, containing the structural unit that isoprene polymerization is formed (is the R of structural formula (I) ₁Be methyl, R ₂And R ₃When being hydrogen atom) occasion because two keys (ethylenic linkage) of this structural unit react effectively with oxygen, so the easy especially oxidation of thermoplastic resin (a), oxygen absorption are good.And isoprene obtains easily, with the easy polymerization of other monomer, so also be suitable from the synthetic cost of thermoplastic resin (a).

The thermoplastic resin (a) that the present invention is used, the preferably multipolymer of aromatic ethylene compound and diolefin.When thermoplastic resin (a) is its polymers of aromatic ethylene compound and diolefin, from the two keys and the oxygen of diolefin react easily, oxygen shielding and deoxidation effect can improve.And then, regulate the copolymerization ratio of aromatic ethylene compound and diolefin, can improve moulding, the processibility of thermoplastic resin (a), in addition, also can make changes in hardness.By regulating the copolymerization ratio of aromatic ethylene compound and diolefin, the specific refractory power that can regulate the thermoplastic resin (a) that obtains.Therefore, as described below, when composition of the present invention contains gas-barrier resin (b), can set the difference of the specific refractory power of the specific refractory power of this gas-barrier resin (b) and thermoplastic resin (a) smaller, its result can obtain the good goods of the transparency.Like this, composition of the present invention can be adjusted to the rerum natura that is fit to various wrapping material.

As the synthetic aromatic ethylene compound that is used for the used thermoplastic resin of the present invention (a), can enumerate vinylbenzene, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-vinyl naphthalene, 3-vinyl toluene, 4-propylstyrene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, 2-ethyl-4-benzyl vinylbenzene, 4-(phenyl butyl) vinylbenzene.Wherein, from cost and easy polymeric viewpoint, most preferably vinylbenzene.

When thermoplastic resin (a) was the multipolymer of aromatic ethylene compound and diolefin, this multipolymer can be random copolymers, segmented copolymer, graft copolymer or their mixture, is not particularly limited.From the mechanical characteristics of manufacturing and thermoplastic resin (a), use the viewpoint of easiness and rate of oxygen absorption, segmented copolymer preferably.

Thermoplastic resin (a) is not particularly limited for its manufacture method, but preferably uses anionic polymerization when being segmented copolymer.At this moment, the number-average molecular weight of aromatic ethylene compound block, preferably 300～100000 scope, more preferably 1000～50000 scope, 3000～50000 scope most preferably.During the molecular weight less than 300 of aromatic ethylene compound block, have the melt viscosity of thermoplastic resin (a) low, the problem of moulding, processibility or the usability difference of resin combination.And then, the low trend of mechanical properties such as intensity and degree of drawing are arranged during as the moulding product.And then as described below, when the state that thermoplastic resin (a) is dispersed in other such resins of gas-barrier resin (b), the dispersiveness of this thermoplastic resin (a) reduces, its result, and the deoxidation performance is low.Surpass at 100000 o'clock at the molecular weight of aromatic ethylene compound block, because the melt viscosity height has damaged thermoplasticity, so the moulding of resin combination, processibility reduce.In addition, because above-mentioned dispersiveness is also low, its result, the trend that has the deoxidation performance to reduce.

The block form of segmented copolymer A (BA) _n, (AB) _nExpression.At this, A represents that the block, the B that are made up of aromatic ethylene compound represent that the block, the n that are made up of diolefin are the integers more than 1.

The thermoplastic resin (a) that the present invention is used, preferably 2 yuan of segmented copolymers or 3 yuan of segmented copolymers, most preferably 3 yuan of segmented copolymers.Wherein, the block of being made up of aromatic ethylene compound is a polystyrene block, and the block of being made up of diolefin is a polyisoprene, sees it is suitable from cost and polymerization easiness viewpoint.Particularly, during 2 yuan of segmented copolymers that thermoplastic resin (a) is made up of polyisoprene blocks that contains structural formula (I) and polystyrene block, from the polymerization easiness, use the viewpoint of easiness, rate of oxygen absorption and cost, be ideal.During 3 yuan of segmented copolymers that thermoplastic resin (a) is made up of the polyisoprene blocks-polystyrene block of polystyrene block-contain structural formula (I), except polymerization easiness, use easiness, rate of oxygen absorption and cost are low, from improving mechanical properties, even more ideal.

And then thermoplastic resin of the present invention (a) preferably disperses peak temperature-40 ℃～60 ℃ scopes by the leading of tan δ of diolefin deutero-block.When the main dispersion peak temperature of tan δ is lower than-40 ℃, the trend that rate of oxygen absorption is slack-off, the deoxidation performance reduces is arranged.When the main dispersion peak temperature of tan δ is higher than 60 ℃, the trend that rate of oxygen absorption is slow at low temperatures, the deoxidation performance reduces is arranged.If consider the deoxidation performance, by the main peak temperature that disperses of the tan δ of diolefin deutero-block, preferably-20 ℃～40 ℃ scope, most preferably-10 ℃～30 ℃ scope.

The segmented copolymer of aromatic ethylene compound and diolefin can obtain by following the whole bag of tricks.Can enumerate as initiator alkyl lithium compounds, aromatic ethenyl compound and diolefin are carried out polymerization, by coupler carry out the method for coupling or with two lithium based compounds as initiator, with diolefin and aromatic ethenyl compound step by step polymeric method etc. but not limited by these as the representative method.As the example of alkyl lithium compounds, the carbonatoms that can enumerate alkyl residue is 1～10 alkylate.Particularly preferably be lithium methide, lithium ethide, benzyl lithium and butyllithium.

As coupler, can use methylene dichloride, methylene bromide, ethylene dichloride, ethylene dibromide etc.As the example of two lithium compounds, can enumerate naphthalene two lithiums, low polystyrene two lithiums, hexyl benzene two lithiums etc.Usage quantity, for being used for polymeric total monomer 100 weight parts, initiator is that 0.01～0.2 weight part, coupler are that 0.04～0.8 weight part is to suit.

Segmented copolymer can be by in the poor solvent that polymerization liquid is joined methyl alcohol etc., and after solidifying, heating or drying under reduced pressure perhaps splash into polymerization liquid in the boiled water, with the solvent azeotropic, remove after, heating or drying under reduced pressure and obtain.

Above-mentioned thermoplastic resin (a) can be single resin, also can be the mixture that various kinds of resin is formed.When being mixture, when expecting the good moulding product of the transparency, be the film of 20 μ m for thickness, to the haze value of its inside, preferably below 10%.

Above-mentioned thermoplastic resin (a), owing to be subjected to oxidation easily on its structure, for example oxidation in order to prevent to preserve also can recommend to add in advance antioxidant.

As above-mentioned examples of antioxidants, can enumerate 2,5-two-tertiary butyl benzoquinones, 2,6-two-Butylated Hydroxytoluene, 4,4 '-thiobis-(6-tert-butyl phenol), 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), octadecyl-3-(3 ', 5 '-two-tertiary butyl-4 '-hydroxy phenyl) propionic ester, 4,4 '-thiobis-(6-tert.-butyl phenol), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, tetramethylolmethane-four (3-lauryl thiopropionate), 2,6-two-(tertiary butyl)-4-sylvan (BHT), 2,2 '-methylene-bis-(6-Butylated Hydroxytoluene), triphenyl phosphite, tricresyl phosphite-(nonyl phenyl ester), Tyox B etc.

The addition of antioxidant is according to the composition kind in the composition, contain its optimum amounts of decision such as proportional, application target, preservation condition.Generally, when being rich in antioxidant, can hinder the reaction of the oxygen that in the resin combination that contains thermoplastic resin (a), sees through and this thermoplastic resin (a).For this reason, the oxygen shielding that can not give full play to the present composition and the situation of deoxidation function are arranged.On the other hand, do not containing antioxidant or its content when very few, just reacting when thermoplastic resin (a) is preserved or during melt-processed, and when reality is used, oxygen absorption can be descended with oxygen.

Under atmosphere of inert gases, preserve or the state than lower temperature or nitrogen envelope under, when fusion cooperates thermoplastic resin (a) to make resin combination, even the amount of antioxidant also can less.

In addition, for promotes oxidn, when adding the oxide catalyst (c) of transition metal salt composition when fusion cooperates, thermoplastic resin (a) also can obtain having the resin combination of good oxygen uptake ability even contain a certain amount of antioxidant.The oxidation preventive content of this moment is 0.01～1 weight %, preferably 0.02～0.5 weight %.This antioxidant as mentioned above, can join in the thermoplastic resin (a) in advance or also can add when mixing each composition of oxygen absorption resin compositions in the same manner with other general additives described later.

Be contained in the oxygen permeation rate of the gas-barrier resin (b) in the oxygen absorption resin compositions of the present invention, preferably the measured value under 20 ℃, the condition of relative humidity 65% is 500ml20 μ m/m ²Below the dayatm.This value is meant that the oxygen permeation rate when being converted into 20 μ m thickness is 500ml/m ²Below the dayatm.If oxygen permeation rate surpasses 500ml20 μ m/m ²During dayatm, gas-barrier property can not be given full play to.In order to obtain good gas-barrier property, preferably the oxygen permeation rate of gas-barrier resin (b) is little.100ml20 μ m/m preferably ²Dayatm is following, 20ml20 μ m/m more preferably ²Dayatm is following, 5ml20 μ m/m most preferably ²Below the dayatm.

Such gas-barrier resin (b) is cooperated with the thermoplastic resin with carbon-to-carbon double bond (a), except shroud of gas effect with resin (b), also bring into play the oxygen of resin (a) and catch effect, its result can obtain having the resin combination of high gas-barrier property.

The specific refractory power of the gas-barrier resin (b) that the present invention is used preferably 1.50～1.56.If break away from this scope, as described below, the resin that the difference of the specific refractory power of the specific refractory power of gas-barrier resin (b) and thermoplastic resin (a) becomes greatly, obtains or the transparency of resin combination reduce.Generally, because the specific refractory power of thermoplastic resin (a) with carbon-to-carbon double bond is mostly in above-mentioned scope, so the refringence of thermoplastic resin (a) and gas-barrier resin (b) diminishes easily, its result can obtain transparent good resin combination.The specific refractory power of gas-barrier resin (b) is preferably more than 1.51, most preferably more than 1.52.In addition, preferably below 1.55, most preferably below 1.54.

The kind of gas-barrier resin (b) has no particular limits.As mentioned above, be 500ml20 μ m/m as satisfying oxygen permeation rate ²Below the dayatm, and specific refractory power is the example of the gas-barrier resin (b) of 1.50～1.56 condition, can enumerate representative resins such as EVOH, polymeric amide, polyvinyl chloride, polyacrylonitrile, but be not limited to these resins.

As gas-barrier resin (b), can enumerate polyvinyl alcohol resin (b1), polymeric amide (b2), polyvinyl chloride (b3) and polyacrylonitrile (b4) etc.

In the above-mentioned gas shielding resin (b), polyvinyl alcohol resin (b1) is to use alkaline catalysts etc., and the monomer-polymer of vinyl ester or vinyl ester and other monomeric multipolymers (the particularly multipolymer of vinyl ester and ethene) are carried out obtaining after the saponification.

As above-mentioned vinyl ester, can enumerate vinyl acetate between to for plastic as representative compounds, but also can use other fatty acid vinyl ester (propylene and ethylene ester, trimethylacetic acid vinyl acetate etc.).

The saponification deg of the vinyl ester composition of above-mentioned polyvinyl alcohol resin, preferably more than 90%, more preferably more than 95%, most preferably more than 97%.During 90 moles of % of saponification deg less than, the gas-barrier property under the high humidity is reduced.In addition, when ethylene-vinyl alcohol copolymer (EVOH), the thermostability variation, the gel pit takes place in moulding product easily that obtain.

When the title complex of polyvinyl alcohol resin the polyvinyl alcohol resin 2 kind or more different by saponification deg is formed, can with by the mean value that cooperates weight ratio to calculate as saponification deg.The saponification deg of such polyvinyl alcohol resin can be tried to achieve by nucleus magnetic resonance (NMR) method.

As the used polyvinyl alcohol resin of the present invention (b1) from melting be shaped, gas-barrier property under high humidity well, even in above-mentioned gas shielding resin, EVOH also is optimum.

The ethylene content of EVOH, preferably 5～60 moles of %.When 5 moles of % of ethylene content less than, the gas-barrier property under high humidity can reduce sometimes, and melt-shaping is variation also.The ethylene content of EVOH, preferably 10 moles of % above, more preferably 15 moles of % above, most preferably 20 moles more than the %.If when ethylene content surpasses 60 moles of %, can not get sufficient gas-barrier property.Ethylene content preferably 55 moles of % following, most preferably 50 moles below the %.The ethylene content of EVOH can be obtained by nucleus magnetic resonance (NMR) method.

The suitable EVOH that utilizes, its ethylene content is that 5～60 moles of %, saponification degs are more than 90%.

When EVOH is made up of the title complex of the different EVOH more than 2 kinds of ethylene content or saponification deg, will be by the mean value that cooperates weight ratio to calculate as ethylene content or saponification deg.

But when cooperating 2 kinds of EVOH, preferably both ethylene content differences are 15 moles below the %, and the difference of saponification deg is below 10%.In these conditions occasion in addition, diminish the transparency of resin combination layer.From obtaining the good transparency viewpoint, more preferably 10 moles below the % of the differences of ethylene content, most preferably 5 moles below the %.In addition, from obtaining same good transparent viewpoint, the difference of saponification deg is more preferably below 7%, most preferably below 5%.

In addition, under the situation for polyvinyl alcohol resin (b1), particularly EVOH, in the scope that does not hinder the object of the invention, also can contain other monomer on a small quantity as copolymer composition.As the examples of monomers that can constitute copolymer composition, can enumerate the alpha-olefin of propylene, 1-butylene, iso-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.; Unsaturated carboxylic acid, its salt of methylene-succinic acid, methacrylic acid, vinylformic acid, maleic anhydride etc., it is ester, its nitrile, its acid amides, its acid anhydride partially or completely; The vinyl silanes based compound of vinyltrimethoxy silane etc.; Unsaturated sulfonic acid or its salt; The alkyl sulfide alcohols; Vinyl pyrrolidone class etc.

Particularly, in EVOH, when containing 0.0002～0.2 mole of % of vinyl silanes based compound, the extrusion molding together or the matching of the fusion viscosity of the substrate resin during injection forming altogether can be improved, the molding of homogeneous can be made as copolymer composition.At this,, for example can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy-oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane etc. as the vinyl silanes based compound.Wherein, particularly preferably be vinyltrimethoxy silane, vinyltriethoxysilane.

And then, also improve the fusion viscosity of EVOH when in EVOH, adding boron compound, obtaining the homogeneous coextrusion or be effective on the injection-molded article altogether.At this, can enumerate boric acid class, boric acid ester, borate, hydroborons class etc. as boron compound.Particularly, as the boric acid class, can enumerate boric acid, ortho-boric acid, metaboric acid, tetraboric acid etc., as boric acid ester, triethyl borate, trimethyl borate etc. can be enumerated,, an alkali metal salt, alkali earth metal salt, borax of above-mentioned various boric acid classes etc. can be enumerated as borate.In these compounds, preferably boric acid, ortho-boric acid, NaBH ₄

When adding boron compound, convert with boron, its content is 20～2000ppm, 50～1000ppm preferably.The EVOH of torque change in the time of in this scope, can being inhibited heating and melting.When not enough 20ppm, sometimes its effect diminish, if when surpassing 2000ppm, gelation, plasticity variation sometimes easily sometimes.

In EVOH, add an alkali metal salt of 5～5000ppm, also can improve interlayer tackiness and consistency effectively with the alkali metal conversion.

The addition preferably of an alkali metal salt, converting with alkali metal is 20-1000ppm, 30～500ppm preferably.As basic metal, can enumerate lithium, sodium, potassium etc., as an alkali metal salt, can enumerate aliphatic carboxylate, aromatic carboxylic acid salt, phosphoric acid salt, metal complex of monovalence metal etc.For example can enumerate sodium-acetate, Potassium ethanoate, sodium phosphate, Trilithium phosphate, sodium stearate, potassium stearate, ethylene dinitrilotetra-acetic acid sodium salt etc.Wherein, preferably sodium-acetate, Potassium ethanoate, sodium phosphate.

In EVOH, convert to add the phosphide of 2～200ppm with phosphoric, preferably with 3～150ppm, most preferably add phosphorus compound with the ratio of 5～100ppm.Phosphorus concentration in EVOH often has problems on melt-shaping and thermostability during less than 2ppm or greater than 200ppm.When particularly carrying out melt-shaping for a long time, be easy to generate gluey pit or coloring problem.

The kind of adding the phosphorus compound among the EVOH to is not particularly limited.Can use the various acid of phosphoric acid, phosphorous acid etc. and its salt etc.As phosphoric acid salt, also can dihydrogen phosphate, any a kind of form contains in the hydrophosphate, phosphoric acid salt.Phosphatic cation type also is not particularly limited, but preferred phosphoric acid salt is an alkali metal salt, alkali earth metal salt.Wherein, the phosphorus compound that preferably adds with the form of SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, Sodium phosphate dibasic, dipotassium hydrogen phosphate.

In addition, as required, also can being pre-mixed thermo-stabilizer, UV light absorber, oxidation inhibitor, tinting material, filling agent, other resin (polymeric amide, polyolefine etc.) in EVOH, to have added the EVOH of above-mentioned boron compound, an alkali metal salt, phosphorus compound etc. on sale on market.

The suitable melt flow rate (MFR) (MFR) of available EVOH of the present invention (under 210 ℃, 2160g load, according to JIS K7210) is 0.1～100g/10 minute, preferably 0.5～50g/10 minute, most preferably 1～30g/10 minute.

Kind as the polyamide resin (b2) of gas-barrier resin (b) does not have particular restriction.For example can enumerate polycaprolactam (nylon-6), poly-undecanoyl amine (nylon-11), polylauryllactam (PA-12), polyhexamethylene adipamide (nylon-6,6), the independent polymkeric substance of fatty polyamide of poly-12 phosphinylidyne hexanediamines (nylon-6,12) etc.; Hexanolactam/lauryl lactam multipolymer (nylon-6/12), hexanolactam/amino undecyl acid copolymer (nylon-6/11), hexanolactam/omega-amino-n-nonanoic acid multipolymer (nylon-6/9), hexanolactam/adipic acid hexamethylenediamine salt multipolymer (nylon 6/6,6), the own di-ammonium salts multipolymer of hexanolactam/adipic acid hexamethylenediamine salt/lauric acid (nylon-6/6,6/6,12) etc. fatty polyamide multipolymer; Toluene di-ammonium salts (MX-nylon), the own di-ammonium salts multipolymer of the own di-ammonium salts/m-phthalic acid of terephthalic acid aromatic polyamides such as (nylon-6 T/6I) between poly-hexanodioic acid.These polyamide resins can be distinguished use separately, also can mix use more than 2 kinds.

In these polyamide resins, preferably polycaprolactam (nylon-6) or PA 66 (nylon-6,6).

As the used polyvinyl chloride (PVC) RESINS of the present invention (b3), except the homopolymer of vinylchlorid or vinylidene chloride, can enumerate multipolymer with vinyl acetate between to for plastic, maleic acid derivatives, senior alkyl vinyl ether etc.

As the used polyacrylonitrile resin of the present invention (b4), except the homopolymer of vinyl cyanide, can enumerate multipolymer with acrylate etc.

In addition, in the present invention, in the scope that does not hinder the object of the invention, also thermo-stabilizer, UV light absorber, antioxidant, tinting material, filler, softening agent, filling agent, other resins (polyolefine etc.) can be mixed with gas-barrier resin (b) in advance.

Resin combination of the present invention preferably contains transition metal salt (c).This transition metal salt (c), preferably with metallic element be scaled 1～10000ppm, more preferably 5～5000ppm, most preferably the ratio of 10～2000ppm contains.Thus, can promote the dioxygen oxidation reaction of thermoplastic resin (a).For example, be present in the oxygen of the wrapping material inside that obtains by the present composition and the oxygen and the thermoplastic resin (a) that see through in the wrapping material can react efficiently.Its result, the oxygen shielding and the deoxidisation that have improved resin combination of the present invention.But, surpassing when using in the scope of 10000ppm if convert with metallic element at the content of transition metal salt (c), the thermostability of resin combination of the present invention reduces, produces significantly decomposition gas and gelling material.From this viewpoint, the content of transition metal salt (c), preferably above-mentioned scope.When composition of the present invention contained in addition thermoplastic resin of gas-barrier resin etc., thermoplastic resin (a), above-mentioned transition metal salt (c) was at 1～5000ppm, preferably at 5～1000ppm, most preferably 10～500ppm scope contains.

The metal that is used for such transition metal salt (c) is preferably selected from the 1st, the 2nd or the 3rd transition series of periodictable.In proper metal, contain manganese, iron, cobalt, nickel, copper, rhodium, titanium, chromium, vanadium and rubidium, but be not limited to these.In these metals, preferably iron, nickel, copper, manganese and cobalt, more preferably manganese and cobalt, most preferably cobalt.

As the metal balance ion that is used for transition metal salt (c), can enumerate from organic acid or muriatic negatively charged ion, organic acid comprises acetic acid, stearic acid, dimethyl dithiocarbamic acid, palmitinic acid, 2 ethyl hexanoic acid, neodecanoic acid, linolic acid, the acid of appropriate that, oleic acid, resinous acid, n-capric acid and naphthenic acid, but is not limited to these.Particularly preferred salt can be enumerated 2 ethyl hexanoic acid cobalt, new cobalt decanoate and cobalt stearate.Metal-salt also can be to have the so-called iolon of polymkeric substance sexual balance ionic.

Composition of the present invention on the degree of not damaging effect of the present invention, also can contain above-mentioned thermoplastic resin (a) and gas-barrier resin (b) thermoplastic resin (d) in addition.As thermoplastic resin (d), be not particularly limited, can enumerate following resin: Alathon and ethylene copolymer (ethene and following monomeric multipolymer: the alpha-olefin of propylene, 1-butylene, iso-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.; The unsaturated carboxylic acid of methylene-succinic acid, methacrylic acid, vinylformic acid, maleic anhydride etc., its salt, its partially or completely ester, its nitrile, its acid amides, its acid anhydride; The vinyl carboxylates class of vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, sad vinyl acetate, laurostearic acid vinyl acetate, stearic acid vinyl ester, eicosanoic acid vinyl acetate etc.; The vinyl silanes based compound of vinyltrimethoxy silane etc.; Unsaturated sulfonic acid or its salt; The alkanethiol class; Vinyl pyrrolidone class etc.), alfon and propylene copolymer (propylene and following monomeric multipolymer: the alpha-olefin of ethene, 1-butylene, iso-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.; The unsaturated carboxylic acid of methylene-succinic acid, methacrylic acid, vinylformic acid, maleic anhydride etc., its salt, its partially or completely ester, its nitrile, its acid amides, its acid anhydride; The vinyl carboxylates class of vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, sad vinyl acetate, lauric acid vinyl acetate, stearic acid vinyl ester, eicosanoic acid vinyl acetate etc.; The vinyl silanes based compound of vinyltrimethoxy silane etc.; Unsaturated sulfonic acid or its salt; The alkanethiol class; Vinyl pyrrolidone class etc.), the polyolefine of poly 4-methylpene-1, polybutene-1 etc.; The polyester of polyethylene terephthalate, polybutylene terephthalate, poly-naphthoic acid glycol ester etc.; Polystyrene, polycarbonate, polyacrylic ester etc.The selection of thermoplastic resin (d) is to carry out according to the structure and the purposes of the moulding product of making.Such selection factor is well-known on structure and purposes, according to them, selects thermoplastic resin (d).

When manufacturing contains the composition of thermoplastic resin (a) and gas-barrier resin (b) and/or thermoplastic resin (d), preferably to consider thermoplastic resin (a) and resin (b) and/or Combination (d).Because the Combination of these resins, the tissue of the validity of the transparency, detergency, Oxygen Scavenger, shielding, mechanical properties, goods etc. is affected sometimes.

The 1st oxygen absorption resin compositions of the present invention comprises above-mentioned thermoplastic resin (a), gas-barrier resin (b) and transition metal salt (c).

Second oxygen absorption resin compositions of the present invention, it is characterized in that containing thermoplastic resin (a) and gas-barrier resin (b) and rate of oxygen absorption is 0.01ml/m ²More than the day.

The 3rd oxygen absorption resin compositions of the present invention contains thermoplastic resin (a) and transition metal salt (c).

The 4th aspect of the present invention comprises it being the thermoplastic resin with said structure formula (I), and the ratio with regulation contains carbon-to-carbon double bond in this structural formula in this resin, and its rate of oxygen absorption is 0.01ml/m ²The thermoplastic resin of the oxygen absorption that day is above.

The content of each composition of above-mentioned composition has no particular limits.But, as the of the present invention the 1st and the 2nd, in order to obtain the good composition of gas-barrier property, oxygen absorption resin compositions of the present invention preferred normally contain thermoplastic resin (a), contains gas-barrier resin (b) with the ratio of 99.9～70 weight % with the ratio of 0.1～30 weight %.Transition metal salt (c) if when adding, at 1～10000ppm, preferably adds in the scope of 1～5000ppm.

Gas-barrier resin (b) contain proportional less than 70 weight % the time, the transparency of moulding product of laminated vessel etc. of resin combination and the gas-barrier property of oxygen or carbon dioxide gas etc. are reduced.Contain proportional when surpassing 99.9 weight % since thermoplastic resin (a) contain proportional diminishing, so have that rate of oxygen absorption reduces, the trend of carrier of oxygen shielding and deoxidation reduction.The proportional preferred range that contains of the thermoplastic resin in the resin combination (a) is that 1～20 weight %, preferred scope are 2～15 weight %.The proportional preferred range that contains of gas-barrier resin (b) is 80～99 weight %, and most preferred scope is 85～98 weight %.

On the other hand, as the occasion of the present invention the 3rd and the 4th, comparing with gas-barrier property when more paying attention to rate of oxygen absorption, the scheme that does not contain gas-barrier resin (b) also is preferred scheme.

In resin combination of the present invention, at the composition that contains gas-barrier resin (b) etc., thermoplastic resin (a) resin in addition, the particle of recommending thermoplastic resin (a) to form is dispersed in this (a) resin (gas-barrier resin (b) and/or thermoplastic resin (d)) in addition and reaches scheme in the matrix that contains following various additives etc. as required.For example when oxygen absorption resin compositions of the present invention is made of thermoplastic resin (a) and gas-barrier resin (b), the particle of recommending thermoplastic resin (a) to constitute is dispersed in the scheme in the matrix of gas-barrier resin (b).In the various moulding product that the composition of this scheme constitutes, deoxidation and gas-barrier property be lasting easily, can pay on the function that gas-barrier resin thermoplastic resin (a) resins in addition such as (b) has is ideal.The transparency is also good.At this moment, preferably its dispersion particle diameter of the particle of thermoplastic resin (a) composition is below the 10 μ m.If when disperseing particle diameter to surpass 10 μ m, the interfacial area of thermoplastic resin (a) and thermoplastic resin (a) resin in addition diminishes, the reduction of carrier of oxygen shielding the time, the deoxidation performance also reduces.From deoxidation, gas-barrier property and the transparency of the moulding product such as laminated vessel that used resin combination, preferably the median size of dispersive thermoplastic resin (a) particle is preferably below the 5 μ m, most preferably below the 2 μ m.

In the resin combination of the present invention, in the composition that contains gas-barrier resin (b) etc., thermoplastic resin (a) thermoplastic resin in addition, in the difference of the specific refractory power of the specific refractory power of thermoplastic resin (a) and thermoplastic resin (a) resin in addition is 0.01 when following, and the transparency of the moulding product that obtained by said composition is good.The difference of specific refractory power surpasses at 0.01 o'clock, and the moulding product that obtained by resin combination have opaque a little trend.In order to obtain the good transparency, above-mentioned specific refractory power poor, preferably below 0.007, most preferably below 0.005.As the difference with the specific refractory power of thermoplastic resin (a) is gas-barrier resin (b) below 0.01, preferably the ethenol system resin of polyvinyl alcohol, poly-(ethylene-vinyl alcohol) etc., polymeric amide, polyvinyl chloride, polyacrylonitrile etc., but be not limited to these.

In resin combination of the present invention, as required, contain various additives.Example as such additive, oxidation inhibitor, softening agent, thermo-stabilizer (melt stability agent), light trigger, reodorant, UV light absorber, static inhibitor, lubricant, tinting material, filler, siccative, filling agent, pigment, dyestuff, processing aid, fire retardant, anti-blushing agent or other macromolecular compound can be enumerated, in the scope that does not hinder action effect of the present invention, these materials can be contained.

As the thermo-stabilizer in the above-mentioned additive (melt stability agent), can use in the metal-salt (for example calcium stearate, Magnesium Stearate etc.) of hydrotalcite compound, senior aliphatic carboxylic acid more than a kind or 2 kinds.These compounds contents, the preferably ratio of 0.01～1 weight % of resin combination total amount.

When resin combination of the present invention contains hydrotalcite compound, in the layer that resin combination is formed, can prevent through the time jello or the flake that take place, can further improve long run stability.

In addition, when resin combination contains the metal-salt of senior aliphatic carboxylic acid, can prevent through the time jello or the flake that take place, can further improve long-time run stability.

The metal-salt of senior aliphatic carboxylic acid is meant the metal-salt of the higher fatty acid of carbonatoms 8～22.As the higher fatty acid of carbonatoms 8～22, can enumerate lauric acid, stearic acid, tetradecyl acid etc.As the salifiable metal of structure, can enumerate sodium, potassium, magnesium, calcium, zinc, barium, aluminium etc.Wherein, alkaline-earth metals such as magnesium, calcium, barium preferably.

Light trigger in the above-mentioned additive is in the lamina that is made of resin combination, packaging film etc., as causing or promoting deoxidation and use.

When in oxygen-absorbing composition of the present invention, containing oxidation inhibitor, also be recommended in the said composition and then contain light trigger more than a kind.In such composition, the irradiation by light in desirable period promotes the reaction of thermoplastic resin (a) and oxygen to begin, and its result can bring into play the deoxidation function of composition.

As this suitable light trigger; can enumerate following compound; but be not limited to these: benzophenone; the O-methoxy benzophenone; methyl phenyl ketone; o-methoxyacetophenone; acenaphthene quinone; methylethylketone; n-butyl phenyl ketone; the hexanoyl benzophenone; α-phenyl butyrophenone; to morpholino propionyl benzene; dibenzosuberone; 4-morpholino benzophenone; benzoin; the benzoin methyl ether; 4-neighbour-morpholino deoxidation benzoin; to diacetyl benzene; the 4-aminobenzophenone; 4 '-methoxyacetophenone; man-; 9-ethanoyl phenanthrene; 2-ethanoyl phenanthrene; the 10-thioxanthone; 3-ethanoyl phenanthrene; 3-ethanoyl indoles; the 9-Fluorenone; the 1-indone; 1; 3; 5-triacetyl benzene; Thiaxanthene-9-ketone; xanthene 9-ketone; 7-H-benzo [de] anthracene-7-ketone; benzoin THP trtrahydropyranyl ether; 4; 4 '-two-(dimethylamino)-benzophenone; 1 '-acetonaphthone; 2 '-acetonaphthone; acetonaphthone and 2; the 3-dimethyl diketone; benzo [a] anthracene-7; the 12-diketone; 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; α; α-diethoxy acetophenone; α, α-dibutoxy methyl phenyl ketone etc.List-attitude oxygen generation light sensitizer, for example Tetrachlorofluorescein, Yamamoto Methylene Blue ZF and tetraphenylporphyrin also can be used as light trigger and use.Except the light trigger of above-mentioned haplotype, also can use polymerization initiator, contain poly--(ethene carbon monoxide) and oligopolymer [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene)-phenyl]-acetone therein].Generally.In order to obtain faster and effectively to cause effect, preferably use light trigger.

When containing light trigger,, can promote to cause the reaction of thermoplastic resin (a) and oxygen if under radioactive rays, shine.The light-initiated dosage that uses changes according to various factors.Light-initiated dosage can be according to the character and the amount of the oxidation inhibitor of the radioactive rays wavelength of the kind of the thermoplastic resin (a) of general use, use and intensity, use, and the light trigger type of using determines aptly.Mode when in addition, light-initiated dosage also uses according to oxygen absorption resin compositions and difference.For example containing the moulding product that the composition of light trigger makes is some opaque laminas, therefore, when the irradiation radioactive rays, just needs the initiator of more amount.

When generally using light trigger, its amount is the scope of 0.01～10 weight % of total composition.

The oxygen-absorbing composition of the present invention that contains above-mentioned light trigger at prescribed period of time irradiation radioactive rays, can cause the said composition deoxidation with this.By the irradiation radioactive rays, can reduce significantly or the disappearance oxygen-absorbing composition catch oxygen inductive phase, cause and catch oxygen or promote to catch oxygen.Be meant that oxygen-absorbing composition is up to the time that begins to cause seizure oxygen above-mentioned inductive phase.

As the radioactive rays of above-mentioned use, for example have about 200～750 nanometers (nm), the ultraviolet of preferably about 200～400nm wavelength or visible light are useful.Because the chemical action radioactive rays have long wavelength, so see it is ideal from cost and to the viewpoint of the influence of human body etc.When shining, preferably thermoplastic resin (a) 1g that is contained in the oxygen-absorbing composition is shone 0.1 joule at least with radioactive rays.The normal content of irradiation is that every 1g thermoplastic resin (a) is 10～100 joules a scope.In addition, radioactive rays also can be about 0.2～20 megarads, the electron beam of preferably about 1～10 megarad line amount.For other radiation source, the ionization radioactive rays have been comprised, for example γ line, X line and corona discharge.Radiation exposure preferably carries out in the presence of oxygen.Irradiation duration changes according to various factors.For its factor, the shape (for example thickness of lamina) of the moulding product that comprise the light-initiated dosage of existence and type thereof, shone, all antioxygen dosage that exists and the wavelength and the intensity of radiation source, but not limited by these.

The oxygen absorption resin compositions of the present invention that contains above-mentioned light trigger carries out the irradiation of radioactive rays and can carry out after said composition being mixed with desirable moulding product or article, also can carry out in preparation.For example if composition of the present invention is used for packing to the oxygen sensitivity goods, the irradiation of radioactive rays can be before packing, in the packing, carry out after the packing.But radiation exposure carries out before must using at the oxygen trapping agent as moulding product or article.In order to shine radioactive rays to greatest extent equably, irradiation should be carried out during for example in smooth flaky process segment at moulding product or article.

In the above-mentioned additive, deodorizing composition (or deodorant, sorbent material; Below they are generically and collectively referred to as deodorizing composition) use in order to reduce the foul smell that the low molecule by product of following resin combination deoxidation of the present invention to be produced causes.

As suitable deodorizing composition,, can enumerate zn cpds, aluminum compound, silicon compound, iron (II) compound, organic acid, iron (II) compound-organic acid composition etc. to its various types of being not particularly limited.They can use separately, also can be multiple mixture or double salt.

As above-mentioned zn cpds, can enumerate zinc silicate, zinc oxide, zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate, zinc carbonate, zinc acetate, zinc oxalate, zinc citrate, zinc fumarate, zinc formate etc.

As aluminum compound, can enumerate Tai-Ace S 150, aluminum phosphate, pure aluminium silicate, potassium aluminium sulfate etc.

As silicon compound, can enumerate phosphoric acid silicon compound, activated silica gel of silicon-dioxide, former phosphoric acid silicon, tetra-sodium silicon-I type, tetra-sodium silicon-II type etc. etc.

As iron (II) compound, can use so long as form any iron cpd of the iron ion of divalent.Iron (II) inorganic salt, the gallic acid that can enumerate ferrous sulfate, iron protochloride, Iron nitrate, ferrous bromide, iron iodide etc. as an example is ferrous, iron (II) organic salt of ferrous malate, Ferrous Fumarate etc., wherein, preferably ferrous sulfate, iron protochloride.

The composition (mixture or double salt) that contains zn cpds and silicon compound also is fit to use.As the object lesson of said composition, preferably the ratio of zinc oxide and silicon-dioxide is counted 1: 5～5: 1 scope, the zinc silicate that major part has amorphous structure with weight ratio, unsetting in fact micropartical.The ratio of zinc oxide and silicon-dioxide, preferably 1: 4～4: 1 scope, most preferably, 1: 3～3: 1 scope.

The composition of zn cpds and aluminum compound is also suitable to be used.As such object lesson, preferably the mixture of zinc oxide and/or zinc carbonate and Tai-Ace S 150 and/or potassium aluminium sulfate, for the zn cpds of 100 weight parts, aluminum compound is 1～1000 weight part, and preferably the ratio of 30～300 weight parts is mixed.

As organic acid, the organic acid of carbonatoms more than 8 preferably, for example aliphatics monoprotic acid, aliphatics polyprotonic acid, aromatic series monoprotic acid, aromatic series polyprotonic acid particularly preferably are aromatic carboxylic acid.Example as the aromatic series polyprotonic acid, can enumerate phthalic acid, terephthalic acid, m-phthalic acid, trimellitic acid, 1,2,3-benzene tricarbonic acid, 1,3,5-benzene tricarbonic acid, Pyromellitic Acid, benzene hexacarboxylic acid, naphthalene dicarboxylic acids, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, xenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, nitrogen benzide tetracarboxylic acid or their acid anhydride, wherein, preferably benzene tricarbonic acid, particularly trimellitic acid.

As iron (II) compound that is used for iron (II) compound-organic acid composition, as described above, can use so long as be dissolved in any a kind of compound that forms the iron ion of divalent in the water.As an example, iron (II) inorganic salt, the gallic acid that can enumerate ferrous sulfate, iron protochloride, Iron nitrate, ferrous bromide, iron iodide etc. is ferrous, iron (II) organic salt of ferrous malate, Ferrous Fumarate etc., wherein, preferably ferrous sulfate, iron protochloride.

As the organic acid that is used for iron (II) compound-organic acid composition, as long as water-soluble is just passable, as an example, carboxylic-acids such as the xitix class of xitix, saccharosonic acid and metal-salt thereof etc., citric acid, isocitric acid, lactic acid, tartrate, oxysuccinic acid preferably, wherein, L-xitix preferably.

Iron (II) compound-organic acid composition that uses, preferably both are used in combination.For example can be with two composition mixed once, the dissolved aqueous solution is carried out spraying drying, freeze-dried etc., prepare after the powdered.Iron (II) compound and organic acid component ratio, in weight ratio, preferably 1: 0.01～1: 1.0 scope, most preferably 1: 0.02～1: 0.80 scope.The organic acid composition is the xitix time-like, iron (II) compound and organic acid component ratio, in weight ratio, preferably 1: 0.02～1: 0.30 scope, more preferably 1: 0.02～1: 0.13, most preferably 1: 0.05～1: 0.13 scope.In the present invention, with (II) compound of the iron more than 2 kinds or the organic acid more than 2 kinds and with also it doesn't matter.In addition, for iron (II) compound-organic acid composition, as the stabilization agent of deodorization function, preferably for the alum that adds 2～20 weight % in iron (II) compound and the organic acid total amount.Be not particularly limited as alum, but preferably potassium alum, ammonla alum, sodium alum.

In addition, as other deodorizing composition, also can use the composition of the metallic compound stabilization of composition that zn cpds and polycarboxylic acid form etc., can use the living body enzyme model compound of iron (II)-titanium cyanines derivative etc., from tung oil tree, the Hiiragi tree, another name for, Farfugium japonicum, Rhizome of Japanese Butterbur, Syringa oblata Lindl., Greenstem Forsythia, chestnut, trees liquid or the extraction component of the plant of alder etc., the aluminosilicate of zeolite etc., sepiolite, ceramic whiteware stone, polygorskite, the hydrous magnesium silicate matter clay mineral of rubble (ラ Off リ Na ィト) etc., active humic acid, active oxygen aluminium, activated carbon etc.In addition, also can use porous matter sorbent material.

In above-mentioned deodorizing composition, preferably the aluminum compound of the silicon compound of the zn cpds of zinc oxide, zinc sulfate etc., silicon-dioxide, former phosphoric acid silicon etc., Tai-Ace S 150, potassium aluminium sulfate etc., contain zn cpds and silicon compound composition, contain the composition of zn cpds and aluminum compound, and then particularly preferably be organic acid, iron (II) compound-organic acid composition.

In these deodorizing compositions,, can enumerate the composition of zinc silicate, zinc oxide and alum as the deodorizing composition that can perform well in resin of the present invention or the resin combination.

In addition, when making multilayered structure, deodorizing composition is contained in the multilayer structure making of the present invention with various forms.As described below, can be contained in the layer or the layer beyond this layer of resin or resin combination formation.In multilayer structure making of the present invention, the interlayer at composition layer and other thermoplastic resin when the adhesion resin layer is set, also can contain deodorizing composition in the adhesion resin layer.Deodorizing composition can cooperate in the one deck in these layers, also can be engaged in more than two layers as required.The content of deodorizing composition is to cooperate 0.1 weight % in the gross weight of layer (resin layer etc.) above, preferably 0.2～50 weight %, most preferably 0.5～10 weight %.

Oxygen absorption resin compositions of the present invention has various excellent characteristic.For example, as mentioned above, the 2nd oxygen absorption resin compositions of the present invention, its rate of oxygen absorption is 0.01ml/m ²More than the day.Oxygen absorption resin compositions for the of the present invention the 1st and the 3rd and oxygen absorption resin of the present invention, rate of oxygen absorption, preferably 0.01ml/m ²More than the day.The rate of oxygen absorption of each resin combination, preferably 0.05ml/m ²Day is above, 0.1ml/m most preferably ²More than the day.The not enough 0.01ml/m of rate of oxygen absorption ²During day, use the oxygen shielding of moulding product of laminated vessel that resin combination of the present invention forms etc. insufficient, in addition, the deoxidation effect is also insufficient.

Above-mentioned rate of oxygen absorption is meant when the film with resin combination is placed in the air of certain volume, in the per unit surface area unit time, its film absorption the volume of oxygen.Concrete measuring method is as shown in following embodiment.

When resin combination of the present invention or resin are used as Oxygen Scavenger, useful removal speed (rate of oxygen absorption), preferably under 20 ℃, 1 air pressure, per 1 day every 1m in air ²Thermoplastic resin (a) layer with carbon-to-carbon double bond absorbs the oxygen of 0.5ml, most preferably absorbs the above oxygen of 5ml.At this moment, the 3rd of the invention described above the and the 4th scheme preferably.

In addition, the deoxidation capacity of resin combination of the present invention or resin, preferably every 1g are the above deoxidation capacity of 1ml.More preferably every 1g is the above deoxidation capacity of 10ml, and most preferably every 1g is the above deoxidation capacity of 50ml.

The suitable melt flow rate (MFR) (MFR) of oxygen absorption resin compositions of the present invention or resin (210 ℃, 2160g load down, according to JIS K7210) preferably 0.1～100g/10 minute, more preferably 0.5～50g/10 minute, most preferably 1～30g/10 minute.The melt flow rate (MFR) of resin combination of the present invention is beyond 0.1～100g/10 minute scope the time, when carrying out melt molding, and the most variation of its processibility.

Oxygen absorption resin compositions of the present invention or resin according to purpose, may be molded to various moulding product.

The method of each composition of mixing, moulding oxygen absorption resin compositions has no particular limits.Order when mixing each composition also has no particular limits.For example thermoplastic resin (a), gas-barrier resin (b) and transition metal salt (c) are cooperated, when making the moulding product, these compositions can be mixed simultaneously, also can be behind the title complex of making thermoplastic resin (a) and transition metal salt (c), (b) mixes with gas-barrier resin.Or behind the title complex of making gas-barrier resin (b) and transition metal salt (c), (a) mixes with thermoplastic resin.Also can be behind the title complex of making thermoplastic resin (a) and gas-barrier resin (b), hybrid transition metal salt (c).And then, also can make the title complex of the title complex of thermoplastic resin (a) and gas-barrier resin (b) and gas-barrier resin (b) and transition metal salt (c) respectively after, they are mixed.

Each composition of these compositions also can cooperate in fusion, as particulate state, supplies with moulding, also can directly supply with moulding behind the dry blending.

As cooperate, the means of mixing above-mentioned each composition, can enumerate the use solvent, dissolve each resinous principle, make the method for solvent evaporation and fusion under the temperature of 50 ℃～300 ℃ of scopes, mixing method (fusion companion method) after the mixing.Easy and the cost viewpoint from operation, preferably fusion companion method, but have no particular limits.As being used for the means that fusion cooperates, can enumerate ribbon mixer, high-speed mixer, kneader, mixing roll, forcing machine, Banbury Banbury mixer, roll skeleton symbol milling device etc.

For example, each composition of composition of the present invention, carry out mixing, granulating with Banbury Banbury mixer, single shaft or twin shaft screw extrusion press etc. after, supply with melt molding.Oxidation takes place in thermoplastic resin (a) when preventing married operation, can carry out the nitrogen envelope, extrude at low temperatures at the hopper mouth.And then, use the high forcing machine of mixing degree, make that each composition is fine to be disperseed equably, when making oxygen absorption energy, the transparency good, can prevent the generation of gel pit or sneak into is ideal.

In order to make each the composition good dispersion in the resin combination, mixing operation is important.In order to obtain having the composition of high dispersing, as mixing roll, the successive type mixing roll of continous way rotating cylinder milling device, kneading type biaxial extruder (equidirectional or different directions) etc. preferably, but also can use batch-type mixing rolls such as Banbury Banbury mixer, rotating cylinder milling device, pressurization kneader.In addition,, also can use the device of the armature of grinding mechanism, for example the KCK mixing extruder of (strain) KCK system with stone mortar sample as other continuous mixing device.As mixing roll, normally used, can enumerate kneading part (ダ Le メ one ジ, CTM etc.) is set in the single shaft forcing machine or simple type mixing roll such as Bradley Bender milling device.

Wherein, most preferred as the object of the invention can be enumerated continous way rotating cylinder milling device.As commercially available machine, the system FCM of Farrel society, the system CIM of (strain) JSW or the made KCM of (strain) Kobe Steel, LCM or ACM etc. are arranged.In fact adopt below these mixing rolls, have device that the mixing and extruding pelletization of single shaft forcing machine carries out simultaneously for preferred.In addition, have kneading disk or mixing twin shaft mixing extruder, for example TEX, the Werner﹠amp of (strain) JSW system with roller; The TEM of ZSK toshiba machine (strain) system of Pfleiderer society, the PCM of pond shellfish ironworker (strain) system etc. also can be used for mixing purpose of the present invention.

When using these successive type mixing rolls, the shape of roller, dish plays an important role.Particularly mixing section and roller top or and the gap (top clearance) of Pan Ding be very important, the narrow wide composition that all can not get having good dispersiveness.As the top clearance, 1～5mm preferably.

The revolution of the roller of mixing roll preferably adopts 100～1200rpm, more preferably 150～1000rpm, the most preferably scope of 200～800rpm.Mixing roll chamber internal diameter (D) is more than the 30mm, preferably the scope of 50～400mm.With the ratio L/D of the chamber length (L) of mixing roll, preferably 4～30.In addition, mixing roll can singlely use, and also can link use more than 2.

Mixing time is long, can obtain good result, but considers from the antioxygen of thermoplastic resin (a) or economy, and preferably 10～600 seconds, more preferably 15～200 seconds scope, most preferably 15～150 seconds.

Resin combination of the present invention is by adopting above-mentioned various forming method aptly, the various moulding product of plastic one-tenth, for example Oxygen Scavenger of film, sheet, container and other wrapping material, different shape etc.

For example, by melt extruding the plastic one-tenth film of moulding, plate, pipe etc., by the plastic one-tenth container shapes of injection molding, in addition, by the hollow container of plastic one-tenth ampuliform of slush molding etc.When slush molding, by the plastic parison of extrusion moulding, with its blowing carry out moulding extrude slush molding and by the injection molding shaping stock, the injection slush molding that its blowing is carried out moulding all can be used as suitable embodiment illustration, but is not limited to these.

Oxygen absorption resin compositions of the present invention as mentioned above, can be used as various wrapping material or container and uses aptly, but from its good oxygen absorption and use, processibility, also is useful as Oxygen Scavenger.Oxygen Scavenger can join and becomes arbitrary shape to obtain oxygen absorption resin compositions of the present invention or resin forming, for example is equipped with in the packaging vessel of food or pharmaceuticals, can remove the oxygen in the packaging vessel effectively.When resin combination of the present invention should not directly contact with content, the moulding product that resin combination of the present invention constitutes can be filled to the partition content, but can see through in the wrapping material of gas.For example, content is so long as have the solid of sufficient median size, and the embodiment that the moulding product that resin combination of the present invention is constituted are filled in the wrapping material of formation such as non-woven fabrics also suits.

The shape of above-mentioned Oxygen Scavenger is not particularly limited, but in order to improve the deoxidation function efficiently, the surface-area that strengthens per unit volume is effectively, makes film like or granularly also suits.

Generally, the outside surface of the various moulding product that will obtain according to above-mentioned purpose also suits with the mode of the coatings such as thermoplastic resin beyond resin combination of the present invention or the resin.For example in the occasion of the container of the content of packing into, except suppressing oxygen absorption resin compositions and content directly contact, by the kind and the thickness of the thermoplastic resin that coats, control enters the intrusion speed of oxygen, the speed of response of adjustable abridged edition invention resin combination and oxygen from the outside.By the rate of oxygen absorption of aforesaid method adjusting resin combination of the present invention, can keep the deoxidation function of resin combination of the present invention for a long time.

The outside surface of the moulding product that resin combination of the present invention is constituted is not particularly limited with other the method for thermoplastic resin coating.Can enumerate at stratified at least one the face superimposed layer thermoplastic resin of resin combination structure of the present invention, make polylayer forest method and with resin combination of the present invention as internal layer, with other thermoplastic resin as outermost multilayer structure polymer particle etc. as suitable embodiment.

In the present invention, the moulding product that obtain by above-mentioned moulding, also individual layer of film or sheet for example uses but make multilayer body with layer that other various resins, metal, paper, fabric or non-woven fabrics constitutes, and from overpaying with function to see it is better.When using resin combination of the present invention with individual layer because big with the oxygen contact area, so often the time length of deoxidation function short, and then behind the deoxidation, physical strength reduces.And, because content or atmospheric moisture often make the oxygen shielding reduce.In order to compensate this point, the layer or the high layer of lamination physical strength that constitute of lamination gas-barrier resin (b) preferably.

In the present invention, with the outer side covers of oxygen absorption resin compositions layer, can suppress the intrusion speed from the oxygen of outside with other resin layer, from keeping the deoxidation function of resin combination for a long time, making that multilayer constitutes is ideal.In addition, the present invention also comprises having multilayer structure making or the laminated vessel that contains oxygen absorption resin compositions or oxygen absorption resin layer.

In the container that multilayer constitutes, form the embodiment of the innermost layer of this container with resin combination of the present invention, deoxidation functional point of view in the quick performance container suits.

Concrete layer as multilayer structure making constitutes, if with thermoplastic resin (a) formation such as resin, metal, paper, fabric or non-woven fabrics in addition layer as the A layer, with thermoplastic resin (a) or the resin combination layer that contains this thermoplastic resin (a) as the B layer, with the adhesion resin layer during as the C layer, can enumerate layers such as A/B, A/B/A, A/C/B, A/C/B/C/A, A/B/A/B/A, A/C/B/C/A/C/B/C/A constitutes, but suitable additional other layers do not have any relation yet on these, not limited by above-mentioned example.When being provided with the layer of a plurality of other resins compositions, can be different types of, also can be identical type.And then the recovery resin layer that the waste materials such as finishing that produce in the time of also can being provided with moulding in addition constitute also can will reclaim mixed with resin in the layer that is made of other resins.Constitute for the thickness of multilayer structure making, also have no particular limits, but when considering formability and cost etc., the B layer is for the thickness ratio of holostrome thickness, and preferably 2～20%.

As the material of the resin layer on the moulding product that are stacked in oxygen absorption resin compositions of the present invention, from processibility etc., preferably thermoplastic resin.As such thermoplastic resin, be not particularly limited, can enumerate following resin: Alathon and ethylene copolymer (ethene and following monomeric multipolymer: the alpha-olefin of propylene, 1-butylene, iso-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.; The unsaturated carboxylic acid of methylene-succinic acid, methacrylic acid, vinylformic acid, maleic anhydride etc., its salt, its partially or completely ester, its nitrile, its acid amides, its acid anhydride; The vinyl carboxylates class of vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, sad vinyl acetate, laurostearic acid vinyl acetate, stearic acid vinyl ester, eicosanoic acid vinyl acetate etc.; The vinyltrimethoxy silane based compound; Unsaturated sulfonic acid or its salt; The alkyl sulfide alcohols; Vinyl pyrrolidone class etc.), alfon and propylene copolymer (propylene and following monomeric multipolymer: the alpha-olefin of ethene, 1-butylene, iso-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.; The unsaturated carboxylic acid of methylene-succinic acid, methacrylic acid, vinylformic acid, maleic anhydride etc., its salt, its partially or completely ester, its nitrile, its acid amides, its acid anhydride; The vinyl carboxylates class of vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, sad vinyl acetate, laurostearic acid vinyl acetate, stearic acid vinyl ester, eicosanoic acid vinyl acetate etc.; The vinyl silanes based compound of vinyltrimethoxy silane etc.; Unsaturated sulfonic acid or its salt; The alkyl sulfide alcohols; Vinyl pyrrolidone class etc.), the polyolefine of poly 4-methylpene-1, polybutene-1 etc.; The polyester of polyethylene terephthalate, polybutylene terephthalate, PEN etc.; The polymeric amide of poly-ε-Ji Neixianan, poly hexamethylene adipamide amine, poly-m-xylene diamide etc.; Polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylic ester etc.Layer by such thermoplastic resin lamination also can be no tensile, single shaft or biaxial stretch-formed or also having no relations of rolling.

In these thermoplastic resins, from good viewpoints such as wet fastness, mechanical characteristic, economy, heat sealabilities, polyolefine suits.In addition, because the transparency of polyester is good, mechanical characteristic is also good, so as big with the availability of the good resin combination lamination of the present invention of the transparency.

In addition, as with the material of the metal level of resin combination lamination of the present invention, can enumerate general steel that uses such as narrow-necked earthen jar container and aluminium etc.

Among the present invention,, can use adhesion resin for resin combination layer of the present invention and other resin layers bonding.Adhesion resin, so long as can getting final product with each interlaminar bonding, be not particularly limited, can preferably use polyurethane series, polyester are arranged is a liquid type or binary liquid shape hardening binding agent, product (carboxyl acid modified polyolefin resin) that unsaturated carboxylic acid or its acid anhydride (maleic anhydride etc.) and olefin polymer or multipolymer are carried out copolymerization or graft modification.

Among these, when adhesion resin is carboxyl acid modified polyolefin resin,, be ideal from the upper layer of polyolefine etc. and the close-burning viewpoint of resin combination layer.As the example of so carboxyl acid modified polyolefin-based resins, can enumerate polyethylene { new LDPE (film grade) (LDPE), straight chain shape new LDPE (film grade) (LLDPE), ultra-low density polyethylene (VLDPE) }, polypropylene, Co-polypropylene, ethylene-vinyl acetate copolymer, ethene-(methyl) acrylate (methyl esters or ethyl ester) multipolymer etc. are carried out carboxyl acid modified product.

When moulding product of the present invention are multi-layer product, the deoxidation layer also can with layer such as " oxygen shielding material ", i.e. oxygen permeation rate, under 20 ℃, per 1 normal atmosphere is 200cm ³/ m ²The layer that the following material of day makes carries out lamination, but may not be so limited.Typical oxygen shielding material comprises poly-(ethylene-vinyl alcohol) polyacrylonitrile, polyvinyl chloride, poly-(vinylidene chloride), polyethylene terephthalate, silicon-dioxide and polymeric amide.Also can use and contain a kind of above-mentioned monomeric multipolymer and metal foil layer.

Other layers also can contain the oxygen perviousness layer more than a kind or a kind.Particularly as 1 example of packaging film, can enumerate and contain (i) oxygen sealing coat, (ii) contain the oxygen absorption resin compositions layer of the present invention and the (iii) lamination packaging film of oxygen perviousness layer arbitrarily with flexibility that food uses.This film can be with (i) layer as the outside, and (iii) layer uses as inboard packing.(i) oxygen sealing coat has limited from the outside to (ii) layer and has invaded oxygen, thus, makes the deoxidation time of layer in (ii) elongated.Layer oxygen perviousness layer (iii) regulated inner oxygen permeation rate, thus, but makes the (ii) interior deoxidation time of layer elongated.In addition, when packing pre-treatment film, it also plays a part to prolong the life-span of deoxidation material.And then layer (iii) can cut off thermoplastic resin (a), transition metal salt (c), other additive or the by product of removal and move to package interior.And then layer (iii) can increase heat sealability, the transparency and/or to the agglutinating resistivity of multilayer film.

As the method that obtains multilayer structure making, can enumerate and extrude lay-up method, dried lay-up method, solvent trickling method, coinjection moulding method, co-extrusion modling method etc., but be not particularly limited.As the co-extrusion modling method, can enumerate coextrusion lay-up method, coextrusion sheet metal forming method, coextrusion film blowing, coextrusion blow molding method etc.

With the plate of the multilayer structure making that obtains like this, film, parison etc., under the temperature below the contained melting point resin, carry out reheat, with hot-forming methods such as companding shaping, roller stretching method, bullating type stretching method or blowing stretching method, blow out the method for forming etc. by single shaft or biaxial stretch-formed, the moulding product that obtained stretching.

Resin combination of the present invention, the kind of the thermoplastic resin of selecting aptly to be contained according to specific refractory power (a), gas-barrier resin (b) etc. can make its transparency good.Therefore, as other resins of lamination,, can be seen the packaging vessel of content easily by selecting the good resin of the transparency.When obtaining the good multilayer structure making of the transparency, to the haze value of inside preferably be controlled at below 10%, more preferably below 5%, most preferably below 3%.

Oxygen absorption resin of the present invention or oxygen absorption resin compositions can arbitrary shapes, use as oxygen absorbent.In addition, use the moulding product, particularly multilayer structure making of their container etc., can be used for various uses.Particularly, use deoxidation extremely strong and, the resin combination of the present invention that the oxygen shielding is also good when being used for various packaging vessel, can be brought into play its great superiority., be very suitable particularly because the existence of oxygen makes the packaging vessel of quality deterioration easily as food, pharmaceuticals, agricultural chemicals etc.And then resin combination of the present invention, particularly also suits as the gasket seal use that container cover is used with liner (pad) as container.The lid that this gasket seal is housed has good gas-barrier property, deoxidation.

And then resin combination of the present invention by the suitable resin of selecting, can have the good transparency, so also be suitable for as the purposes of seeing the packaging vessel of content easily.As when such transparency to packaging vessel requires performance strict, use the big mode of availability of resin combination of the present invention, for example can enumerate following 2 kinds of embodiments.

Promptly, the one, contain oxygen absorption resin compositions of the present application or the layer that the oxygen absorption resin is formed, and thick by holostrome be the container that the multilayer film below the 300 μ m are formed, the 2nd, the laminated vessel that layer of being made up of the oxygen absorption resin compositions of the present application or oxygen absorption resin and thermoplastic polyester layer are formed.Below, be illustrated successively for these embodiments.

Containing layer that the resin combination of the present application forms and holostrome thick is the container that the following multilayer film of 300 μ m constitute, and is the soft container that is made of the multilayer structure making that total layer thickness relatively approaches, is processed to the shape of pouch etc. usually.

Generally, as the container that requires the good transparency, be meant the container of making all thin thickness by thin each resin layer that constitutes multilayer structure making.For example when crystalline resins such as use polyolefine, when thickness is big, because the crystalline scattering make transparent variation mostly, and the container of thin thickness can obtain the good transparency.In addition, generally say, the resin of no stretch crystallizationization, even the transparency poor, but the orientation stretching post crystallization resin transparent improve.This with single shaft or biaxial stretch-formed film, common thin thickness, from this point, the multilayer structure making of thin thickness has the good transparency mostly.

Resin combination of the present invention by the resin of selecting to suit, can make the transparency very good.Therefore, demanding for the transparency, the container that the multilayer film of thin thickness constitute is applicable.For so thin film, though through the time ground transparent variation, the transparency is also better.

The thickness of this multilayer film is not particularly limited, and preferably below the 300 μ m, keeps the good transparency easily.More preferably below the 250 μ m, most preferably below the 200 μ m.On the other hand, also be not particularly limited for the lower value of thickness, but if be considered as the mechanical strength of container, preferably more than the 10 μ m, more preferably more than the 20 μ m, most preferably more than the 30 μ m.

Be not particularly limited for layer structure, but can obtain multilayer film by methods such as resin combination layer of the present invention and other the dried lamination of thermoplastic resin, coextrusion lamination are carried out multiple stratification.

For the occasion of dried lamination, can use no oriented film, single axle drawn membrane, biaxially oriented film, calendered film.Among these, see goodly from intensity, the transparency etc., can enumerate biaxial stretch-formed polypropylene film, biaxial stretch-formed pet film, biaxial stretch-formed poly-ε-Ji Neixianan film.The moisture resistance of biaxial stretch-formed polypropylene film is good, so be particularly preferred.

For sealed package, the multilayer film that preferably constitute this packaging vessel one side the most surperficial at least are provided with heat sealable resin and constitute layer.As such resin, can enumerate polyolefine such as polyethylene, polypropylene.

In addition, behind reheat behind the lamination, the hot-forming method of companding shaping etc., roller stretching method, convergent-divergent stretching method or inflation stretching method etc., by single shaft or biaxial stretch-formed, the multilayer film that also can obtain stretching.

The multilayer film that obtain like this can be processed pouch, and the filling content is as packaging vessel.Because soft, easy, and the transparency, gas-barrier property, deoxidation are good, so for the packings such as content, particularly food owing to the easy deterioration of existence of oxygen, be extremely useful.

The laminated vessel that layer that is made of the resin combination of the present application and thermoplastic polyester layer constitute by selecting resin aptly, can obtain the good transparency, and gas-barrier property, deoxidation are also good.

Generally, the transparency of vibrin is good, with resin combination lamination of the present invention, can obtain the good multilayer structure making of the transparency.

The form of the laminated vessel that layer of forming for the resin combination of the present application and thermoplastic polyester layer are formed has no particular limits, and can enumerate bag-like container, cup-like container, slush molding container etc., but wherein, importantly the slush molding container.Method for making for the slush molding container is not particularly limited, and can enumerate blow molding, injection molding etc., but in the practicality, blow molding is important, wherein, the doleiform shape be important.

The blow molding bottle that thermoplastic polyester constitutes is widely used in beverage container at present.On such purposes, when content need prevent deterioration, also require the human consumer can fully see beverage clearly as content.For example, packing as beer and so on because its local flavor when very easily suffering the content of deterioration because of the effect of oxygen, requires to have high gas-barrier property and deoxidation performance, but will satisfy this requirement, be very difficult.

The multilayer blow moulding bottle that layer that is made of the resin combination of the present application and thermoplastic polyester layer are formed, when can keep transparent, the maintenance performance of content quality is also extremely good, so be optimum to this purposes.

Vibrin as the laminated vessel that is used for the present application that layer that oxygen absorption resin compositions or oxygen absorption resin constitute and thermoplastic polyester layer form can use aromatic dicarboxylic acid or their alkyl ester and the glycol polycondensate as principal constituent.Particularly to achieve the object of the present invention, preferably with the vibrin of ethylene glycol terephthalate composition as principal constituent.For vibrin used in the present invention, generally, the total ratio of terephthalic acid units and ethylene glycol unit (mole %) is with respect to the unitary total mole number of entire infrastructure that constitutes polyester, preferably 70 moles more than the %, most preferably 90 moles more than the %.If during 70 moles of % of total ratio less than of terephthalic acid units in the polyester and ethylene glycol unit, the polyester that obtains becomes non-crystalline, so big, the poor heat resistance of shrinkability during for stretched container heating filling (hot filling), intensity has also descended.And then, when reducing the solid state polymerization that the oligopolymer that is contained in the resin carries out because resin is softening, take place easily deadlocked, cause and produce difficulty.

Above-mentioned vibrin as required, in the scope that processibility, intensity, thermotolerance etc. are not subjected to damage significantly, can contain terephthalic acid units and ethylene glycol unit 2 functional compound unit in addition.As its ratio (mole %), with respect to the total mole number of the full structural unit that constitutes polyester, preferably 30 moles below the %, more preferably 20 moles below the %, most preferably 10 moles below the %.

As the 2 good functional compound unit that can contain, can enumerate and select at least a kind 2 functional compound unit from dicarboxylic acid units, diol units and hydroxycarboxylic acid unit.These no matter be in 2 functional compound unit of aliphatic 2 functional compound unit, ester ring type, the aromatic 2 functional compound unit any a kind can.

In addition, from the viewpoint of the formability and the transparency, thermoplastic polyester, preferably with ethylene glycol terephthalate as principal constituent, and its fusing point is 240～250 ℃ a thermoplastic polyester.

When fusing point surpassed 250 ℃, because the crystallization speed of vibrin is fast, during injection molding or during blow molding, because the easy crystallization of heating, its result often was easy to generate albefaction, the infringement transparency on the bottle that makes.In addition, stretch orientation reduction sometimes, plastic property is the variation situation also.For this reason, the scope of creating conditions that can make good goods narrows down, scrap rate increases.So optimum fusing point is below 248 ℃.

On the other hand, when 240 ℃ of fusing point less thaies, the thermotolerance of laminated vessel reduces.In addition, because the crystallinity of vibrin also is lower than limit, so stretch orientation reduction, intensity have also reduced.And then because fusing point reduces, it is low that solid phase polymerization temperature is also had to, thereby reduce the problem that causes that productivity reduces owing to speed of response.So preferred fusing point is more than 242 ℃, most preferably more than 244 ℃.

In order to obtain having the vibrin of such fusing point, as long as it is just passable to make the copolymer composition of appropriate amount and glycol phthalate composition carry out copolymerization as the vibrin of principal constituent.Particularly, with respect to the unitary total mole number of whole formations that constitutes polyester, preferably contain the copolymer composition of 1～6 mole of %.More preferably 1.5～5 moles of %, 2～4 moles of % most preferably.

The copolymerization amount of the glycol ether of by-product when consider making adds other comonomer, can obtain the resin of the copolymerization amount of above-mentioned scope.Comonomer as other is not particularly limited.Above-mentioned various monomers can be used, but wherein preferably dimethyltrimethylene glycol, cyclohexanedimethanol, cyclohexane dicarboxylic acid, m-phthalic acid, naphthalene dicarboxylic acids can be enumerated.

When particularly using the copolyester that obtains as comonomer with m-phthalic acid, because it is wide to obtain creating conditions of superior prod, so formability is good.Its result has the low advantage of scrap rate.And then, from suppressing crystallization speed, can prevent the albefaction aspect of moulding product from seeing it is ideal.

1,4 cyclohexane dimethanol unit or 1, the 4-cyclohexane dicarboxylic acid, from the dropping strength of the moulding product that obtain thus good on, be preferred.

In addition, naphthalene dicarboxylic acids, from the second-order transition temperature height of the polyester that obtains, its result, the container thermotolerance that finally obtains is seen on improving, is preferred.And then, as copolymer composition, contain the polyester of naphthalene dicarboxylic acids, can absorb ultraviolet ray, so content is useful especially because ultraviolet ray is easy to generate the occasion of deterioration.For example at the content of beer sample because oxidation, since ultraviolet ray easily the occasion of deterioration be useful.

In Coinjection stretch blow molded container, prevent ultraviolet ray during at the protection content as purpose, thermoplastic polyester with respect to full dicarboxylic acid composition, preferably contains 0.5～15 mole of %, and more preferably 2 of 1.0～10 moles of %, 6-naphthalene dicarboxylic acids composition.

When in making polyester, using polycondensation catalyst, can use those catalyzer that are generally used for making polyester, for example can enumerate the antimony compounds of ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.; The germanium compound of germanium dioxide, tetraethoxy germanium, four n-butoxy germanium etc.; The titanium compound of tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium butoxide etc.; The tin compounds of di-n-butyl tin dilaurate, di-n-butyl tin-oxide, dibutyl tin diacetate esters etc. etc., these catalyst compound can use separately, also can be used in combination more than 2 kinds.In these polymerizing catalysts, from the excellent color tone aspect of the polyester that obtains, germanium compound preferably is from catalyzer cost aspect, preferably antimony compounds.As germanium compound, germanium dioxide most preferably, as antimony compounds, ANTIMONY TRIOXIDE SB 203 99.8 PCT most preferably.Polycondensation catalyst with respect to dicarboxylic acid 100 weight parts, preferably adds 0.02～0.8 weight part.

From the formability viewpoint, adopt germanium compound, more suitable than antimony compounds.That is, general, the crystallization velocity of using antimony compounds polymeric polyester is than fast with germanium polymeric polyester, thus during injection molding or during blow molding, because heating, crystallization easily, its result is easy to generate albefaction on the bottle that makes, the transparency is compromised.And stretch orientation reduction sometimes, plastic property be variation also.For this reason, the scope of creating conditions that can obtain good goods narrows down, and scrap rate rises easily.

Therefore, when using the polyethylene terephthalate of the glycol ether copolymer composition in addition that does not contain by-product, compare because of the polyethylene terephthalate of a small amount of modification of other copolymer compositions with use, its crystallization velocity is fast, so the selection of catalysts particularly important is preferably used germanium compound.

The manufacture method of the vibrin that uses in the thermoplastic polyester layer for multilayer blow moulding bottle of the present invention is not particularly limited.By usual method, use above-mentioned glycol, dicarboxylic acid, polymerizing catalyst, can prepare with usual method.

Method for making for the flask in the laminated vessel with above-mentioned thermoplastic polyester layer is illustrated.

Manufacture method for such container is not particularly limited.On productivity etc., the suitable injection blow molding method of forming altogether of using.Altogether in the injection blow molding method of forming, container precursor (parison) with multilayered structure can be by using the shaper of 2 injection cylinder bodies, in single mould, carry out 1 matched moulds operation, oxygen absorption resin compositions with fused vibrin (PES) and the present application, from dividing the mutual injection in time ground of staggering of other injection cylinder body, or injection simultaneously in the nozzle of concentric circles, or its both and with and obtain.For example, (1) the PES injection of at first ectonexine being used, then, to inject simultaneously as the resin combination and the ectonexine in middle layer, make the method or PES that (2) are at first the used ectonexine injection of container of 3 layers of formation of PES/ resin combination/PES, then, resin combination and ectonexine are injected simultaneously, and then, meanwhile, or thereafter, to inject simultaneously as PES and above-mentioned each layer of central core, the methods of the container of 5 layers of formation of making PES/ resin combination/PES/ resin combination/PES etc., the general method that the die bed base is arranged of enclosing the PES layer with internal layer fully obtains, and is not particularly limited on equipment.In addition, during above-mentioned layer constitutes, between PES layer and resin combination layer, as required, also configurable adhesion resin layer.

Condition during as injection molding that the die bed base is arranged, preferably PES injects in 250 ℃～330 ℃ temperature range, more preferably injects in 270 ℃～320 ℃ temperature range, most preferably injects in 280 ℃～310 ℃ temperature range.During 250 ℃ of the injection temperature less thaies of PES, the fully fusion of PES particle so sneak into not melts (flake) in the moulding product, produces the bad order phenomenon.In addition, the intensity of moulding product is reduced.And then in extreme occasion, the screw rod torque rises, and causes shaper to break down.On the other hand, when the injection temperature of PES surpassed 330 ℃, PES obviously decomposed, because molecular weight reduces, caused that the intensity of moulding product reduces.In addition, gases such as the acetaldehyde that generates during dispersion not only damage the physical property that is filled in the moulding product, and the oligopolymer that generates during owing to dispersion greatly pollutes mould, has damaged the outward appearance of moulding product.

Oxygen absorption resin compositions is preferably injected in 170～250 ℃ temperature range, more preferably injects in 180～240 ℃ temperature range, most preferably injects in 190～230 ℃ temperature range.

During 170 ℃ of the injection temperature deficiencies of resin combination, because fully fusion of resin composition pellet so sneak into not melts (flake) in the moulding product, causes bad order.And then in extreme occasion, the screw rod torque rises, and causes shaper to break down.On the other hand, when the injection temperature of resin combination surpassed 250 ℃, thermoplastic resin (a) carried out oxidation, and the oxygen uptake ability of resin combination reduces, and also causes gas-barrier property and deoxidation reduction easily.Simultaneously, because painted and gelation thing causes the bad order of moulding product, or because decomposition gas and gelation thing make flowability inhomogeneous or hindered, the resin combination layer also produces damaged.In extreme occasion, owing to produce the gelation thing, can not injection molding.Oxidation when suppressing fusion is preferably sealed raw material supplying hopper nitrogen with nitrogen.

Oxygen absorption resin compositions of the present invention is in advance thermoplastic resin (a), gas-barrier resin (b) to be reached as required, also has transition metal salt fusions such as (c) to cooperate, and makes particle, then it is supplied with shaper.Or also can supply with shaper with doing each mixed material.

The temperature of the hot runner part that PES and resin combination flow into is preferably injected in 220 ℃～300 ℃ scope, more preferably injects in 240 ℃～280 ℃ scope, most preferably injects in 250 ℃～270 ℃ scope.

When 220 ℃ of the temperature deficiencies of hot runner part, the crystallization of PES takes place, partly solidified at hot runner, so difficult forming.On the other hand, when the temperature of hot runner part surpassed 300 ℃, the oxygen uptake ability that oxidation, resin combination take place thermoplastic resin (a) reduced, and causes gas-barrier property and deoxidation reduction easily.Simultaneously, because painted and gelation thing causes moulding product bad order or because decomposition gas and gelation thing make mobile inhomogeneously, or hinders flowability that the resin combination layer produces damaged part.In extreme occasion, can not injection molding owing to produce the gelation thing.

Have the die bed base stretch blow-molded with above-mentioned, for making the laminated vessel that obtains good anti-delamination (anti-splitting) property, the transparency are arranged, when above-mentioned injection molding, it is important suppressing the PES of parison and the crystallization of gas-barrier resin (b) as far as possible.Thus, can obtain the good moulding product of uniform stretchiness, anti-delamination, the transparency and shape.For the PES that suppresses parison and the crystallization of gas-barrier resin (b), preferably die temperature is controlled at 0 ℃～70 ℃ scopes, more preferably 5 ℃～50 ℃ scopes, 10～30 ℃ of scopes most preferably.If 0 ℃ of die temperature less than because the mould dewfall is damaged the parison outward appearance, can not get good moulding product.In addition, when die temperature surpasses 70 ℃, promoted the PES of parison and the crystallization of gas-barrier resin (b), can not get uniform stretchiness, the anti-delamination reduction of the stretch blow-molded moulding product that obtain is difficult to obtain investing the moulding product of design shape.And then, because the crystallization of PES has damaged the transparency.

For the thickness of parison, preferred total thickness is that 2～5mm, oxygen absorption resin compositions layer add up to 10～500 μ m.

The multilayer parison that obtains so directly, or with behind reheat to 75～150 under the heating elements such as block heater, infrared heater ℃, is delivered in the stretch-blow operation under the condition of high temperature.Behind 1～5 times of longitudinal stretching,, obtain the multi-layered polyester stretch blow molded containers of single shaft or biaxial stretch-formed PES resin layer and oxygen absorption resin compositions layer with blow moldings to 1 such as pressurized air～4 times.

At this moment, if make the temperature in multilayer parison when heating too high,, damage outward appearance because the easy crystallization of polyester makes the stretch blow molded containers albefaction.In addition, because the delamination incidence of stretch blow molded containers increases, be unfavorable.On the other hand, the temperature during as if the heating of multilayer parison is low excessively, because polyester produces be full of cracks, becomes pearl, so the damage transparency.For this reason, the temperature of the multilayer parison during heating, preferably 85～140 ℃, more preferably 90 ℃～130 ℃, most preferably 95～120 ℃.

The body total thickness of the blow-molded container among the present invention generally is 100～2000 μ m, and preferably 150～1000 μ m distinguish use according to purposes.The total thickness of the oxygen absorption resin compositions layer of this moment is preferably in 2～200 mu m ranges, most preferably in 5～100 mu m ranges.

Like this, can obtain the laminated vessel that the layer that is made of the thermoplastic resin composition of the present application or thermoplastic resin and thermoplastic polyester layer are formed.This container can be modulated into has good transparency, and gas-barrier property and deoxidation are extremely good.Therefore, because the content of the easy deterioration of existence of oxygen, so be useful on the packing of food, pharmaceuticals etc. for example., be extremely useful particularly as beverage container such as Beer Bottles.

Embodiment

Below, specifically describe the present invention with examples such as embodiment, but the present invention is not limited by these examples.Analysis in following embodiment and estimate following carrying out.

(1) about the styrene content of thermoplastic resin (a), with the content (ethylenic linkage content) and the carbon-to-carbon double bond content of the structural unit of structural formula (I) expression:

By weighing chloroform as solvent ¹H-NMR (nucleus magnetic resonance) spectrum (measuring with NEC society's system " JNM-GX-500 type ") is measured thermoplastic resin (a), identifies this resin structure.Thus, calculate above-mentioned content.

Wherein, styrene content is meant the cinnamic ratio (mole %) in the total monomer that constitutes this resin, and the ratio (promptly forming the ratio of ethylenic linkage) that is meant the structural unit of representing with structural formula (I) in total diene monomers in the diene block with the content (ethylenic linkage content) of the structural unit of structural formula (I) expression (%).The content of carbon-to-carbon double bond can be obtained by the mole number (eq/g) that calculating is contained in the two keys in the 1g resin.

(2) melt flow rate (MFR):

Use fusion index instrument L244 (precious Industrial Co., Ltd system) to measure.Sheet with sample resins (resin or resin combination) is filled in the barrel of internal diameter 9.55mm, length 162mm specifically, after 210 ℃ of following fusions, for the fused sample resins, adds load equably with the piston that weighs 2160g, diameter 9.48mm.Mensuration is the resin take-off rate (g/10 minute) that the orifice of 2.1mm is extruded from the diameter that is located at barrel central authorities, with it as melt flow rate (MFR).

(3) specific refractory power of resin:

The resin that use should be measured carries out the film extrusion moulding, obtains the non-stretched film of thickness 20 μ m.The film that use obtains by Abbe refractometer (the system 4T of ァ go society of Co., Ltd. type, the system SL-Na-1 of society of Toshiba Corporation lamp), is measured specific refractory power.In addition, the extrusion temperature of film is 210 ℃ when the EVOH resin, be 260 ℃ during at polyamide resin, be 160 ℃ during in polyvinyl chloride (PVC) RESINS, be 200 ℃ during at polyacrylonitrile resin.

(4) haze value (turbidity value):

The resin that should measure or resin combination carry out extrusion moulding, obtain the non-stretched film that thickness is 20 μ m.The film that use obtains according to ASTM D1003-61, is measured the internal haze value by Bo Yike (Port ィッ Network) the full light reflectance meter of integrating sphere type light penetration (color technical institute system " HR-100 type " in the village).Also carry out identical mensuration for multilayer film.And then, for the multilayer bottle, be on circumference, to be divided into 4 parts 4 places in bottle body central authorities, measure internal haze value everywhere, with the haze value (turbidity value) of its mean value as bottle.

(5) from the main peak temperature that disperses of the tan δ of the diolefin deutero-block of resin:

Should measure resin or resin combination and carry out extrusion moulding, obtain the no oriented film of thickness 20 μ m.The film that use obtains, by RHEOLOGY Co., LTD system " DVERHEOSPECTOLER DVE-V4 ", at frequency 11Hz, displacement amplitude 10 μ m, chuck spacing 20mm, wide 5mm, measure temperature range-150 ℃～150 ℃, under the condition that heat-up rate is 3 ℃/minute, mensuration is from the main peak temperature that disperses of the tan δ of the diolefin deutero-block of resin.

(6) ethylene content and the saponification deg of polyvinyl alcohol resin (b1):

The ethylene content of polyvinyl alcohol resin (b1) and saponification deg by with the heavy-hydrogenated dimethyl sulfoxide (DMSO) as solvent ¹H-NMR (nucleus magnetic resonance) spectrum (measuring by NEC society system " JNM-GX-500 type ") is measured.

(7) containing ratio of each structural unit of polyester:

The containing ratio of each structural unit of polyester can by with the heavy-hydrogenated trifluoracetic acid as the polyester of solvent ¹H-NMR (nucleus magnetic resonance) spectrum (measuring by NEC society system " JNM-GX-500 type ") is measured.

(8) phosphate content of polyvinyl alcohol resin (b1):

Phosphate content is as phosphate ion (PO according to following method ₄ ^3-) content obtains.To join as the polyvinyl alcohol resin 10g that sample drying finishes among the 0.01 normal aqueous hydrochloric acid 50ml, stir 6 hours down at 95 ℃.The aqueous solution with after stirring carries out quantitative analysis with chromatography of ions, obtains phosphate ion content.Chromatographic column is used the CIS-A23 of (strain) horizontal river motor system, and elutriant makes the aqueous solution of the sodium bicarbonate of the yellow soda ash that contains 2.5mM and 1.0mM.In addition, in the time of quantitatively, use the inspection amount line of in phosphate aqueous solution, making.

(9) Na, the K in the polyvinyl alcohol resin (b1), Mg ionic content:

To join as the dry sliced 10g of sample among the 0.01 normal aqueous hydrochloric acid 50ml, stir 6 hours down at 95 ℃.Use the aqueous solution after chromatography of ions will stir to carry out quantitative analysis, Na ion, K ion and Mg ionic weight are carried out quantitatively.Chromatographic column is used the ICS-C25 of (strain) Yokogawa Motor system, and elutriant makes 2 of the tartrate that contains 5.0mM and 1.0mM, the aqueous solution of dipicolimic acid 2.In the time of quantitatively, use the inspection amount line that makes with sodium-chlor, Repone K and magnesium chloride brine respectively.From Na ion, K ion and the Mg ionic weight that obtains like this,, obtain basic metal and alkali earth metal salt amount in dry sliced in metal conversion amount.

(10) rate of oxygen absorption

(10-1) rate of oxygen absorption of resin combination:

Use oxygen absorption resin compositions, carry out extrusion moulding, obtain the film of thickness 20 μ m.The single thin film 0.01m that accurate weighing obtains ²(0.1m * 0.1m; Surface-area 0.02m ²), be rolled into the roller shape after make at film 1 hour, under 20 ℃, join in the Glass Containers of internal capacity 260ml of the air that is full of 65%RH.Air in the Glass Containers contains 21: 79 oxygen and nitrogen with volume ratio.The Glass Containers mouth is placed down at 20 ℃ with after containing the multilayer tablet of aluminium lamination and sealing with Resins, epoxy.After the inclosure, carry out the sampling of inner air through time ground, use this oxygen concentration of air of gas Chromatographic Determination with needle tubing.During mensuration, seal with the pore that Resins, epoxy will be opened on multilayer tablet at every turn.The oxygen that obtains from gas-chromatography and the volume ratio of nitrogen are calculated the reduction of oxygen, obtain the oxygen absorbed dose of composition.From its result, calculate the rate of oxygen absorption (ml/m of the resin combination of utmost dispatch point by the figure line slope ²Day).Embodiment 1 adopts this method.

(10-2) rate of oxygen absorption of resin combination:

Use resin combination, carry out extrusion moulding, obtain the film of thickness 20 μ m.With the single thin film 0.9m that obtains ²(0.2m * 4.5m; Surface-area 1.8m ²), behind 5 hours of made membrane, be rolled into the roller shape, under 20 ℃, put into the Erlenmeyer flask of the internal capacity 375ml of the air that is full of 65%RH.Air in the Erlenmeyer flask contains 21: 79 oxygen and nitrogen with volume ratio.Use contains the multilayer tablet of aluminium lamination and Resins, epoxy seal the Erlenmeyer flask mouth after, place down at 20 ℃.To enclose after 48 hours, after 96 hours and the inner air after 192 hours take a sample with needle tubing, use this oxygen concentration of air of gas Chromatographic Determination.The pore of at every turn opening on multilayer tablet during mensuration is all sealed with Resins, epoxy.Mensuration is to obtain by the reduction (oxygen absorbed dose) of the volume ratio calculating oxygen of oxygen that obtains from gas-chromatography and nitrogen.By after 2 days～oxygen reduction between after 8 days 6 days calculates the rate of oxygen absorption (ml/m of resin combination divided by number of days and surface-area ² Day).Embodiment 2～8 and comparative example 1 have adopted this method.

(11) oxygen permeation rate of gas-barrier resin (b)

(b) carries out extrusion moulding with gas-barrier resin, obtains the no oriented film of thickness 20 μ m.The film that obtains is adjusted to the humiture of 20 ℃-65%RH, uses oxygen transit dose determinator (modern control society system, OX-TRAN-10/50A), measure the oxygen transit dose.In addition, the extrusion temperature of film is 210 ℃ during the EVOH resin, be 260 ℃ during polyamide resin, be 160 ℃ during polyvinyl chloride (PVC) RESINS, be 200 ℃ during polyacrylonitrile resin.

(12) limiting viscosity of polyester:

Cut out the sample thin film layer from the polyester layer of laminated vessel body, be dissolved in phenol and tetrachloroethane etc. in the weight mixed solvent.Under 30 ℃, measure with Ubbelohde type viscometer (woods is made made " HRK-3 type ").

(13) second-order transition temperature of polyester and fusing point:

Cut out sample thin film layer (sample) from the polyester layer of laminated vessel body,,, be determined as follows with differential thermal analysis method (DSC) according to JISK7121.Use Seiko electronic industry (strain) system differential scanning calorimeter (DSC) RDC 220/SSC 5200H type, sample is remained on after 280 ℃ temperature reaches 5 minutes, condition 100 ℃/minute of cooling rates is issued to 30 ℃ temperature, and then, keep under the condition of 10 ℃/minute of heat-up rates, measuring after 5 minutes.But,, use indium and lead for temperature correction.In addition, the said second-order transition temperature of the present invention be meant among the above-mentioned JIS said intermediate point second-order transition temperature (Tmg) and then, said fusing point is meant said dissolving peak temperature (Tpm) among the above-mentioned JIS among the present invention.

(14) the oxygen transit dose (1) of multilayer film:

Be adjusted in humiture under the atmosphere of 20 ℃-85%RH, use oxygen transit dose determinator (modern society's system, the OX-TRAN-10/50A of controlling), measure the oxygen transit dose of laminate film.But, mensuration is nitrogen supply pool side from oxygen supply pond side direction, according to the order of stretched polypropene film layer/polyurethane series adhesive layer/oxygen screening film layer/polyurethane series adhesive layer/deoxidation thin film layer/polyurethane series adhesive layer/oriented polypropylene rete, layer is provided with film side by side to carry out.Mensuration is behind the system film after 24 hours, carries out measuring in 720 hours through time ground.Adopt this method among the embodiment 1.

(15) the oxygen transit dose (2) of multilayer film:

The laminate film that uses resin combination layer and stretched polypropene film lamination to constitute.Be adjusted in humiture under the atmosphere of 20 ℃-85%RH, use oxygen transit dose determinator (modern society's system, the OX-TRAN-10/50A of controlling), measure the oxygen transit dose of this film.Mensuration be behind the system film 24 hours with after time ground carried out 300 hours.Adopt this method in embodiment 2～8 and the comparative example 1.

(16) the oxygen absorbed dose of laminated vessel:

In the bag that uses multilayer film to obtain, be full of 20 ℃, the air 300ml of 65%RH.Air in bag contains 21: 79 oxygen and nitrogen with volume ratio.Place down at 20 ℃, after the inclosure, with needle tubing through the time oxygen concn is taken a sample, measure with gas-chromatography.In addition, during mensuration, use Resins, epoxy that the pore of opening on each multilayer tablet is all sealed.By the oxygen that obtains from gas-chromatography and the volume ratio of nitrogen, calculate the reduction of oxygen, obtain rate of oxygen absorption.

(17) the oxygen transit dose of laminated vessel:

At the doleiform shape that obtains intactly, after under air atmosphere, the humiture of bottle outside being adjusted to 20 ℃～65%RH, the inner humiture of bottle and being adjusted to 20 ℃～100%RH, with the determinator (modern society's system, the OX-TRAN-10/50A of controlling) of oxygen transit dose, measure the oxygen transit dose (ml/containerdayatm) of each container of moulding after 10 days.Then, with the bottle outside under 20 ℃-65%RH air atmosphere, bottle is inner under the state of 20 ℃-100%RH nitrogen atmosphere, keeping three months, and then measure the oxygen transit dose (ml/containerdayatm) of each container.

Embodiment 1

Added the thermoplastic resin (a) of antioxidant with following method preparation.

With dry nitrogen purge stirred autoclave in add hexanaphthene 600 parts by volume, N,N,N (TMEDA) 0.16 parts by volume, as n-BuLi 0.094 parts by volume of initiator.After temperature is warmed up to 50 ℃, add the styrene monomer of 4.25 parts by volume, make its polymerization 1.5 hours.Then, temperature drops to after 30 ℃, adds the isoprene monomer of 120 parts by volume, makes its polymerization 2.5 hours.Continue, temperature is warmed up to after 50 ℃ once more, adds the styrene monomer of 4.25 parts by volume, makes its polymerization 1.5 hours.

In the reaction solution that obtains, add the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate and tetramethylolmethane four (3-lauryl thiopropionate) respectively as antioxidant, its add-on is, each is respectively 0.15phr with respect to the total amount of vinylbenzene and isoprene.Reaction solution is injected methyl alcohol, make the triblock copolymer precipitation, be dried, use as the thermoplastic resin that has added antioxidant (a).

The number-average molecular weight of the triblock copolymer that obtains is 85000, the molecular weight of the styrene block in the multipolymer is 8500 respectively, styrene content is that vinyl bonds content in 14mol%, the isoprene block is 55%, is 55% with the content of the structural unit of structural formula (I) expression.The content of carbon-to-carbon two keys in the triblock copolymer that obtains is that 0.014eq/g, melt flow rate are 7.7g/10 minute.In this resin, contain the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate 0.12 weight % and tetramethylolmethane four (3-lauryl thiopropionate) 0.12 weight %.

Mensuration contains the specific refractory power and the haze value (turbidity value) of the thermoplastic resin (a) of above-mentioned antioxidant, is respectively 1.531 and 1.0%.In addition, measure this resin to disperse peak temperature by the tan δ in the diolefin deutero-block main be-3 ℃.

With above-mentioned thermoplastic resin 100 weight parts and cobalt stearate (II) 0.8484 weight part (is 0.0800 weight part as cobalt atom) dry blending, use 30mm φ biaxial extruder ((strain) TEX-30SS-30CRW-2V of JSW), under 210 ℃, screw speed 300rpm, 25kg/ hour condition of extrusion resin amount, extrude, after the granulation, under decompression in 30 ℃, 16 hours, carry out drying, obtain oxygen absorption resin compositions.The melt flow rate (MFR) of this resin combination (210 ℃-2160g load) is 7.1g/10 minute.

Use above-mentioned resin combination, under 210 ℃ of extrusion temperatures, carry out extrusion moulding, obtain the film of thickness 20 μ m.Measuring the haze value of this film inside, is 0.5%.Use the assay method of the rate of oxygen absorption (1) of resin combination in addition, when measuring the oxygen absorbed dose of film, obtain result shown in Figure 1.Its result, the absorption rate of resin combination is 95ml/m ²Day.

With the film (oxygen absorption film) that above-mentioned resin combination obtains, make following stack membrane.At the stretched polypropylene films (the eastern セロ system OP-#20U-1 of Co., Ltd.) of superimposed layer thickness 20 μ m of this film, with polyurethane series tackiness agent (Japan モ one ト Application system, trade(brand)name: AD335A and stiffening agent (Japan モ one ト Application system, trade(brand)name: toluene Cat-10)/methylethylketone mixing solutions (weight ratio 1: 1)) bond.Then the stretched polypropylene films (the eastern セロ system OP-#20U-1 of Co., Ltd.) of laminated thickness 15 μ m oxygen shielding films (the system ェバ one Le film EF-F#15 of Kuraray Co., Ltd.) and thickness 20 μ m successively on the another side of film uses above-mentioned polyurethane series adhesives.So just obtained having the oriented polypropylene rete/multilayer film that the layer of polyurethane series adhesive layer/oxygen shielding rete/polyurethane series adhesive layer/oxygen absorption rete/polyurethane series adhesive layer/oriented polypropylene rete constitutes.The haze value of this multilayer film is 2.7%.Use this multilayer film in addition, when measuring the oxygen transit dose through time ground, its result as shown in Figure 2.

And then, use above-mentioned multilayer film, make the layer that becomes the outside/oriented polypropylene rete/polyurethane series adhesive layer/oxygen shielding rete/polyurethane series adhesive layer/oxygen absorption rete/polyurethane series adhesive layer/oriented polypropylene rete/content side constitute 2 pieces of such coincidences, heat-sealing, make the pocket of 30cm * 30cm, the pocket that use obtains, when measuring the oxygen absorbed dose in the pocket, its result as shown in Figure 3.

Embodiment 2

The thermoplastic resin (a) that contains antioxidant with the method preparation identical with embodiment 1.Use the EVOH of polyvinyl alcohol resin (b1) as gas-barrier resin (b).This EVOH is that 32 moles of % of ethylene content, saponification deg 99.5%, melt flow rate (MFR) (210 ℃-2160g load) are 8.4g/10 minute.Measuring the phosphate content of this EVOH and Na, K, Mg ion content, is respectively 100ppm, 20ppm, 60ppm, 20ppm.And then the specific refractory power of mensuration EVOH, be 1.553.Oxygen permeation rate is 0.4ml20 μ m/m in addition ²Dayatm.

With above-mentioned thermoplastic resin (a) 5 weight parts, EVOH 95 weight parts and cobalt stearate (II) 0.2121 weight part (is 0.0200 weight part as cobalt atom) dry blending, use 30mm φ biaxial extruder ((strain) TEX-30SS-30CRW-2V of JSW), under 210 ℃, screw speed 300rpm, 25kg/ hour condition of extrusion resin amount, extrude, after the granulation, under decompression in 30 ℃, 16 hours, carry out drying, obtain resin composition pellet.The melt flow rate (MFR) of this resin combination (210 ℃-2160g load) is 9.5g/10 minute.With the broadwise out section of electron microscope observation resin composition pellet, be dispersed in the matrix that constitutes by EVOH as the particle before and after about 1 μ m of the above-mentioned triblock copolymer of thermoplastic resin (a).

The resin combination that use obtains carries out film extruding forming under 210 ℃ of extrusion temperatures, obtain the film of thickness 20 μ m.Measuring the haze value of this unitary film inside, is 1.0%.Then, measure the oxygen absorbed dose of film, obtain result shown in Figure 4.Measurement result after (48 hours) on the 2nd and (192 hours) on the 8th calculates (rate of oxygen absorption (2) with resin combination is calculated), and the rate of oxygen absorption of resin combination is 0.498ml/m ²Day.

The stretched polypropylene films (the eastern セロ system OP-#20U-1 of Co., Ltd.) of the film two sides superimposed layer thickness 20 μ m that make of above-mentioned resin combination, with polyurethane series tackiness agent (Japan モ one ト Application system, trade(brand)name: AD335A and stiffening agent (Japan モ one ト Application system, trade(brand)name: toluene Cat-10)/methylethylketone mixing solutions (weight ratio 1: 1)) bond, obtain stack membrane.The haze value of this stack membrane is 2.3%.Use this stack membrane in addition, measure the oxygen transit dose through time ground, its result as shown in Figure 5.

Then, use above-mentioned resin combination and carry out common injection blow molding moulding, be molded into blow molded bottle with the thermoplastic polyester of following method manufacturing.

It is the product that polymerizing catalyst prepares that thermoplastic polyester is to use with the germanium dioxide.With the content of each structural unit of NMR mensuration vibrin, consequently, the content of the terephthalic acid units in this polyester, ethylene glycol unit and glycol ether unit is respectively 50.0 moles of %, 48.9 moles of % and 1.1 moles of %.

Limiting viscosity, fusing point, second-order transition temperature are respectively 0.83dl/g, 252 ℃, 80 ℃.

In being total to the injection blow molding moulding, use day Coinjection stretch blow molded machine of smart ASB system (ASB-50HT type 750ml, 2), under the condition of 15 ℃ of 260 ℃ of hot-runner mould spleniums, the injection mold core temperature at 290 ℃ of PES side injection machine temperature, 220 ℃ of thermoplastic resin composition's side injection machine temperature, PES and this resin combination interflow, 15 ℃ of injection molding cavity temperatures, carry out coinjection moulding, obtain PES/ resin combination/PES, three stratotype bases of the resin of two kinds.

Then, the surface temperature of parison is heated to 105 ℃, carry out stretch blow-moldedly, obtain the mean thickness of body, internal layer PES is that 200 μ m, middle layer resin combination are that 20 μ m, outer PES are 3 layers multilayer constituting of two kinds of resins of 70 μ m injection blow molding shaped bottles altogether.

The bottle that use obtains, for the haze value of the body of bottle and moulding after 10 days and the oxygen transit dose of keeping bottle after 3 months measure, be 2.7% respectively, 0.00cc/containerdayatm and 0.00cc/containerdayatm.

Embodiment 3

EVOH 95 weight parts and cobalt stearate (II) 0.1060 weight part (is 0.0100 weight part as cobalt atom) that thermoplastic resin (a) 5 weight parts that use embodiment 1 obtains, embodiment 2 use obtain oxygen absorption resin compositions in the same manner with embodiment 2.The melt flow rate (MFR) of this resin combination (210 ℃-2160g load) is 9.3g/10 minute.During with the observable thermoplastic resin composition's particulate of electron microscope broadwise out section, the particle before and after about 1 μ m of the triblock copolymer of thermoplastic resin (a) is dispersed in the matrix that is made of EVOH.

The resin combination that obtains being carried out film extruding forming under 210 ℃ of extrusion temperatures, obtain the film of thickness 20 μ m, measure the unitary film internal haze value that obtains, is 0.9%.Then measure the oxygen absorbed dose of film, its result is illustrated among Fig. 4.After 2 days and the measurement result rate of oxygen absorption that calculate, resin combination (rate of oxygen absorption (2) with resin combination is calculated) after 8 days be 0.280ml/m ²Day.

Then, make stack membrane in the same manner with embodiment 2.The haze value of this stack membrane is 2.2%.Use this stack membrane, measure the oxygen transit dose through time ground, obtain the result that Fig. 5 represents.

The thermoplastic polyester that the resin combination that use obtains and embodiment 2 are identical carries out multilayer injection blow molding moulding altogether in the same manner with embodiment 2, and the multilayer blow moulding bottle is made in moulding.Obtain the mean thickness by body, 3 layers the multilayer that 2 kinds of resins of internal layer PES 200 μ m, middle layer resin combination 20 μ m, outer PES 70 μ m constitute is the injection blow molding shaped bottle altogether.

The bottle that use obtains, for the haze value of the body of bottle and moulding after 10 days and the oxygen transit dose of keeping bottle after 3 months measure, be 2.6% respectively, 0.00cc/containerdayatm and 0.00cc/containerdayatm.

Embodiment 4

EVOH 90 weight parts and cobalt stearate (II) 0.2121 weight part (is 0.0200 weight part as cobalt atom) that thermoplastic resin (a) 10 weight parts that use embodiment 1 obtains, embodiment 2 use obtain oxygen absorption resin compositions in the same manner with embodiment 2.The melt flow rate (MFR) of this resin combination (210 ℃-2160g load) is 9.0g/10 minute.During with the broadwise out section of the observable resin composition pellet of electron microscope, the particle before and after about 1 μ m of the triblock copolymer of thermoplastic resin (a) is dispersed in the matrix that is made of EVOH.

The resin combination that obtains is carried out film extruding forming under 210 ℃ of extrusion temperatures, obtain the film of thickness 20 μ m, measure the oxygen absorbed dose of film, its result is illustrated among Fig. 4.After 2 days and the measurement result after 8 days calculate that (rate of oxygen absorption (2) with resin combination is calculated) go out, the rate of oxygen absorption of resin combination is 0.595ml/m ²Day.

Then, make stack membrane in the same manner with embodiment 2.Use this stack membrane, measure the oxygen transit dose through time ground, obtain the result that Fig. 5 represents.

The thermoplastic polyester that the resin combination that use obtains and embodiment 2 are identical carries out multilayer injection blow molding moulding altogether in the same manner with embodiment 2, and the multilayer blow moulding bottle is made in moulding.Obtain being total to the injection blow molding shaped bottle by the mean thickness internal layer PES 200 μ m of body, 3 layers the multilayer that 2 kinds of resins of middle layer resin combination 20 μ m, outer PES 70 μ m constitute.

The bottle that use obtains, for moulding after 10 days and the keeping 3 months after the bottle the oxygen transit dose measure, all are 0.00cc/containerdayatm.

Embodiment 5

Thermoplastic resin (a) 5 weight parts, 44 moles of % of ethylene content, saponification deg 99.5%, melt flow rate (MFR) (210 ℃-2160g load) 13.0g/10 minute, specific refractory power 1.528, the oxygen permeation rate 1.50ml20 μ m/m that use embodiment 1 to obtain ²The EVOH95 weight part of dayatm and cobalt stearate (II) 0.2121 weight part (is 0.0200 weight part as cobalt atom) obtain oxygen absorption resin compositions in the same manner with embodiment 2.The melt flow rate (MFR) of this resin combination (210 ℃-2160g load) is 10.5g/10 minute.During with the broadwise out section of the observable resin composition pellet of electron microscope, the particle before and after about 1 μ m of the above-mentioned triblock copolymer of thermoplastic resin (a) is dispersed in the matrix that is made of EVOH.

The resin combination that obtains is carried out film extruding forming under 210 ℃ of extrusion temperatures, obtain the film of thickness 20 μ m.Measure the unitary film internal haze value that obtains this moment, is 1.7%.Then measure the oxygen absorbed dose of film, its result is illustrated among Fig. 4.After 2 days and the measurement result after 8 days calculate that (rate of oxygen absorption (2) with resin combination is calculated) go out, the rate of oxygen absorption of resin combination is 1.344ml/m ²Day.

Then, make stack membrane in the same manner with embodiment 2.The haze value of this stack membrane is 2.9%.Then, use this multilayer film, measure the oxygen transit dose through time ground, obtain the result that Fig. 5 represents.

Use above-mentioned resin combination and the thermoplastic polyester identical, carry out common injection blow molding moulding in the same manner, moulding making multilayer blow moulding bottle with embodiment 2 with embodiment 2.Obtain being total to the injection blow molding shaped bottle by the mean thickness internal layer PES 200 μ m of body, 3 layers the multilayer that 2 kinds of resins of middle layer resin combination 20 μ m, outer PES 70 μ m constitute.

The bottle that use obtains, for the haze value of the body of bottle and moulding after 10 days and the oxygen transit dose of keeping bottle after 3 months measure, be 3.3% respectively, 0.00cc/containerdayatm and 0.00cc/containerdayatm.

Comparative example 1

Use separately EVOH resin among the embodiment 2, under 210 ℃ of extrusion temperatures, carry out film extruding forming, obtain the film of thickness 20 μ m, measure the internal haze value of the unitary film that obtains this moment.Be 0.7%.Measure the oxygen absorbed dose of film in addition, its result is illustrated among Fig. 4.After 2 days and measurement result after 8 days calculate, the rate of oxygen absorption of this EVOH resin is 0.000ml/m ²Day.

Then, make stack membrane in the same manner with embodiment 2.The haze value of this stack membrane is 2.0%.Then use this stack membrane, measure the oxygen transit dose through time ground, obtain the result that Fig. 5 represents.

Use above-mentioned EVOH resin and the thermoplastic polyester identical, carry out common injection blow molding moulding in the same manner with embodiment 2, moulding multilayer blow moulding bottle with embodiment 2.Obtain the mean thickness by body, 3 layers the multilayer that 2 kinds of resins of internal layer PES 200 μ m, middle layer EVOH 20 μ m, outer PES 70 μ m constitute is the injection blow molding shaped bottle altogether.

The bottle that use obtains, for the haze value of the body of bottle and moulding after 10 days and the oxygen transit dose of keeping bottle after 3 months measure, be 2.4% respectively, 0.02cc/containerdayatm and 0.02cc/containerdayatm.

Above-mentioned test-results is summarised in the table 1.

Table 1

	Thermoplastic resin (a)	Gas-barrier resin (b)		Transition metal salt (c)	Resin combination		Multilayer film	The multilayer bottle
	Thermoplastic resin (a)	Gas-barrier resin (b)		Transition metal salt (c)	Resin combination		Multilayer film	The multilayer bottle		Use level (weight part)	Ethylene content (mole %)	Use level (weight part)	Use level (ppm)	Rate of oxygen absorption (ml/m ²·day)	Mist degree (%)	Mist degree (%)	The oxygen transit dose ^*1)	Mist degree (%)
	Embodiment 2	5	32	95	200	0.498	1.0	2.3	0.00	Use level (weight part)	Ethylene content (mole %)	Use level (weight part)	Use level (ppm)	Rate of oxygen absorption (ml/m ²·day)	Mist degree (%)	Mist degree (%)	The oxygen transit dose ^*1)	Mist degree (%)	2.7
Embodiment 3	Embodiment 2	5	32	95	200	0.498	1.0	2.3	0.00	5	32	95	100	0.280	0.9	2.2	0.00	2.6	2.7
Embodiment 3	Embodiment 4	10	32	90	200	0.595	-	-	0.00	5	32	95	100	0.280	0.9	2.2	0.00	2.6	-
Embodiment 5	Embodiment 4	10	32	90	200	0.595	-	-	0.00	5	44	95	200	1.344	1.7	2.9	0.00	3.3	-
Embodiment 5	Comparative Examples 1	0	32	100	0	0.000	0.7	2.0	0.02	5	44	95	200	1.344	1.7	2.9	0.00	3.3	2.4

^*1)ml/container·day·atm

Embodiment 6

The thermoplastic resin (a) that contains antioxidant with the method preparation identical with embodiment 1.(space portion is emerging to produce, trade(brand)name: 1030B) to use polycaprolactam as gas-barrier resin (b).Measuring the specific refractory power of this polycaprolactam, is 1.533.The oxygen permeation rate of this polycaprolactam is 80ml20 μ m/m in addition ²Dayatm.

With above-mentioned thermoplastic resin (a) 5 weight parts, polycaprolactam 95 weight parts and cobalt stearate (II) 0.2121 weight part (is 0.0200 weight part as cobalt atom) dry blending, use 30mm φ biaxial extruder ((strain) TEX-30SS-30CRW-2V of JSW), under 260 ℃, screw speed 300rpm, 25kg/ hour condition of extrusion resin amount, extrude, after the granulation, under decompression in 30 ℃, 16 hours, carry out drying, obtain resin composition pellet.With the broadwise out section of electron microscope observation resin composition pellet, the particle before and after about 1 μ m of the above-mentioned triblock copolymer of thermoplastic resin (a) is dispersed in the matrix of polycaprolactam formation.

With the resin combination that obtains, under 260 ℃ of extrusion temperatures, carry out film extruding forming, obtain the film of thickness 20 μ m.Measuring the haze value of this unitary film inside, is 1.2%.Then, measure the oxygen absorbed dose of film, obtain result shown in Figure 6.Measurement result calculating (rate of oxygen absorption (2) with resin combination is calculated) after (48 hours) on the 2nd and (192 hours) on the 8th goes out, and the rate of oxygen absorption of resin combination is 2.618ml/m ²Day.

The stretched polypropylene films of the film two sides superimposed layer thickness 20 μ m that obtain with above-mentioned resin combination (the eastern セロ system OP-#20U-1 of Co., Ltd.), with polyurethane series tackiness agent (Japan モ one ト Application system, trade(brand)name: AD 335A and stiffening agent (Japan モ one ト Application system, trade(brand)name: toluene Cat-10)/methylethylketone mixing solutions (weight ratio 1: 1)) bond, obtain stack membrane.The haze value of this stack membrane is 2.4%.Use this stack membrane in addition, the oxygen transit dose after the survey customised films after 4 days, consequently 6.8ml20 μ m/m ²Dayatm.

Then, use above-mentioned resin combination and carry out common injection blow molding moulding with the thermoplastic polyester of following method manufacturing, the multilayer blow moulding bottle is produced in moulding.

In being total to the injection blow molding moulding, use day Coinjection stretch blow molded machine of smart ASB system (ASB-50HT type 750ml, 2), under the condition of 15 ℃ of 280 ℃ of hot-runner mould spleniums, the injection mold core temperature at 290 ℃ of PES side injection machine temperature, 260 ℃ of thermoplastic resin composition's side injection temperature, PES and this resin combination interflow, 15 ℃ of injection molding cavity temperatures, carry out coinjection moulding, obtain PES/ resin combination/PES, three stratotype bases of two kinds of resins.

Then, the surface temperature of parison is heated to 105 ℃, carry out stretch blow-moldedly, obtain by the mean thickness in the body, internal layer PES is that 200 μ m, middle layer resin combination are that 20 μ m, outer PES are that 3 layers the multilayer that two kinds of resins of 70 μ m constitute constitutes injection blow molding shaped bottle altogether.

The bottle that use obtains is measured for the haze value of the body of bottle and the oxygen transit dose of bottle, is respectively 2.7% and 0.02cc/containerdayatm.

Embodiment 7

The thermoplastic resin (a) that contains antioxidant with the method preparation identical with embodiment 1.Use polyvinyl chloride (ponding chemical industry system, trade(brand)name: ェスメディカ V6142E) as gas-barrier resin (b).Measuring the specific refractory power of this polyvinyl chloride, is 1.535.This polyvinyl chloride oxygen permeation rate is 160ml20 μ m/m in addition ²Dayatm.

With above-mentioned thermoplastic resin (a) 5 weight parts, polyvinyl chloride 95 weight parts and cobalt stearate (II) 0.2121 weight part (is 0.0200 weight part as cobalt atom) dry blending, use 30mm φ biaxial extruder ((strain) TEX-30SS-30CRW-2V of JSW), under 160 ℃, screw speed 300rpm, 25kg/ hour condition of extrusion resin amount, extrude, after the granulation, under decompression in 30 ℃, 16 hours, carry out drying, obtain resin composition pellet.With the broadwise out section of electron microscope observation resin composition pellet, be dispersed in the matrix that polyvinyl chloride constitutes as the particle before and after about 2 μ m of the above-mentioned triblock copolymer of thermoplastic resin (a).

With the resin combination that obtains, under 160 ℃ of extrusion temperatures, carry out film extruding forming, obtain the film of thickness 20 μ m.Measuring the haze value of this unitary film inside, is 2.9%.Then, measure the oxygen absorbed dose of film, obtain result shown in Figure 6.Measurement result calculating (rate of oxygen absorption (2) with resin combination is calculated) after (48 hours) on the 2nd and (192 hours) on the 8th goes out, and the rate of oxygen absorption of resin combination is 4.105ml/m ²Day.

Then, obtain stack membrane in the same manner with embodiment 6.The haze value of this stack membrane is 3.5%.Use this stack membrane in addition, the oxygen transit dose after the survey customised films after 4 days, consequently 12.8ml20 μ m/m ²Dayatm.

Embodiment 8

The thermoplastic resin (a) that contains antioxidant with the method preparation identical with embodiment 1.Use polyacrylonitrile (Mitsui Chemicals industry system, trade(brand)name: バレッ Network ス 1000) as gas-barrier resin (b).Measuring the specific refractory power of this polyacrylonitrile, is 1.525.This polyacrylonitrile oxygen permeation rate is 6.9ml20 μ m/m in addition ²Dayatm.

With above-mentioned thermoplastic resin (a) 5 weight parts, polyacrylonitrile 95 weight parts and cobalt stearate (II) 0.2121 weight part (is 0.0200 weight part as cobalt atom) dry blending, use 30mm φ biaxial extruder ((strain) TEX-30SS-30CRW-2V of JSW), under 200 ℃, screw speed 300rpm, 25kg/ hour condition of extrusion resin amount, extrude, after the granulation, under decompression in 30 ℃, 16 hours, carry out drying, obtain resin composition pellet.With the broadwise out section of electron microscope observation resin composition pellet, be dispersed in the matrix that polyacrylonitrile constitutes as the particle before and after about 2 μ m of the above-mentioned triblock copolymer of thermoplastic resin (a).

With the resin combination that obtains, under 200 ℃ of extrusion temperatures, carry out film extruding forming, obtain the film of thickness 20 μ m.Measuring the haze value of this unitary film inside, is 4.9%.Then, measure the oxygen absorbed dose of film, obtain result shown in Figure 6.Measurement result calculating (rate of oxygen absorption (2) with resin combination is calculated) after (48 hours) on the 2nd and (192 hours) on the 8th goes out, and the rate of oxygen absorption of resin combination is 1.770ml/m ²Day.

Then, obtain stack membrane in the same manner with embodiment 6.The haze value of this stack membrane is 6.5%.Use this stack membrane in addition, the oxygen transit dose after the survey customised films after 4 days, consequently 0.7ml20 μ m/m ²Dayatm.

Above-mentioned test-results is summarised in the table 2.

Table 2

	Thermoplastic resin (a)	Gas-barrier resin (b)		Transition metal salt (c)	Resin combination		Multilayer film		The multilayer bottle
	Thermoplastic resin (a)	Gas-barrier resin (b)		Transition metal salt (c)	Resin combination		Multilayer film		The multilayer bottle		Use level (weight part)	Compound	Use level (weight part)	Use level (ppm)	Rate of oxygen absorption	Mist degree	The oxygen transit dose	Mist degree	The oxygen transit dose	Mist degree
	(ml/m ²·day)	(％)	^*4)	(％)	^*5)	(％)									Rate of oxygen absorption	Mist degree	The oxygen transit dose	Mist degree	The oxygen transit dose	Mist degree
	(ml/m ²·day)	(％)	^*4)	(％)	^*5)	(％)	Embodiment 6	5	^*1)	95					200	2.618	1.2	6.8	2.4	0.02	2.7
Embodiment 7	5	^*2)	95	200	4.105	2.9	Embodiment 6	5	^*1)	95	12.8	3.5	-	-	200	2.618	1.2	6.8	2.4	0.02	2.7
Embodiment 7	5	^*2)	95	200	4.105	2.9	Embodiment 8	5	^*3)	95	12.8	3.5	-	-	200	1.77	4.9	0.7	6.5	-	-

^*1) poly-ε-Ji Neixianan

^*2) polyvinyl chloride

^*3) polyacrylonitrile

^*4)ml·20μm/m ²·day·atm

^*5)ml/container·day·atm

Embodiment 9

The stack membrane that embodiment 1 is made strikes out the gasket shape that can overlap with the screw-cap body of the polypropylene system of external diameter 65mm, bottom thickness 1.2mm, on the screw-cap body be with, the state of the structure of lid side/oriented polypropylene rete/polyurethane series adhesive layer/oxygen shielding rete/polyurethane series adhesive layer/oriented polypropylene rete/content layer is installed.Then, the gasket seal lid that has that obtains is supplied on the mould of compressed moulding with the gasket seal shaper, in addition, supply with ethene-butene-1 copolymer (shell chemistry system " POLYBUTYLENE 8240 ": 1-butylene (99 moles more than the %), ethene (1 mole below the %) multipolymer, density 0.908g/cm to this compressed moulding with the gasket seal shaper ³, MFR=2.0g/10 minute (210 ℃, 2160g load)), make the lid have multi-layer sealed pad by compressed moulding.At this moment, the barrel temperature of compacting shape machine being adjusted in 245 ℃, nozzle temperature is adjusted in 235 ℃, die temperature and is adjusted in 30 ℃.

Stopping property with the such lidded container of making of following method evaluation.

In the blow molded bottle of the polyester cylindraceous of inner capacities 500ml, add 200ml water, load onto screw-cap, tighten lid according to the described main points of following evaluation method.Then, the body of holding bottle with hand high vibration 20 times up and down.Its result observes liquid and leaks state, estimates classification with following 4 grades.

A: only just tighten lightly and do not leak fully with finger.

B: only tighten the back lightly and leak the spire of wetting lid with finger.

C: only tighten the back lightly with finger and leak, water is diffused into the outside of lid, but does not leak after tightening powerfully.

D: also leak after tightening consumingly.

The result who estimates is " A ", has shown good sealing property.

Embodiment 10

The stack membrane that uses embodiment 2 to obtain carries out the test identical with embodiment 9.Its result obtains the evaluation of A.

Embodiment 11

The stack membrane that uses embodiment 6 to obtain carries out the test identical with embodiment 9.Its result obtains the evaluation of A.

According to the present invention, can obtain good resin combination of oxygen absorption or resin.Such resin or resin combination add and are easy to man-hour, can be modulated into the moulding product of arbitrary shape.Use these synthetic moulding product, for example when film, container, its oxygen absorption and gas-barrier property are good, and then, by the appropriate selection resin, can obtain the good transparency.Therefore, with the container that resin combination of the present invention or resin make, be very useful when being used for preserving food, medicine etc. and being subject to deterioration because of oxygen.In addition, on the easiness of the removal function of its good oxygen and use, also can be used as oxygen scavenger and use.

Use the multilayer structure making of above-mentioned resin or resin combination, for example the wrapping material of multilayer film formation also have above-mentioned premium properties, so also be used aptly.Particularly the container that constitutes of the following multilayer of holostrome thickness 300 μ m or the laminated vessel that constitutes with the thermoplastic polyester layer laminate except having above-mentioned oxygen absorption or gas-barrier property, can also suitably be used on the container that requires transparent purposes.

Simply accompanying drawing is illustrated below.

Fig. 1 is the time dependent figure of oxygen absorbed dose of the unitary film of embodiment 1.

Fig. 2 is the time dependent figure of oxygen transit dose of the multilayer film of embodiment 1.

Fig. 3 is the time dependent figure of bag internal oxygen absorbed dose that the multilayer film of embodiment 1 constitutes.

Fig. 4 is the time dependent figure of oxygen absorbed dose of the EVOH resin of the resin combination of embodiment 2～5 and comparative example 1.

Fig. 5 is the time dependent figure of oxygen transit dose of the multilayer structure making of embodiment 2～5 and comparative example 1.

Fig. 6 is the time dependent figure of oxygen absorbed dose of the resin combination of embodiment 6～8.

Claims

1. oxygen absorption resin compositions contains

Thermoplastic resin (a) with carbon-to-carbon double bond;

Oxygen permeation rate is 500ml20 μ m/m ²The gas-barrier resin (b) that dayatm (20 ℃, 65%RH) is following; And

Transition metal salt (c);

Wherein gas-barrier resin (b) is select from polyvinyl alcohol resin, polymeric amide, polyvinyl chloride and polyacrylonitrile at least a,

Wherein the particle of thermoplastic resin (a) formation is dispersed in the matrix of described gas-barrier resin (b),

Wherein its dispersion particle diameter of the particle of thermoplastic resin (a) composition is below the 10 μ m, and

Wherein based on the total resin weight that is contained in the resin combination, the content of thermoplastic resin (a) is 0.1～30 weight %, and the content of gas-barrier resin (b) is 99.9-70 weight %.

2. by the described resin combination of claim 1, its rate of oxygen absorption is 0.01ml/m ²More than the day.

3. by claim 1 or 2 described resin combinations, wherein said thermoplastic resin (a) contains the carbon-to-carbon double bond of the above ratio of 0.0001eq/g.

4. by any one described resin combination in the claim 1～3, wherein said thermoplastic resin (a) is the multipolymer of aromatic ethenyl compound and diolefin.

5. by any one described resin combination in the claim 1～4, it is 1000～500000 scopes that wherein said thermoplastic resin (a) contains a kind of structural unit and number-average molecular weight with structural formula (I) expression at least,

In the formula, R ₁Be alkyl, aryl, alkylaryl or the alkoxyl group of carbonatoms 1～10, R ₂And R ₃Be respectively hydrogen atom, carbonatoms 1～10 alkyl, substituted aryl, non-substituted aryl ,-COOR ₄,-OCOR ₅, cyano group or halogen atom, R ₄And R ₅Be respectively alkyl, aryl, alkylaryl or the alkoxyl group of carbonatoms 1～10 independently.

6. by any one described resin combination in the claim 1～5, the specific refractory power of wherein said gas-barrier resin (b) is 1.50～1.56.

7. by any one described resin combination in the claim 1～6, wherein said gas-barrier resin (b) is 5～60 moles of % of ethylene content, the ethylene-vinyl alcohol copolymer of saponification deg more than 90%.

8. by any one described resin combination in the claim 1～7, wherein said transition metal salt (c) is select from molysite, nickel salt, mantoquita, manganese salt and cobalt salt at least a.

9. press any one described resin combination in the claim 1～8, the described transition metal salt (c) that wherein contains, being converted into metallic element is the ratio of 1～5000ppm.

10. by any one described resin combination in the claim 1～9, the difference of the specific refractory power of wherein said thermoplastic resin (a) and gas-barrier resin (b) is below 0.01.

11. moulding product, it contains any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin among the claim 1-10.

12. a multilayer structure making, it has and contains the layer that right requires any one described oxygen absorption resin compositions among the 1-10 or oxygen absorption thermoplastic resin.

13. a laminated vessel, it has and contains the layer that right requires any one described oxygen absorption resin compositions among the 1-10 or oxygen absorption thermoplastic resin.

14. a laminated vessel, it is by containing the layer that any one described oxygen absorption resin compositions among the claim 1-10 or oxygen absorption thermoplastic resin constitute, and holostrome thickness is that the following multilayer film of 300 μ m constitutes.

15. a laminated vessel, it have by any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin among the claim 1-10 constitute the layer and the thermoplastic polyester layer constitute the layer.

16. a lid, it is equipped with the gasket seal that is made of any one described oxygen absorption resin compositions or oxygen absorption thermoplastic resin among the claim 1-10.