JP2012126772A - Oxygen barrier resin composition, and packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxygen barrier resin composition which is excellent particularly in transparency and excellent also in oxygen barrier property and moldability, and contains a conjugated diene polymer cyclized substance as an oxygen absorbing component.SOLUTION: The oxygen barrier resin composition having an oxygen absorbing property is obtained by mixing an oxygen absorbing resin composition containing a conjugated diene polymer cyclized substance, a thermoplastic resin including a polymer compound having a carboxyl group on the terminal thereof, and a compatibilizer including a compound having a functional group to react with a carboxyl group to form a bond.

Description

  The present invention relates to an oxygen-barrier resin composition and a packaging material having oxygen-absorbing properties, and more particularly, contents that are excellent in oxygen-absorbing properties, oxygen-barrier properties, transparency, and moldability, and deteriorate due to contact with oxygen. The present invention relates to an oxygen-barrier resin composition containing a conjugated diene polymer cyclized product as an oxygen-absorbing component, which is suitably used as a material for a packaging material such as a container for storing slag.

  Foods, beverages, pharmaceuticals, and the like are required to be stored so that they do not come into contact with oxygen as much as possible because quality deteriorates when they come into contact with oxygen. Therefore, an inert gas such as nitrogen is also filled in a container or package for storing foods, beverages, pharmaceuticals, and the like. However, this method has a problem that the cost is increased at the time of manufacturing, and once the bag is opened, air flows in from the outside, and it is impossible to prevent quality deterioration thereafter. For this reason, various studies have been conducted on techniques for removing oxygen remaining in containers or packaging.

  In recent years, as a technique for removing oxygen remaining in a container or a package, a technique in which the container or the package is configured using a resin composition having oxygen absorbability, and the container or the package itself absorbs oxygen has attracted attention. . For example, Patent Document 1 includes a gas barrier resin having an oxygen transmission rate equal to or lower than a specific value, a thermoplastic resin such as a styrene-isoprene-styrene triblock copolymer, a compatibilizing agent, and a transition metal salt. A resin composition having oxygen absorbability (oxygen scavenging function) is disclosed. Patent Document 2 describes a container made of a material containing polyethylene terephthalate, an oxygen absorbent composed of an aromatic polyester, a polyolefin and a transition metal catalyst, and an antioxidant. In the techniques described in these patent documents, oxygen absorption is achieved by oxidizing reaction of a thermoplastic resin such as styrene-isoprene-styrene triblock copolymer, aromatic polyester, or polyolefin by the action of a transition metal catalyst. Demonstrated. Further, the presence of the thermoplastic resin to be oxidized in the resin having a high oxygen barrier property also serves to prevent oxygen from entering the container from the outside of the container.

  However, in the technique of oxidizing a thermoplastic resin by the action of a transition metal catalyst as described in these patent documents, the polymer deteriorates as the reaction proceeds and the mechanical strength is significantly reduced. May be difficult to apply, depending on the application.

  Therefore, a resin composition using a conjugated diene polymer cyclized product as an oxygen-absorbing component has been proposed as a resin composition capable of exhibiting excellent oxygen-absorbing properties without containing a transition metal catalyst. For example, Patent Document 3 discloses a resin composition containing an oxygen-absorbing resin such as a conjugated diene polymer cyclized product and a softening agent as an oxygen-absorbing resin composition excellent in oxygen-absorbing property, and a specific polyester resin. An oxygen-absorbing resin composition is disclosed that is dispersed in a resin having a low oxygen permeability. According to this oxygen-absorbing resin composition, it is possible to exhibit excellent oxygen absorbency without requiring the presence of a transition metal-based catalyst, so the problem of mechanical strength reduction and the problem of transition metal catalyst elution Is resolved.

  However, the oxygen-absorbing resin composition obtained by blending a conjugated diene polymer cyclized product or the like with a polyester resin has a surface inferior to that of a plain polyester resin, and is used for applications requiring high transparency. There was a problem that it was difficult to apply.

JP 2002-146217 A JP 2004-131118 A International Publication No. 2008/102701

  The present invention provides an oxygen-barrier resin composition containing a conjugated diene polymer cyclized product as an oxygen-absorbing component, which is particularly excellent in transparency, excellent in oxygen absorption, oxygen barrier properties, and moldability. Objective.

  As a result of intensive studies in order to achieve the above object, the present inventor has an epoxy group and an oxazoline group in obtaining an oxygen barrier resin composition by mixing a polyester resin and a cyclized product of polyisoprene. It has been found that when a compatibilizing agent comprising a compound is blended, the dispersion state of the cyclized product of polyisoprene in the polyester resin is improved. And as a result of improving a dispersed state, it discovered that the transparency of the resin composition obtained was improved significantly, and also oxygen absorption property, oxygen barrier property, and moldability were also improved. As a result of further intensive studies based on this knowledge, the present invention has been completed.

  Thus, according to the present invention, an oxygen-absorbing resin composition containing a conjugated diene polymer cyclized product, a thermoplastic resin composed of a polymer compound having a carboxyl group at the terminal, and a carboxyl group are reacted to form a bond. An oxygen-barrier resin composition having oxygen absorbability obtained by mixing a compatibilizing agent comprising a compound having a functional group capable of being provided is provided.

  In the above oxygen barrier resin composition, the compatibilizer is preferably a compound having at least one of an epoxy group and an oxazoline group as a functional group capable of reacting with a carboxyl group to form a bond.

  In the above oxygen-barrier resin composition, the thermoplastic resin is preferably a polyester resin, and particularly preferably a polyethylene terephthalate resin or a modified polyethylene terephthalate resin.

  Moreover, according to this invention, the packaging material which uses said oxygen barrier property resin composition is provided.

  According to the present invention, an oxygen-barrier resin composition in which an oxygen-absorbing resin composition containing a conjugated diene polymer cyclized product is well dispersed in a thermoplastic resin composed of a polymer compound having a carboxyl group at the terminal is obtained. As a result, it is possible to provide an oxygen barrier resin composition that is particularly excellent in transparency and further excellent in oxygen absorption, oxygen barrier properties, and moldability.

  The oxygen-barrier resin composition having oxygen-absorbing property of the present invention is a heat comprising an oxygen-absorbing resin composition containing a conjugated diene polymer cyclized product as an oxygen-absorbing component and a polymer compound having a carboxyl group at the terminal. It is formed by mixing a plastic resin and a compatibilizer made of a compound having a functional group capable of reacting with a carboxyl group to form a bond.

  The conjugated diene polymer cyclized product used as an oxygen-absorbing component (effective component for oxygen absorption) in the oxygen-absorbing resin composition is obtained by cyclizing the conjugated diene polymer in the presence of an acid catalyst. And having a ring structure in the molecule and having at least one double bond in the ring structure.

  The conjugated diene polymer used for obtaining the conjugated diene polymer cyclized product includes a conjugated diene monomer homopolymer, a copolymer of two or more conjugated diene monomers, and a conjugated diene monomer. Copolymers with other monomers copolymerizable with this can be used. The conjugated diene monomer is not particularly limited, and specific examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1, Examples include 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of other monomers copolymerizable with the conjugated diene monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and p-tert. Fragrances such as butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2,4-dibromo styrene, vinyl naphthalene Group vinyl monomers, chain olefin monomers such as ethylene, propylene and 1-butene, cyclic olefin monomers such as cyclopentene and 2-norbornene, 1,5-hexadiene, 1,6-heptadiene, 1,7 Non-conjugated diene monomers such as octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, ( Examples include (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and other (meth) acrylic acid derivatives such as (meth) acrylonitrile and (meth) acrylamide. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Further, the copolymerization mode is not particularly limited, and may be, for example, a block copolymer or a random copolymer.

  Specific examples of the conjugated diene polymer include natural rubber (NR), styrene-isoprene rubber (SIR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer. Examples thereof include a combined rubber (IIR), an ethylene-propylene-diene copolymer rubber (EPDM), a butadiene-isoprene copolymer rubber (BIR), a styrene-isoprene block polymer, and a styrene-butadiene block polymer. Among these, polyisoprene rubber, polybutadiene rubber, and styrene-isoprene block polymer are preferably used, polyisoprene rubber and styrene-isoprene block polymer are more preferably used, and polyisoprene rubber is most preferably used. These conjugated diene polymers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the conjugated diene monomer unit in the conjugated diene polymer is not particularly limited, but is usually 40 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more. The production method of the conjugated diene polymer may be in accordance with a conventional method. For example, using a suitable catalyst such as a Ziegler polymerization catalyst, an alkyl lithium polymerization catalyst, or a radical polymerization catalyst, a conjugated diene polymer may be produced by a solution polymerization method or an emulsion polymerization method. By polymerizing the monomer, a conjugated diene polymer can be obtained. A conjugated diene polymer obtained by polymerization with a Ziegler polymerization catalyst and then metathesis decomposition using a catalyst such as ruthenium or tungsten can also be used.

  The microstructure of the conjugated diene polymer is not particularly limited. For example, when polyisoprene rubber is used as the conjugated diene polymer, the cis-1,4-bond unit content is preferably 23 to 99%, and the trans-1,4-bond unit content is 1 to 28. %, And the 3,4-bond unit content is preferably 0 to 55%.

  The conjugated diene polymer cyclized product can be obtained by subjecting the conjugated diene polymer as described above to a cyclization reaction in the presence of an acid catalyst. Known acid catalysts can be used for the cyclization reaction. Specific examples thereof include sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, alkylbenzenesulfonic acid having an alkyl group having 2 to 18 carbon atoms, anhydrides and alkyl esters thereof, and the like. Organic sulfonic acid compounds: boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, ethylammonium chloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, iron chloride, etc. A Lewis acid. These acid catalysts may be used alone or in combination of two or more. Further, tertiary butyl chloride, trichloroacetic acid or the like may be used in combination as a cocatalyst. Among these, an organic sulfonic acid compound is preferably used, and p-toluenesulfonic acid and xylenesulfonic acid are more preferably used. The usage-amount of an acid catalyst is 0.05-10 weight part normally per 100 weight part of conjugated diene polymers, Preferably it is 0.1-5 weight part, More preferably, it is 0.3-2 weight part.

  The cyclization reaction is usually performed by dissolving the conjugated diene polymer in a solvent. The solvent is not particularly limited as long as it does not inhibit the cyclization reaction, but is an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene; n-pentane, n-hexane, n-heptane, n-octane, etc. Hydrocarbon solvents such as aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclopentane and cyclohexane; are preferably used. The boiling point of these hydrocarbon solvents is preferably 70 ° C. or higher. The solvent used for the polymerization reaction of the conjugated diene polymer and the solvent used for the cyclization reaction may be of the same type. In this case, an acid catalyst for cyclization reaction can be added to the polymerization reaction solution after completion of the polymerization reaction, and the cyclization reaction can be carried out following the polymerization reaction. The amount of the hydrocarbon solvent used is such that the solid content concentration of the conjugated diene polymer is usually 5 to 60% by weight, preferably 20 to 40% by weight.

  The cyclization reaction can be performed under pressure, reduced pressure, or atmospheric pressure, but is preferably performed under atmospheric pressure from the viewpoint of ease of operation. When the cyclization reaction is performed in a dry air flow, particularly in an atmosphere of dry nitrogen or dry argon, side reactions caused by moisture can be suppressed. The reaction temperature and reaction time in the cyclization reaction are not particularly limited. The reaction temperature is usually 50 to 150 ° C., preferably 70 to 110 ° C., and the reaction time is usually 0.5 to 10 hours, preferably 2 to 5 hours. After carrying out the cyclization reaction, the acid catalyst is inactivated, the acid catalyst residue is removed, and then the hydrocarbon solvent is removed by a conventional method to obtain a solid conjugated diene polymer cyclized product.

  The unsaturated bond reduction rate of the conjugated diene polymer cyclized product is not particularly limited, but is preferably 40% or more, more preferably 52 to 70%, and 59 to 65%. Is particularly preferred. By using a conjugated diene polymer cyclized product having an unsaturated bond reduction rate in such a range, the oxygen barrier resin composition can be provided with good oxygen absorption performance, and the odor associated with oxygen absorption can be reduced. Occurrence can be suppressed. In addition, as the conjugated diene polymer cyclized product, two or more conjugated diene polymer cyclized products having different unsaturated bond reduction rates may be used in combination.

  The unsaturated bond reduction rate of the conjugated diene polymer cyclized product is an index representing the degree to which the unsaturated bond is reduced by the cyclization reaction in the conjugated diene monomer unit portion in the conjugated diene polymer. It is a numerical value obtained by That is, by proton NMR analysis, in the conjugated diene monomer unit portion in the conjugated diene polymer, the ratio of the peak area of the proton directly bonded to the double bond to the peak area of all protons is measured before and after the cyclization reaction, respectively. Calculate the reduction rate. Specifically, the unsaturated bond reduction rate of the conjugated diene polymer cyclized product can be determined as described below. That is, in the conjugated diene monomer unit portion in the conjugated diene polymer, the total proton peak area before the cyclization reaction is SBT, the peak area of the proton directly bonded to the double bond is SBU, and the total proton after the cyclization reaction Assuming that the peak area is SAT and the peak area of the proton directly bonded to the double bond is SAU, the peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is expressed by the formula: SB = SBU / SBT The peak area ratio (SA) of protons directly bonded to the double bond after the cyclization reaction is represented by the formula: SA = SAU / SAT. The unsaturated bond reduction rate is obtained by the formula: unsaturated bond reduction rate (%) = 100 × (SB−SA) / SB.

  The unsaturated bond reduction rate of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the amount of acid catalyst, reaction temperature, reaction time, etc. in the cyclization reaction of the conjugated diene polymer.

  The weight average molecular weight of the conjugated diene polymer cyclized product is usually 1000 to 1,000,000, preferably 50,000 to 500,000, more preferably as a standard polystyrene conversion value measured by gel permeation chromatography. 80,000-300,000. The weight average molecular weight of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the weight average molecular weight of the conjugated diene polymer subjected to cyclization. When the conjugated diene polymer cyclized product is a conjugated diene-aromatic vinyl monomer block copolymer cyclized product, the weight average molecular weight of the aromatic vinyl polymer block is 1000 to 300,000. Is preferred. By appropriately setting the weight average molecular weight of the conjugated diene polymer cyclized product, the solution viscosity at the time of the cyclization reaction becomes appropriate, and the workability and machine of the oxygen barrier resin composition finally obtained are improved. The mechanical strength is good.

  The molecular weight distribution of the conjugated diene polymer cyclized product is the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the block copolymer measured as standard polystyrene conversion values by gel permeation chromatography. The ratio (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.0. By using a conjugated diene polymer cyclized product having a small molecular weight distribution, the obtained oxygen barrier resin composition has particularly good oxygen absorptivity, and has little coloring and odor.

  The content of the gel in the conjugated diene polymer cyclized product is usually 10% by weight or less, preferably 5% by weight or less, and particularly preferably substantially free of gel, as the content of toluene insolubles. . When there is much content of gel, the workability of the oxygen barrier resin composition obtained may worsen.

  The glass transition temperature of the conjugated diene polymer cyclized product is not particularly limited, but is usually 40 ° C. or higher, preferably 50 ° C. or higher, and more preferably 55 ° C. to 80 ° C. The glass transition temperature of the conjugated diene polymer cyclized product is to adjust the reduction rate of unsaturated bond of the conjugated diene polymer cyclized product according to the type of conjugated diene polymer used to obtain the conjugated diene polymer cyclized product. It can be adjusted by.

  The oxygen-absorbing resin composition may be composed of only a conjugated diene polymer cyclized product as an active component for oxygen absorption, but may also comprise other components. For example, a softening agent can be blended in the oxygen-absorbing resin composition for the purpose of adjusting the glass transition temperature of the oxygen-absorbing resin composition as a whole.

  As the softening agent, a liquid material having a glass transition temperature of −30 ° C. or lower is preferably used. Further, the softener is preferably compatible with the conjugated diene polymer cyclized product, and is preferably incompatible with the thermoplastic resin composed of a polymer compound having a carboxyl group at the terminal, which will be described later. . Specific examples of the softener include hydrocarbon oils such as isoparaffinic oil, naphthenic oil, liquid paraffin; polybutene, polyisobutylene, atactic polypropylene, ethylene-α-olefin copolymer (linear low density polyethylene (LLDPE)) Olefin polymers (low molecular weight) such as linear ultra-low density polyethylene (LVLDPE); hydrogenated conjugated diene polymers (low molecular weight) such as polyisoprene and polybutadiene; styrene-conjugated diene polymers Hydrides (of low molecular weight); fatty acids such as oleic acid, erucic acid, stearic acid, isostearic acid; fatty acid esters. Of these, hydrocarbon oils and / or fatty acids are preferably used, and liquid paraffin and / or erucic acid is particularly preferably used. These softeners may be used alone or in combination of two or more.

  The blending amount of the softening agent is determined according to the type and blending ratio of each component of the oxygen-absorbing resin composition so that the glass transition temperature of the oxygen-absorbing resin composition can be within the target range. The oxygen-absorbing resin composition is generally 0 to 40% by weight, preferably 1 to 35% by weight, and more preferably 3 to 30% by weight.

  The oxygen-absorbing resin composition used in the present invention preferably has a glass transition temperature of −5 ° C. to + 20 ° C. By using an oxygen-absorbing resin composition having such a glass transition temperature, the oxygen-absorbing resin composition is particularly excellent in oxygen absorption performance at room temperature. The glass transition temperature of the oxygen-absorbing resin composition can be easily adjusted by adjusting the compounding ratio of each component in consideration of the glass transition temperature of each component constituting the oxygen-absorbing resin composition. it can.

  You may mix | blend antioxidant with an oxygen absorptive resin composition as needed. By blending an antioxidant, the stability of the oxygen-absorbing resin composition is improved, and handling during processing becomes easy. The content of the antioxidant in the oxygen-absorbing resin composition is not particularly limited, but is usually 5000 ppm by weight or less, preferably 3000 ppm by weight or less, more preferably 2000 ppm by weight or less, and particularly preferably 500 ppm by weight or less. . When there is too much content of antioxidant, there exists a possibility of inhibiting the oxygen absorption of an oxygen absorptive resin composition.

  The antioxidant is not particularly limited as long as it is usually used in the field of resin materials and rubber materials. Typical examples of such antioxidants include hindered phenol-based, phosphorus-based and lactone-based antioxidants. These antioxidants can also be used in combination of two or more. Among these, it is preferable to use a phosphorus-based antioxidant. In addition to these antioxidants, an amine light stabilizer (HALS) may be further added.

  In addition to the conjugated diene polymer cyclized product, another resin may be added to the oxygen-absorbing resin composition. For example, when a poly α-olefin resin is blended, the mechanical strength of the resulting composition can be improved. The poly α-olefin resin may be any one of α-olefin homopolymers, copolymers of two or more α-olefins, and copolymers of α-olefins and monomers other than α-olefins. In addition, these (co) polymers may be modified. Specific examples of the poly α-olefin resin include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), metallocene polyethylene, polypropylene, metallocene polypropylene, Examples thereof include polymethylpentene, polybutene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, and ethylene-cycloolefin copolymer. The poly α-olefin resin may be used alone or in combination of two or more.

  In addition, an oxidation catalyst that promotes the oxidation reaction of the conjugated diene polymer cyclized product may be added to the oxygen-absorbing resin composition. Typical examples of the oxidation catalyst include salts of transition metals (transition metal catalysts) such as manganese, iron, cobalt, nickel, copper, rhodium, and ruthenium. Examples of transition metal salt forms include chloride, acetate, stearate, palmitate, ethyl 2-ethylhexanoate, neodecanoate, and naphthoate. However, the conjugated diene polymer cyclized product used for constituting the oxygen-absorbing resin composition in the present invention is a resin that exhibits sufficient oxygen absorption even in the absence of an oxidation catalyst. It is not always necessary to add a catalyst, and an oxidation catalyst (transition metal-based catalyst) is included in the oxygen-absorbing resin composition in order not to cause a problem of a decrease in mechanical strength of the oxygen barrier resin composition or a problem of elution of the transition metal catalyst. ) Is not substantially contained.

  You may mix | blend another component with an oxygen absorptive resin composition as needed. Specific examples of other components that can be blended include fillers such as calcium carbonate, alumina and titanium oxide; tackifiers (hydrogenated petroleum resins, hydrogenated terpene resins, castor oil derivatives, sorbitan higher fatty acid esters, low molecular weight polybutenes) ); Surfactant; leveling agent; ultraviolet absorber; light stabilizer; dehydrating agent; pot life extending agent (acetylacetone, methanol, methyl orthoacetate, etc.); repellent improver;

  The thermoplastic resin which is an essential component for constituting the oxygen-barrier resin composition having oxygen absorbability of the present invention is a thermoplastic resin composed of a polymer compound having a carboxyl group at the terminal. Specific examples of the thermoplastic resin composed of a polymer compound having a carboxyl group at the terminal include polyester resins and polyamide resins, but are not limited thereto. In addition, the thermoplastic resin which consists of a high molecular compound which has a carboxyl group at the terminal may be used individually by 1 type, and can also be used in combination of 2 or more type.

  From the viewpoint of making the oxygen barrier resin composition of the present invention particularly excellent in transparency, a haze of thermoplastic resin comprising a polymer compound having a carboxyl group at the terminal (a 1 mm thick plate obtained by injection molding). The value measured based on JIS K7136) is preferably 5% or less, and more preferably 3% or less.

  Further, from the viewpoint of making the oxygen barrier resin composition of the present invention particularly excellent in transparency and solvent resistance, a polyester resin is used as a thermoplastic resin comprising a polymer compound having a carboxyl group at the terminal. Of these, polyethylene terephthalate resin or modified polyethylene terephthalate resin is preferably used.

  The modified polyethylene terephthalate resin is a polyester resin obtained by copolymerizing other components in addition to ethylene glycol and terephthalic acid. Other components that can be copolymerized in obtaining the modified polyethylene terephthalate resin include polycarboxylic acids such as isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and propylene. Examples thereof include polyhydric alcohols such as glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, diethylene glycol, and triethylene glycol. In the present invention, among the modified polyethylene terephthalate resins, a modified polyethylene terephthalate resin used as a component for copolymerizing at least one of isophthalic acid and 1,4-cyclohexanedimethanol is particularly preferably used.

  In the oxygen barrier resin composition of the present invention, the content ratio of the conjugated diene polymer cyclized product and the thermoplastic resin comprising a polymer compound having a carboxyl group at the terminal is not particularly limited, but the thermoplastic resin The content of the conjugated diene polymer cyclized product with respect to 100 parts by weight is usually 0.05 to 60 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight. .

  The compatibilizing agent, which is an essential component for constituting the oxygen barrier resin composition of the present invention, comprises a compound having a functional group capable of reacting with a carboxyl group to form a bond, and is a conjugated diene polymer cyclized product. And the polymer compound having a carboxyl group at the end thereof. The compatibilizer may be a compound having any structure as long as it is a compound having a functional group capable of reacting with a carboxyl group to form a bond, and a conjugated diene polymer cyclized product and From the viewpoint of better improving the compatibility with the polymer compound having a carboxyl group at the terminal, a compound having a site having an affinity for the conjugated diene polymer cyclized product is preferable.

  Examples of the functional group that can form a bond by reacting with a carboxyl group of a compound used as a compatibilizing agent in the present invention include an epoxy group, an oxazoline group, and a carbodiimide group, but are not limited thereto. Is not to be done. From the viewpoint of making the oxygen barrier resin composition of the present invention particularly excellent in transparency and oxygen barrier properties, epoxy groups and oxazoline groups may be used as functional groups capable of reacting with carboxyl groups to form bonds. It is preferable to use a compound having at least one as a compatibilizing agent.

  The compatibilizing agent is preferably a polymer compound from the viewpoint of preventing the compatibilizing agent from eluting from the oxygen barrier resin composition, and in particular, a site having affinity for the conjugated diene polymer cyclized product and A structural unit derived from a hydrocarbon monomer and a structural unit derived from a functional group-containing monomer containing a functional group capable of reacting with a carboxyl group to form a bond. Is particularly preferably used. Examples of hydrocarbon monomers that can be used to constitute such polymers include α-olefins such as ethylene and propylene, conjugated dienes such as butadiene and isoprene, and aromatic vinyls such as styrene and methylstyrene. As the functional group-containing monomer, a monomer containing an epoxy group such as glycidyl acrylate or glycidyl methacrylate and an ethylenically unsaturated bond, an oxazoline group such as 2-vinyl-2-oxazoline, and an ethylenically unsaturated group A monomer containing a bond is exemplified.

  Specific examples of the compatibilizer particularly preferably used in the present invention include an ethylene-glycidyl methacrylate copolymer (available as “LOTADER AX8840” manufactured by Arkema Co., Ltd.), an ethylene-glycidyl methacrylate-vinyl acetate copolymer (Sumitomo Chemical). Available as "Bond Fast 2B", etc.), ethylene-glycidyl methacrylate-methyl acrylate copolymer (available as "Bond Fast 7M", manufactured by Sumitomo Chemical Co., Ltd.), styrene- (2-vinyl-2-oxazoline) ) Copolymer (available as “Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.). In addition, a compatibilizing agent may be used individually by 1 type, and can also be used in combination of 2 or more type.

  In the oxygen barrier resin composition of the present invention, the content of the compatibilizer comprising a compound having a functional group capable of reacting with a carboxyl group to form a bond is not particularly limited, but oxygen absorption The content of the compatibilizer is usually 0.01 to 30 parts by weight, preferably 0.05 to 100 parts by weight of the total amount of the thermoplastic resin composed of the polymerizable resin composition and the polymer compound having a carboxyl group at the terminal. -20 parts by weight, more preferably 0.1-10 parts by weight.

  The oxygen barrier resin composition of the present invention reacts with the aforementioned oxygen-absorbing resin composition containing a conjugated diene polymer cyclized product, a thermoplastic resin comprising a polymer compound having a carboxyl group at the terminal, and a carboxyl group. It may be formed by mixing only a compatibilizing agent composed of a compound having a functional group capable of forming a bond, or may be a mixture of other components. Specific examples of other components that can be incorporated into the oxygen barrier resin composition include: a heat stabilizer; an ultraviolet absorber; a colorant; a pigment; a neutralizer; a plasticizer such as a phthalate ester and a glycol ester; Fillers such as alumina and titanium oxide; Tackifiers (hydrogenated petroleum resins, hydrogenated terpene resins, castor oil derivatives, sorbitan higher fatty acid esters, low molecular weight polybutenes); surfactants; leveling agents; ultraviolet absorbers; Agents; dehydrating agents; pot life extenders (acetylacetone, methanol, methyl orthoacetate, etc.); repellent improvers;

  The method of mixing each component in order to obtain the oxygen barrier resin composition is not particularly limited, and a known method may be adopted. However, the bonding by the reaction between the carboxyl group of the thermoplastic resin and the functional group of the compatibilizer From the viewpoint of promoting the formation and obtaining an oxygen barrier resin composition having more excellent transparency and the like, a melt-kneading method is preferred. The apparatus used when adopting the melt-kneading method is not particularly limited, and examples thereof include a screw kneader such as a single-screw kneader and a twin-screw kneader, a mixer such as a Banbury mixer, and a roll-type kneader. The kneading temperature is usually in the range of 50 to 320 ° C, preferably in the range of 170 to 300 ° C. The melt-kneaded oxygen barrier resin composition may be used for molding into a packaging material or the like in a molten state, or may be recovered as a molding material in the form of pellets or the like.

  The order in which the components are mixed to obtain the oxygen barrier resin composition is not particularly limited, and all the components may be mixed at once, or the components may be sequentially mixed in an arbitrary order. Further, at least one of the oxygen-absorbing resin composition containing a conjugated diene polymer cyclized product and a compatibilizer comprising a compound having a functional group capable of reacting with a carboxyl group to form a bond, preferably both, A master batch of an oxygen barrier resin composition mixed with a thermoplastic resin at a relatively high concentration is manufactured in advance, and this is a thermoplastic resin made of a polymer compound having a carboxyl group at the terminal in a molding machine. By mixing, an oxygen barrier resin composition can also be obtained. By obtaining the oxygen barrier resin composition through such an oxygen barrier resin composition master batch, the convenience in obtaining the oxygen barrier resin composition is improved. The order of mixing the components when obtaining the master batch of the oxygen barrier resin composition is not particularly limited, and all the components may be mixed at once, or the components may be sequentially mixed in any order. Although it is good, an oxygen-absorbing resin composition and a compatibilizing agent are mixed to obtain a mixture thereof, and then the mixture and a thermoplastic resin are mixed to obtain a master batch of the oxygen-barrier resin composition. As a result, the finally obtained oxygen barrier resin composition can be made particularly excellent in transparency and oxygen barrier properties.

  The type of the thermoplastic resin used in the master batch of the oxygen barrier resin composition is not particularly limited, but is composed of a polymer compound having a carboxyl group at the terminal used for obtaining the oxygen barrier resin composition. It is preferable that it is the same thermoplastic resin as a thermoplastic resin. Further, the content ratio of the conjugated diene polymer cyclized product in the master batch of the oxygen barrier resin composition is not particularly limited, but the content of the conjugated diene polymer cyclized product with respect to 100 parts by weight of the thermoplastic resin, It is preferable that it is 10-70 weight part. The content ratio of the compatibilizer comprising a compound having a functional group capable of reacting with a carboxyl group in the master batch of the oxygen barrier resin composition to form a bond is not particularly limited, The content of the compatibilizer with respect to 100 parts by weight of the total amount of the resin composition and the thermoplastic resin is preferably 1 to 40 parts by weight.

  In the oxygen barrier resin composition obtained as described above, the oxygen-absorbing resin composition and the thermoplastic resin can be mixed in a well dispersed state. Since a significant decrease in the transparency of the resin is prevented, this oxygen barrier resin composition has excellent transparency. The haze of the oxygen barrier resin composition (value measured based on JIS K7136 for a 1 mm thick plate obtained by injection molding) is usually 20% or less, preferably 17% or less.

  The oxygen absorption amount of the oxygen barrier resin composition may be determined by adjusting the blending amount of the conjugated diene polymer cyclized product according to the required oxygen absorption amount, and is not particularly limited. The amount of oxygen absorbed per 1 g of the barrier resin composition is preferably 1 cc / g or more, and more preferably 1.2 cc / g or more. The oxygen absorption amount per 1 g of the oxygen barrier resin composition is obtained by molding the target oxygen barrier resin composition into a 9 cm × 5.5 cm × 0.1 cm plate using an injection molding machine. When this plate is enclosed in an aluminum pouch together with 100 cc of air and this aluminum pouch is left to stand at 23 ° C. for 60 days, the plate is obtained based on the amount of oxygen absorbed by the plate of the oxygen barrier resin composition.

If the oxygen permeability of the oxygen barrier resin composition is also determined by adjusting the blending amount of the conjugated diene polymer cyclized product or selecting the thermoplastic resin to be used according to the required oxygen barrier property. Although not particularly limited, the oxygen permeability of the oxygen barrier resin composition is 0.5 cc / m ² · day · atm or less as a value at 30 ° C. and a relative humidity of 85%. Is preferably 0.3 cc / m ² · day · atm or less. Note that the oxygen permeability of the oxygen barrier resin composition was determined by molding the target oxygen barrier resin composition into a 1 mm thick plate using an injection molding machine, and JIS K7126-2 Measured under the conditions of 30 ° C. and 85% relative humidity.

  The packaging material of the present invention is a packaging material using the oxygen barrier resin composition obtained as described above. The form of the packaging material of the present invention is not particularly limited as long as it is a packaging material using the oxygen barrier resin composition of the present invention as at least a part of the material or the material thereof. For example, a film, a sheet, It can be made into the form used as materials of packaging materials, such as a parison, a preform, and a tube, and the form of packaging materials, such as a bottle, a cup, a bag, and a tray.

  What is necessary is just to select the shaping | molding method of an oxygen barrier resin composition suitably according to the form of the target packaging material. Specific examples of the molding method when the oxygen barrier resin composition is in the form of a film include a solution casting method and a melt molding method. When a multilayer film of the oxygen barrier resin composition of the present invention and another material is used, a single layer film of each layer constituting the multilayer film may be obtained and laminated, or the multilayer film may be directly formed. May be. In the case of directly forming a multilayer film, a known coextrusion molding method can be used. For example, extrusion may be performed using a multilayer multiple die using a number of extruders corresponding to the type of resin. Specific examples of the coextrusion molding method include a coextrusion lamination method, a coextrusion sheet molding method, a coextrusion inflation molding method, and a coextrusion blow molding method.

  When a hollow container such as a bottle is obtained using the oxygen barrier resin composition, a hollow molding method may be applied. As the hollow molding method, an extrusion hollow molding method in which a parison of a single layer of an oxygen barrier resin composition or a multilayer parison of an oxygen barrier resin composition and another material is molded by extrusion molding and then blown to mold. Alternatively, there is an injection hollow molding method in which an oxygen barrier resin composition single layer preform or a multilayer preform of an oxygen barrier resin composition and another material is molded by injection molding and then blown to perform molding. Is preferred. The oxygen barrier resin composition of the present invention is excellent in transparency, oxygen absorption, oxygen barrier properties, and moldability, and further has sufficient mechanical strength. It can use especially suitably as a material of a container.

  The packaging material of the present invention is useful as a packaging material or a material for packaging the contents that deteriorate due to contact with oxygen. The contents to be packaged are not particularly limited. For example, beverages such as beer, green tea, wine, juice drinks, soft drinks, fruits, nuts, vegetables, meat products, infant foods, coffee, boiled foods Foods such as foods, dairy products, jams, mayonnaise, ketchup, cooking oil, dressings, sauces, health care products such as shampoos, pharmaceutical products, cosmetics, dye inks, industrial products such as organic EL elements Can do.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

  Various measurements were performed according to the following methods.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of cyclized conjugated diene polymer]
Gel permeation chromatography using tetrahydrofuran as an eluting solvent (equipment: HLC8020 (manufactured by Tosoh Corporation), column: TSK gels G2000HXL, G4000HXL and G5000HXL (manufactured by Tosoh Corporation) connected in series, flow rate: 1.0 ml / min. And a temperature of 40 ° C., a detector: a differential refractometer) based on a value measured as a standard polystyrene equivalent molecular weight.

[Reduction rate of unsaturated bond of cyclized conjugated diene polymer]
(I) M.M. A. Golub and J.M. Heller, Can. J. et al. Chem. 41, 937 (1963). And (ii) Y. Tanaka and H.M. Sato, J .; Polym. Sci: Poly. Chem. Ed. 17, 3027 (1979). It was determined by proton NMR measurement with reference to the method described in the literature. In the conjugated diene monomer unit portion in the conjugated diene polymer, the total proton peak area before the cyclization reaction is SBT, the peak area of the proton directly bonded to the double bond is SBU, and the total proton after the cyclization reaction Assuming that the peak area is SAT and the peak area of the proton directly bonded to the double bond is SAU, the peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is expressed by the formula: SB = SBU / SBT The peak area ratio (SA) of protons directly bonded to the double bond after the cyclization reaction is represented by the formula: SA = SAU / SAT. Therefore, the unsaturated bond reduction rate is obtained by the formula: unsaturated bond reduction rate (%) = 100 × (SB−SA) / SB.

〔Glass-transition temperature〕
Using a differential scanning calorimeter (“EXSTAR 6000 DSC” manufactured by Seiko Instruments Inc.), the temperature was measured at a heating rate of 10 ° C./min in a nitrogen stream.

[Haze]
A thermoplastic resin or oxygen barrier resin composition as a sample was molded into a 9 cm × 5.5 cm × 0.1 cm plate using an injection molding machine (“ROBOSHOT S-2000i100A” manufactured by FANUC). About this board, the haze was measured based on JISK7136 using the haze meter (Nippon Denshoku Industries Co., Ltd. "NDH2000").

[Oxygen absorption amount of oxygen barrier resin composition]
The oxygen barrier resin composition as a sample was molded into a 9 cm × 5.5 cm × 0.1 cm plate using an injection molding machine (“ROBOSHOT S-2000i100A” manufactured by FANUC). This plate was sealed in an aluminum pouch together with 100 cc of air, and the aluminum pouch was allowed to stand for 60 days at 23 ° C. After standing for 60 days, 5 cc of the gas inside the aluminum pouch was sampled and the oxygen concentration was measured using an oxygen concentration meter (“LC-750F” manufactured by Toray Engineering Co., Ltd.). Based on this measurement value, an oxygen barrier resin The amount of oxygen absorbed per gram of the composition was determined.

[Oxygen permeability of oxygen barrier resin composition]
The oxygen barrier resin composition as a sample was molded into a 9 cm × 5.5 cm × 0.1 cm plate using an injection molding machine (“ROBOSHOT S-2000i100A” manufactured by FANUC). About this board, the oxygen permeability under 30 degreeC and 85% of relative humidity conditions was measured based on JISK7126-2 using the oxygen permeability measuring apparatus ("OX-TRAN" by MOCON).

[Moldability of oxygen barrier resin composition]
In the production example, when the pellet of the oxygen barrier resin composition was produced, the melt-kneaded strand of the oxygen barrier resin composition was observed, and based on the evaluation of the stability of the strand, the oxygen barrier resin composition The moldability was evaluated. The evaluation criteria are as follows.
Excellent: There is tension in the strand and the strand can be pulled very stably. Good: The strand cannot be pulled stably. Swell is generated and the strand cannot be pulled stably.

[Production Example 1]
Polyisoprene (cis-1,4 bond unit content 67.6%, trans-1,4 bond unit cut to 10 mm square in a pressure-resistant reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube 300 parts) was charged together with 700 parts of toluene, with a content of 23.8%, a 3,4-bond unit content of 8.6%, and a weight average molecular weight of 223,000. After purging the inside of the reactor with nitrogen, the mixture was heated to 85 ° C. and the polyisoprene was completely dissolved in toluene with stirring, and then p-toluenesulfonic acid (in toluene, so that the water content was 150 ppm or less, The product was reflux-dehydrated 2.4 parts, and the cyclization reaction was carried out while controlling the temperature so as not to exceed 85 ° C. After reacting for 5 hours, the reaction was stopped by adding a 25% aqueous sodium carbonate solution containing 0.83 parts of sodium carbonate. Next, the catalyst residue in the reaction system was removed by washing the oil layer components three times using 300 parts of ion-exchanged water (per once) under the condition of 85 ° C. And a part of toluene was distilled off from the obtained solution, and further toluene was removed by vacuum drying to obtain a solid polyisoprene cyclized product. The weight average molecular weight of the cyclized product of polyisoprene was 210,000, the molecular weight distribution was 1.7, the unsaturated bond reduction rate was 64%, and the glass transition temperature was 58 ° C.

  The obtained solid polyisoprene cyclized product was obtained by using a single-screw kneading extruder (40φ, L / D = 25, die diameter 3 mm × 1 hole, manufactured by Ikekai Co., Ltd.), cylinder 1: 140 ° C., cylinder 2 : 150 ° C., Cylinder 3: 160 ° C., Cylinder 4: 170 ° C., Die temperature 170 ° C., Kneading conditions of 25 rpm, and pelletized by a pelletizer to obtain a pelletized polyisoprene cyclized product.

[Production Example 2]
Modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd., haze 0.2%), cyclized product of pellet-shaped polyisoprene obtained in Production Example 1, The compatibilizer ethylene-glycidyl methacrylate copolymer ("LOTADER AX8840" manufactured by Arkema) and the liquid paraffin ("High Coal K-350" manufactured by Kaneda) of 80/20/8/5 were used. By weight ratio, using a biaxial kneader (“KZW15TW-60MG-NH” manufactured by Technobel), cylinder 1: 20 ° C., cylinder 2: 160 ° C., cylinder 3-8: 220 ° C., head and die: 220 ° C. Kneading under a kneading condition of 700 rpm, forming a pellet through a strand It is to obtain a master batch pellets A oxygen barrier resin composition. For the purpose of measuring the glass transition temperature of the oxygen-absorbing resin composition in the oxygen-barrier resin composition, a cyclized product of polyisoprene and liquid paraffin were similarly kneaded at a weight ratio of 20/5. The glass transition temperature of the oxygen-absorbing resin composition measured was 15 ° C.

[Production Example 3]
Instead of a modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd.), a polyethylene terephthalate resin (PET, “EASTWEST CHEMICAL” manufactured “EASTPET A12”, haze 0. 5%), and the kneading conditions were changed to Cylinder 1: 20 ° C., Cylinder 2: 230 ° C., Cylinder 3-8: 280 ° C., Head and Dies: 280 ° C., and Rotational Speed 700 rpm, Similarly, a master batch pellet B of the oxygen barrier resin composition was obtained.

[Production Example 4]
Modified polyethylene terephthalate resin (I-PET, Bell Polyester Products) copolymerized with isophthalic acid instead of the modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd.) A master batch pellet C of the oxygen barrier resin composition was obtained in the same manner as in Production Example 2 except that “IP252B” manufactured by the company was used.

[Production Example 5]
Instead of a modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd.), a modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol (PCTG, A master batch pellet D of an oxygen barrier resin composition was obtained in the same manner as in Production Example 2 except that “Easter EB062” manufactured by EASTMAN CHEMICAL, haze 0.3%) was used.

[Production Example 6]
As a compatibilizing agent, ethylene-glycidyl methacrylate-vinyl acetate copolymer (Sumitomo Chemical "Bond Fast 2B") was used instead of ethylene-glycidyl methacrylate copolymer ("LOTADER AX8840" manufactured by Arkema). Except for the above, a master batch pellet E of an oxygen barrier resin composition was obtained in the same manner as in Production Example 2.

[Production Example 7]
As a compatibilizer, an ethylene-glycidyl methacrylate-methyl acrylate copolymer (Sumitomo Chemical Co., Ltd., “Bond Fast 7M”) was used in place of the ethylene-glycidyl methacrylate copolymer (“LOTADE AX8840” manufactured by Arkema). Except for this, a master batch pellet F of an oxygen barrier resin composition was obtained in the same manner as in Production Example 2.

[Production Example 8]
As a compatibilizing agent, instead of an ethylene-glycidyl methacrylate copolymer ("LOTADER AX8840" manufactured by Arkema), a styrene- (2-vinyl-2-oxazoline) copolymer ("Epocross RPS-1005" manufactured by Nippon Shokubai Co., Ltd.) ) Was used in the same manner as in Production Example 2 to obtain a master batch pellet G of the oxygen barrier resin composition.

[Production Example 9]
Cyclized product of pellet-shaped polyisoprene obtained in Production Example 1, ethylene-glycidyl methacrylate copolymer as a compatibilizer (“LOTADER AX8840” manufactured by Arkema), and liquid paraffin (“High Coal” manufactured by Kaneda) as a softener. K-350 ") at a weight ratio of 20/8/5 using a twin-screw kneader (" KZW15TW-60MG-NH "manufactured by Technobel), cylinder 1: 20 ° C, cylinder 2: 160 ° C, cylinder 3 to 8: 180 ° C., head and die: 180 ° C., kneading conditions of a rotation speed of 700 rpm, and after passing through strands, were formed into pellets. Subsequently, the obtained pellet and a modified polyethylene terephthalate resin (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd., haze 0.2%) copolymerized with 1,4-cyclohexanedimethanol were used in a weight ratio of 33/80. Then, using a twin-screw kneader (“KZW15TW-60MG-NH” manufactured by Technobel) set at 220 ° C., cylinder 1: 20 ° C., cylinder 2: 160 ° C., cylinder 3-8: 220 ° C., head and Dice: Kneaded under kneading conditions of 220 ° C. and rotation speed of 700 rpm, and formed into pellets through strands, thereby obtaining master batch pellets H of an oxygen barrier resin composition.

[Comparative Production Example 1]
A master batch pellet I of an oxygen-barrier resin composition was obtained in the same manner as in Production Example 2, except that the compatibilizing agent ethylene-glycidyl methacrylate copolymer (“LOTADE AX8840” manufactured by Arkema) was not used. It was.

[Comparative Production Example 2]
A master batch pellet J of the oxygen barrier resin composition was obtained in the same manner as in Production Example 3 except that the compatibilizer ethylene-glycidyl methacrylate copolymer ("LOTADER AX8840" manufactured by Arkema) was not used. It was.

[Comparative Production Example 3]
As a compatibilizing agent, instead of an ethylene-glycidyl methacrylate copolymer ("LOTADER AX8840" manufactured by Arkema), an ethylene-acrylic acid ester having no functional group capable of reacting with a carboxyl group to form a bond A master batch pellet K of an oxygen barrier resin composition was obtained in the same manner as in Production Example 2, except that a maleic anhydride copolymer (“BONDINE LX4110” manufactured by Arkema Co., Ltd.) was used.

[Example 1]
Modified polyethylene terephthalate resin copolymerized with master batch pellet A of the oxygen barrier resin composition obtained in Production Example 2 and 1,4-cyclohexanedimethanol (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd., haze 0.2 %) Was supplied to an injection molding machine (FANUC “ROBOSHOT S-2000i100A”) set at a mold temperature of 40 ° C. and a resin temperature of 280 ° C. at a weight ratio of 113/1887, and an injection speed of 5 mm / s, It was molded into a plate shape of 9 cm × 5.5 cm × 0.1 cm under the conditions of a holding pressure of 1000 kg / cm ² and a cooling time of 50 seconds. About this board, haze, oxygen absorption, and oxygen permeability were measured. The results are shown in Table 1.

[Example 2]
Master batch pellet B of the oxygen barrier resin composition obtained in Production Example 3 and polyethylene terephthalate resin (PET, “EASTPET A12” manufactured by EASTWEST CHEMICAL, 0.5% haze) at a weight ratio of 113/1877 Supplied to an injection molding machine (FANUC "ROBOSHOT S-2000i100A") set at a mold temperature of 30 ° C and a resin temperature of 270 ° C, injection speed of 30mm / s, holding pressure of 800kg / cm ² , cooling time of 25 seconds Under the conditions, it was formed into a 9 cm × 5.5 cm × 0.1 cm plate shape. About this board, haze, oxygen absorption, and oxygen permeability were measured. The results are shown in Table 1.

Example 3
A modified polyethylene terephthalate resin obtained by copolymerizing 1,4-cyclohexanedimethanol using the master batch pellet C of the oxygen barrier resin composition obtained in Production Example 4 instead of the master batch pellet A of the oxygen barrier resin composition. Instead of (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd.), a modified polyethylene terephthalate resin (I-PET, Bell Polyester Products “IP252B”, haze 1.3%) copolymerized with isophthalic acid was used. Except for this, a plate was molded in the same manner as in Example 1, and its haze, oxygen absorption amount and oxygen permeability were measured. The results are shown in Table 1.

Example 4
Modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol using the master batch pellet D of the oxygen barrier resin composition obtained in Production Example 5 instead of the master batch pellet A of the oxygen barrier resin composition In place of (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd.), a modified polyethylene terephthalate resin copolymerized with 1,4-cyclohexanedimethanol (“PCTG, EASTMAN CHEMICAL“ EasterEB062 ”, haze 0.3%) is used. Except having used, the board | plate was shape | molded similarly to Example 1, and the haze, oxygen absorption amount, and oxygen permeability were measured. The results are shown in Table 1.

[Examples 5 to 8]
Instead of the master batch pellet A of the oxygen barrier resin composition, the same as in Example 1, except that the master batch pellets E to H of the oxygen barrier resin composition obtained in Production Examples 6 to 9 were used. The plate was molded, and its haze, oxygen absorption amount and oxygen permeability were measured. The results are shown in Table 1.

[Comparative Example 1]
Modified polyethylene terephthalate resin copolymerized with master batch pellet I of the oxygen barrier resin composition obtained in Comparative Production Example 1 and 1,4-cyclohexanedimethanol (PETG, “Sky Green J2003” manufactured by SK Chemical Co., Ltd. 2%) at a weight ratio of 105/1895 and supplied to an injection molding machine (FANUC “ROBOSHOT S-2000i100A”) set at a mold temperature of 40 ° C. and a resin temperature of 280 ° C., and an injection speed of 5 mm / s. The plate was molded into a 9 cm × 5.5 cm × 0.1 cm plate under the conditions of a holding pressure of 1000 kg / cm ² and a cooling time of 50 seconds. About this board, haze, oxygen absorption, and oxygen permeability were measured. The results are shown in Table 1.

[Comparative Example 2]
Master batch pellet J of oxygen barrier resin composition obtained in Comparative Production Example 2 and polyethylene terephthalate resin (PET, EASTWEST CHEMICAL “EASTPET A12”, haze 0.5%) at a weight ratio of 105/1895, Supplied to an injection molding machine (FANUC "ROBOSHOT S-2000i100A") set at a mold temperature of 30 ° C and a resin temperature of 270 ° C, injection speed of 30mm / s, holding pressure of 800kg / cm ² , cooling time of 25 seconds Under the conditions, it was formed into a 9 cm × 5.5 cm × 0.1 cm plate shape. About this board, haze, oxygen absorption, and oxygen permeability were measured. The results are shown in Table 1.

[Comparative Example 3]
A plate was obtained in the same manner as in Example 1 except that the master batch pellet A of the oxygen barrier resin composition obtained in Comparative Production Example 3 was used instead of the master batch pellet A of the oxygen barrier resin composition. Molding was performed, and the haze, oxygen absorption and oxygen permeability were measured. The results are shown in Table 1.

  As can be seen from the results shown in Table 1, as in the oxygen barrier resin compositions of Examples 1 to 8, the oxygen-absorbing resin composition containing the conjugated diene polymer cyclized product and a high carboxyl group-containing terminal An oxygen-barrier resin composition having an oxygen absorption property obtained by mixing a thermoplastic resin comprising a molecular compound and a compatibilizing agent comprising a compound having a functional group capable of reacting with a carboxyl group to form a bond. Can be said to have small haze, large oxygen absorption, small oxygen permeability and excellent formability. In contrast, the compatibilization comprising the oxygen barrier resin composition of Comparative Examples 1 and 2 that does not contain the compatibilizer itself, or a compound that does not have a functional group capable of reacting with a carboxyl group to form a bond. The oxygen barrier resin composition of Comparative Example 3 containing an agent has a larger haze, a smaller oxygen absorption amount, a higher oxygen permeability, and a molding compared to the oxygen barrier resin compositions of Examples 1 to 8. It was inferior in nature. Therefore, it can be said that the oxygen barrier resin composition of the present invention is excellent in transparency, oxygen absorbability, oxygen barrier property, and moldability.

Claims (5)

  An oxygen-absorbing resin composition containing a conjugated diene polymer cyclized product, a thermoplastic resin comprising a polymer compound having a carboxyl group at the terminal, and a compound having a functional group capable of reacting with the carboxyl group to form a bond An oxygen barrier resin composition having an oxygen absorption property obtained by mixing a compatibilizing agent comprising:   The oxygen barrier resin composition according to claim 1, wherein the compatibilizing agent is a compound having at least one of an epoxy group and an oxazoline group as a functional group capable of reacting with a carboxyl group to form a bond.   The oxygen barrier resin composition according to claim 1 or 2, wherein the thermoplastic resin is a polyester resin.   The oxygen barrier resin composition according to claim 3, wherein the thermoplastic resin is a polyethylene terephthalate resin or a modified polyethylene terephthalate resin.   The packaging material formed using the oxygen barrier resin composition in any one of Claims 1-4.