JP5385494B2 - Resin composition and multilayer container - Google Patents

Description

  The present invention relates to a resin composition having an oxygen scavenging function. In addition to the oxygen scavenging function, the present invention also relates to a resin composition having excellent gas barrier properties, moisture resistance, fragrance retention, and flavor barrier properties, and a multilayer container using the resin composition.

  A gas barrier resin such as an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) can be melt-molded and has excellent oxygen or carbon dioxide gas barrier properties. Therefore, for example, a multilayer structure including a layer made of EVOH and a layer of a thermoplastic resin excellent in moisture resistance, mechanical properties, etc. (for example, thermoplastic polyester; hereinafter, the thermoplastic polyester may be abbreviated as PES). The body is used for various molded bodies (for example, films, sheets, bottles, containers, etc.) that require gas barrier properties. For example, such multilayer structures are used in various fields as multilayer containers, particularly in the form of bags, bottles, cups, pouches and the like. For example, it is widely used in the fields of food, cosmetics, medical chemicals, toiletries and the like.

  Although the multilayer container is excellent in barrier properties such as oxygen and carbon dioxide, the permeability of gas such as oxygen is limited to zero, such as metal materials used for canning and glass used for bottling. It is not close, but permeates a negligible amount of gas. In particular, in containers such as foods, there is a concern about deterioration of the quality due to oxidation of the contents when stored for a long period of time, so improvement of oxygen barrier properties is strongly desired.

  On the other hand, when filling the contents, oxygen may be mixed in the container together with the contents. If the contents are prone to oxidation, this small amount of oxygen may reduce the quality of the contents, and in order to prevent this, it has been proposed to give the container material an oxygen scavenging function. Yes. In this case, oxygen that tends to enter the inside from the outside of the container is also scavenged, so that the gas barrier property of the packaging material is also improved.

  For example, as a method for imparting an oxygen scavenging function to the gas barrier resin constituting the container material, (1) by adding an oxidation catalyst such as a transition metal to EVOH, the EVOH is easily oxidized and scavenged with oxygen. (2) A method for imparting an oxygen scavenging function by adding a metal catalyst to polyvinyl chloride so that the polyvinyl chloride can be easily oxidized (Japanese Patent Laid-Open No. 4-21444). (3) A method of imparting an oxygen scavenging function to EVOH by dispersing a resin composition comprising a polyolefin and an oxidation catalyst, that is, a polyolefin in an easily oxidized state in EVOH (Japanese Patent Laid-Open No. 5-45144). No. 156095); (4) EVOH, polyolefin and oxidation catalyst are blended to make EVOH and polyolefin easily oxidized. Method of imparting oxygen scavenging function (Japanese Unexamined Patent Publication No. 5-170980) are known. However, the above methods (1) and (2) are not sufficient in improving the oxygen barrier property, and the methods (3) and (4) have the problem that the transparency of the gas barrier resin is significantly impaired. Have.

  Furthermore, in the multilayer container, in particular, when an adhesive resin layer is not provided between the layers, a thermoplastic resin layer (for example, a PES layer) can be obtained by applying an impact such as filling the container with a beverage, food or the like and dropping it. Peeling (delamination) is likely to occur between the EVOH layer and this is a major problem in appearance.

Problems to be solved by the invention

  An object of the present invention is to provide a resin composition having an oxygen scavenging function. Another object of the present invention is to provide a resin composition having excellent gas barrier properties, transparency, moisture resistance, aroma retention, and flavor barrier properties in addition to the oxygen scavenging function. Still another object of the present invention is to provide a multi-layer container excellent in impact peel resistance and having a good appearance, particularly good transparency, including a layer made of the resin composition.

Means for solving the problem

The first resin composition of the present invention has a gas barrier resin (A) having an oxygen permeation rate of 500 ml · 20 μm / m ² · day · atm (20 ° C., 65% RH) or less, 40 to 99.8% by weight, A resin composition containing 0.1 to 30% by weight of a thermoplastic resin (B) other than the gas barrier resin (A) and 0.1 to 30% by weight of a compatibilizer (C), wherein the thermoplastic resin The resin (B) has a carbon-carbon double bond, and the oxygen absorption rate of the resin composition is 0.001 ml / m ² · day or more.

  In a preferred embodiment, the first resin composition further contains a transition metal salt (D).

The second resin composition of the present invention has a gas barrier resin (A) having an oxygen transmission rate of 500 ml · 20 μm / m ² · day · atm (20 ° C., 65% RH) or less, 40 to 99.8% by weight, Resin composition containing 0.1-30 wt% of thermoplastic resin (B) other than gas barrier resin (A), 0.1-30 wt% of compatibilizer (C), and transition metal salt (D) The thermoplastic resin (B) has a carbon-carbon double bond.

  In a preferred embodiment, when the first resin composition contains a transition metal salt (D), the content of the transition metal salt in the composition, and the transition contained in the second resin composition The content of the metal salt (D) in the composition is 1 to 5000 ppm in terms of metal element, based on the total weight of the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C). It is.

  In a preferred embodiment, the transition metal salt (D) has at least one transition metal selected from the group consisting of iron, nickel, copper, manganese and cobalt.

  In a preferred embodiment, the thermoplastic resin (B) contains a carbon-carbon double bond at a rate of 0.0001 eq / g or more.

  In a preferred embodiment, the thermoplastic resin (B) has the following structural formula (I):

Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂ is a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group, and R ₃ and R ₄ Each independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, —COOR ₅ , —OCOR ₆ , a cyano group, or a halogen atom, and R ₅ and R ₆ are each independently an alkyl group. , An aryl group, an alkylaryl group, an arylalkyl group, or an alkoxy group).

  In a preferred embodiment, the thermoplastic resin (B) has a number average molecular weight of 1,000 to 500,000.

  In a preferred embodiment, the gas barrier resin (A) is EVOH having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more.

  In a preferred embodiment, the difference in refractive index between the gas barrier resin (A) and the thermoplastic resin (B) is 0.01 or less.

  In a preferred embodiment, the particles made of the thermoplastic resin (B) are dispersed in a matrix of the gas barrier resin (A).

  The third resin composition of the present invention is a resin composition containing a thermoplastic resin (B) and a compatibilizer (C), and the thermoplastic resin (B) has the following structural formula (I)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are as described above).
And a carbon-carbon double bond at a rate of 0.0001 eq / g or more, and the number average molecular weight of the thermoplastic resin (B) is 1000 to 500,000, and the resin The oxygen absorption rate of the composition is 0.1 ml / m ² · day or more.

  In a preferred embodiment, the third resin composition contains a transition metal salt (D).

  The fourth resin composition of the present invention is a resin composition containing a thermoplastic resin (B), a compatibilizer (C) and a transition metal salt (D), wherein the thermoplastic resin (B) is The following structural formula (I)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are as described above).
And a carbon-carbon double bond at a rate of 0.0001 eq / g or more, and the number average molecular weight of the thermoplastic resin (B) is 1,000 to 500,000.

  In a preferred embodiment, when the third resin composition contains a transition metal salt (D), the content of the transition metal salt in the composition, and the transition contained in the fourth resin composition The content of the metal salt (D) in the composition is 1 to 50000 ppm in terms of metal element, based on the total weight of the thermoplastic resin (B) and the compatibilizer (C).

  In a preferred embodiment, the transition metal salt (D) has at least one transition metal selected from the group consisting of iron, nickel, copper, manganese and cobalt.

  In a preferred embodiment, the compatibilizer (C) is at least one functional selected from the group consisting of a carboxyl group, a boronic acid group, and a boron-containing group that can be converted to a boronic acid group in the presence of water. It is a thermoplastic resin having a group

  In a preferred embodiment, the thermoplastic resin (B) has an aromatic vinyl compound unit and a diene compound unit. In a more preferred embodiment, the diene compound unit is at least one selected from the group consisting of isoprene units and butadiene units. In a more preferred embodiment, the aromatic vinyl compound unit is a styrene unit. In a more preferred embodiment, the thermoplastic resin (B) is a block copolymer.

  The multilayer structure of the present invention includes at least one layer made of any of the first to fourth resin compositions.

  The multilayer container of the present invention includes at least one layer composed of any one of the first to fourth resin compositions and a thermoplastic polyester layer.

The present invention is described in detail below.
As used herein, “scavenging” oxygen means absorbing or consuming oxygen from a given environment or reducing its amount.

The kind of gas barrier resin (A) contained in the first resin composition and the second resin composition of the present invention is not particularly limited, and any resin having good gas barrier properties may be used. it can. Specifically, a resin having an oxygen transmission rate of 500 ml · 20 μm / m ² · day · atm (20 ° C., 65% RH) or less is used. This means that when measured in an environment of 20 ° C. and a relative humidity of 65%, the oxygen volume permeating through a film having an area of 1 m ² and a thickness of 20 μm per day in a state where there is an oxygen differential pressure of 1 atm. It means 500 ml or less. If the oxygen permeation rate exceeds 500 ml · 20 μm / m ² · day · atm, the resulting resin composition has insufficient gas barrier properties. The oxygen permeation rate of the gas barrier resin (A) is preferably 100 ml · 20 μm / m ² · day · atm or less, more preferably 20 ml · 20 μm / m ² · day · atm or less, and more preferably Is 5 ml · 20 μm / m ² · day · atm or less.

  The refractive index of the gas barrier resin (A) is preferably in the range of 1.50 to 1.56. If it deviates from this range, as described later, the difference between the refractive index of the gas barrier resin (A) and the refractive index of the thermoplastic resin (B) increases, and the transparency of the resulting resin composition may decrease. is there. In general, since the refractive index of the thermoplastic resin (B) having oxygen absorptivity is often in the above range, the difference in refractive index between the thermoplastic resin (B) and the gas barrier resin (A) can be reduced. As a result, it becomes possible to obtain a resin composition having good transparency. The refractive index of the gas barrier resin (A) is more preferably 1.51 or more, and further preferably 1.52 or more. Moreover, it is preferably 1.55 or less, and more preferably 1.54 or less.

  Examples of the gas barrier resin (A) as described above include polyvinyl alcohol resins, polyamide resins, polyvinyl chloride resins, polyacrylonitrile resins, and the like, but are not limited to these resins.

  Among the gas barrier resins (A), the polyvinyl alcohol resin is a vinyl ester homopolymer or a copolymer of vinyl ester and other monomers (particularly a copolymer of vinyl ester and ethylene). Saponified using an alkali catalyst or the like. As the vinyl ester, vinyl acetate is a typical compound, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used.

  The saponification degree of the vinyl ester component of the polyvinyl alcohol resin is preferably 90% or more, more preferably 95% or more, and further preferably 96% or more. If the degree of saponification is less than 90 mol%, the gas barrier properties under high humidity are reduced. Moreover, when the said polyvinyl alcohol-type resin (A) is EVOH, thermal stability becomes inadequate and it will become easy to generate | occur | produce a gel and a brittle at the time of shaping | molding.

  When the polyvinyl alcohol resin (A) is composed of a mixture of two or more types of polyvinyl alcohol resins having different saponification degrees, the average value calculated from the mixing weight ratio is defined as the saponification degree.

  Among the polyvinyl alcohol resins (A) as described above, EVOH is preferable because it can be melt-molded and has good gas barrier properties under high humidity.

  The ethylene content of EVOH is preferably 5 to 60 mol%. When the ethylene content is less than 5 mol%, the gas barrier property under high humidity may be lowered and the melt moldability may be deteriorated. The ethylene content of EVOH is preferably 10 mol% or more, more preferably 15 mol% or more, and most preferably 20 mol% or more. On the other hand, if the ethylene content exceeds 60 mol%, sufficient gas barrier properties may not be obtained. The ethylene content is preferably 55 mol% or less, and more preferably 50 mol% or less.

  As described above, EVOH that is preferably used has an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more. When a multilayer container containing the resin composition of the present invention is desired to have excellent impact peel resistance, the ethylene content is 25 mol% or more and 55 mol% or less, and the saponification degree is 90% or more and 99% or less. It is preferred to use less than EVOH.

  When EVOH consists of a mixture of two or more types of EVOH having different ethylene contents, the average value calculated from the mixing weight ratio is taken as the ethylene content. In this case, it is preferable that the difference in ethylene content between EVOHs having the most distant ethylene contents is 30 mol% or less and the difference in the degree of saponification is 10% or less. When these conditions are not satisfied, the transparency of the resin composition layer may be impaired. The difference in ethylene content is more preferably 20 mol% or less, and even more preferably 15 mol% or less. Further, the difference in the degree of saponification is more preferably 7% or less, and further preferably 5% or less. In the multilayer container containing the resin composition of the present invention, when it is desired to have a balance at a higher level of impact resistance and gas barrier properties, the ethylene content is 25 mol% or more and 55 mol% or less, EVOH (a1) having a saponification degree of 90% or more and less than 99% and EVOH (a2) having an ethylene content of 25 mol% or more and 55 mol% or less and a saponification degree of 99% or more It is preferable to use a mixture such that a1 / a2 is 5/95 to 95/5.

  The ethylene content and saponification degree of EVOH can be determined by a nuclear magnetic resonance (NMR) method.

  As described above, this EVOH can also contain a small amount of a monomer other than ethylene and vinyl alcohol as a copolymerization component as long as the object of the present invention is not impaired. Examples of such monomers include the following compounds: α-olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; itaconic acid, Unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, salts thereof, partial or complete esters thereof, nitriles, amides thereof, anhydrides thereof; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy- Ethoxy) silanes, vinylsilane compounds such as γ-methacryloxypropyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidones.

  In particular, when the vinyl silane compound is contained in EVOH as a copolymerization component in an amount of 0.0002 to 0.2 mol%, the composition of the present invention containing the EVOH is co-polymerized with a resin (for example, PES) to be a base material. When a multilayer structure is obtained by extrusion molding or co-injection molding, the consistency of the melt viscosity with the base resin is improved, and a homogeneous molded product can be produced. As the vinylsilane compound, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

  Furthermore, when a boron compound is added to EVOH, it is effective in that the melt viscosity of EVOH is improved and a homogeneous co-extrusion or co-injection molded product is obtained. Examples of the boron compound include boric acids, boric acid esters, borates, borohydrides, and the like. Specifically, examples of boric acids include orthoboric acid (hereinafter sometimes abbreviated as boric acid), metaboric acid, tetraboric acid and the like, and boric acid esters include triethyl borate, trimethyl borate and the like. Examples of the borate include alkali metal salts, alkaline earth metal salts, and borax of the various boric acids described above. Of these compounds, orthoboric acid is preferred.

  When a boron compound is added, the content thereof is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element. By being in this range, EVOH in which torque fluctuation during heating and melting is suppressed can be obtained. If it is less than 20 ppm, the effect of adding a boron compound may be insufficient. On the other hand, if it exceeds 2000 ppm, gelation tends to occur and moldability may be deteriorated.

  Adding an alkali metal salt to EVOH, preferably 5 to 5000 ppm in terms of alkali metal element, is also effective for improving interlayer adhesion and compatibility. The addition amount of the alkali metal salt is more preferably 20 to 1000 ppm, further preferably 30 to 500 ppm in terms of alkali metal element. Examples of the alkali metal include lithium, sodium, potassium, and the like, and examples of the alkali metal salt include an alkali metal aliphatic carboxylate, an aromatic carboxylate, a phosphate, and a metal complex. For example, sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid, etc. Among these, sodium acetate, potassium acetate, sodium phosphate are preferred. is there.

  It is also preferable to add the phosphoric acid compound to EVOH in a proportion of preferably 20 to 500 ppm, more preferably 30 to 300 ppm, and most preferably 50 to 200 ppm in terms of phosphate radical. By blending the phosphoric acid compound within the above range, the thermal stability of EVOH can be improved. In particular, it is possible to suppress the occurrence of gelled spots and coloring when performing melt molding for a long time.

  The kind of phosphorus compound added to EVOH is not particularly limited, and various acids such as phosphoric acid and phosphorous acid, salts thereof, and the like can be used. The phosphate may be in any form of primary phosphate, secondary phosphate, and tertiary phosphate. The cationic species of the phosphate is not particularly limited, but the cationic species is preferably an alkali metal or alkaline earth metal. Among these, it is preferable to add the phosphorus compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate.

  A suitable melt flow rate (MFR) of EVOH (under 210 ° C. and 2160 g load, based on JIS K7210) is 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably 1-30 g / 10 min.

  Of the gas barrier resin (A), the type of polyamide resin is not particularly limited. For example, polycaproamide (nylon-6), polyundecanamide (nylon-11), polylaurolactam (nylon-12), polyhexa Aliphatic polyamide homopolymers such as methylene adipamide (nylon-6,6), polyhexamethylene sebacamide (nylon-6,10); caprolactam / laurolactam copolymer (nylon-6 / 12), caprolactam / Aminoundecanoic acid copolymer (nylon-6 / 11), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), caprolactam / hexamethylene adipamide copolymer (nylon-6 / 6,6) ), Caprolactam / hexamethylene adipamide / hexamethylene sebacamide copolymer (Nai) Aliphatic polyamide copolymers such as N-6 / 6, 6/6, 10); polymetaxylylene adipamide (MX-nylon), hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (nylon) Aromatic polyamides such as 6T / 6I). These polyamide resins can be used alone or in combination of two or more. Among these, polycaproamide (nylon-6) and polyhexamethylene adipamide (nylon-6, 6) are preferable from the viewpoint of gas barrier properties.

  Examples of the polyvinyl chloride resin include homopolymers of vinyl chloride or vinylidene chloride, and copolymers with vinyl acetate, maleic acid derivatives, higher alkyl vinyl ethers, and the like.

  Examples of the polyacrylonitrile resin include acrylonitrile homopolymers and copolymers with acrylic acid esters and the like.

  One of these may be used as the gas barrier resin (A), or a mixture of two or more may be used. Among these, polyvinyl alcohol resin is preferable, and EVOH having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more is more preferable.

  In the present invention, a heat stabilizer, an ultraviolet absorber, an antioxidant, a colorant, a filler, and other resins (polyamide, polyolefin, etc.) are preliminarily applied to the gas barrier resin (A) as long as the object of the present invention is not impaired. It can also be blended.

  The thermoplastic resin (B) contained in the resin composition of the present invention contains a carbon-carbon double bond. Since the carbon-carbon double bond reacts efficiently with oxygen, such a thermoplastic resin (B) has an oxygen scavenging function. In the present invention, the carbon-carbon double bond includes a conjugated double bond, but does not include a multiple bond contained in an aromatic ring.

  In the first resin composition and the second resin composition of the present invention, the type of the thermoplastic resin (B) is a resin having the above characteristics and a resin other than the gas barrier resin (A). If it is, it will not specifically limit. Moreover, in the 3rd resin composition and 4th resin composition of this invention, the kind of thermoplastic resin (B) will not be specifically limited if it is resin which has the said characteristic.

  In the third resin composition and the fourth resin composition of the present invention, the carbon-carbon double bond is contained in the thermoplastic resin (B) in an amount of 0.0001 eq / g (equivalent / g) or more. And is preferably contained in an amount of 0.0005 eq / g or more, more preferably 0.001 eq / g or more. When the content of the carbon-carbon double bond is less than 0.0001 eq / g, the oxygen scavenging function of the obtained resin composition becomes insufficient. Moreover, also in the 1st resin composition and 2nd resin composition of this invention, it is preferable that content of a carbon-carbon double bond is more than said numerical value.

  The carbon-carbon double bond may be contained in the main chain of the thermoplastic resin (B) and may be contained in the side chain, but the one having a larger amount of double bonds contained in the side chain (that is, From the viewpoint of the efficiency of the reaction with oxygen, it is preferable that the side chain has more groups having a carbon-carbon double bond. The carbon-carbon double bond contained in the side chain is preferably a double bond contained in the structural unit represented by the following structural formula (I):

Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂ is a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group, and R ₃ and R ₄ Each independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, —COOR ₅ , —OCOR ₆ , a cyano group, or a halogen atom, and R ₅ and R ₆ are each independently an alkyl group. An aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group). In the above R ₂ , R ₃ , R ₄ , R ₅ and R ₆ , the alkyl group preferably has 1 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms. The alkyl aryl group and arylalkyl group preferably have 7 to 11 carbon atoms, and the alkoxy group preferably has 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, and butyl groups; examples of aryl groups include phenyl groups; examples of alkylaryl groups include tolyl groups; examples of arylalkyl groups include benzyl groups. Examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the halogen atom include a chlorine atom.

  Among the structural units represented by the structural formula (I), a structural unit derived from a diene compound is preferable. This is because it is easy to produce a thermoplastic resin having the structure. Examples of such a diene compound include isoprene, butadiene, 2-ethylbutadiene, and 2-butylbutadiene. Only one of these may be used, or two or more may be used in combination. Table 1 shows the relationship between examples of diene compounds and the types of groups represented by the structural formula (I) derived from the diene compounds.

Among these, from the viewpoint of the efficiency of reaction with oxygen, those in which R ₂ is an alkyl group having 1 to 5 carbon atoms are preferable, and those in which R ₂ is a methyl group (that is, a structural unit derived from isoprene) are more preferable. preferable. Since isoprene is easily available and can be copolymerized with other monomers, it is preferable from the viewpoint of the production cost of the thermoplastic resin (B). In addition, butadiene is also preferable from the viewpoint of easy availability and copolymerization with other monomers.

  When the structural unit represented by the structural formula (I) is derived from a diene compound, the ratio of the structural unit represented by the structural formula (I) to all structural units derived from the diene compound is preferably 10% or more, 20% or more is more preferable, and 30% or more is even more preferable. In order to make the said ratio 10% or more, the method generally used in the said field | area which carries out the anion polymerization of the diene compound using an Lewis base as a cocatalyst in an inert organic solvent is employ | adopted.

  In order to obtain the thermoplastic resin (B) having the structural unit represented by the structural formula (I), it is preferable to use a Lewis base as a cocatalyst when the monomer containing the diene compound is polymerized. Examples of the Lewis base include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol diethyl ether and ethylene glycol dimethyl ether; N, N, N ′, N′-tetramethylethylenediamine (TMEDA). ), Tertiary amines such as triethylenediamine, and ether-containing amines such as N-methylmorpholine and N-ethylmorpholine. These Lewis bases are usually used in an amount of 0.1 to 400 parts by weight per 100 parts by weight of the initiator described later.

  The thermoplastic resin (B) used in the resin composition of the present invention is preferably a copolymer of an aromatic vinyl compound and the diene compound. When the thermoplastic resin (B) is the copolymer, the carbon-carbon double bond portion derived from the diene compound easily reacts with oxygen, and the resulting resin composition has an oxygen barrier property and an oxygen scavenging function. improves. In addition, the melting behavior and hardness of the thermoplastic resin (B) can be controlled by adjusting the copolymerization ratio of the aromatic vinyl compound and the diene compound. Furthermore, the refractive index of a thermoplastic resin (B) can be made into a desired value by adjusting this copolymerization ratio. Therefore, the difference between the refractive index of the gas barrier resin (A) and the refractive index of the thermoplastic resin (B) can be reduced, and as a result, a product having excellent transparency can be obtained.

  Examples of the aromatic vinyl compound include styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-vinylnaphthalene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned. Among these, styrene is most preferable from the viewpoint of cost and ease of polymerization. On the other hand, examples of the diene compound include the aforementioned compounds.

  The form of the copolymer of the aromatic vinyl compound and the diene compound may be any form such as a random copolymer, a block copolymer, a graft copolymer, or a composite thereof. From the viewpoint of ease of production, mechanical properties of the resulting thermoplastic resin (B), ease of handling, and oxygen scavenging function, a block copolymer is preferred.

  In the block copolymer, the molecular weight of the aromatic vinyl compound block is preferably 300 to 100,000, more preferably 1000 to 50000, and further preferably 3000 to 50000. When the molecular weight of the aromatic vinyl compound block is less than 300, the melt viscosity of the thermoplastic resin (B) becomes low, and there may be a problem in moldability, workability and handling properties of the resulting resin composition. Furthermore, the mechanical properties when formed into a molded product may deteriorate. In addition, the dispersibility of the thermoplastic resin (B) in the gas barrier resin (A) may decrease, and the transparency, gas barrier property, and oxygen scavenging function may decrease. On the other hand, when the molecular weight of the aromatic vinyl compound block exceeds 100,000, the melt viscosity of the thermoplastic resin (B) becomes high and the thermoplasticity is impaired, so that the moldability and workability of the resulting resin composition are lowered. There is a case. Further, in the same manner as described above, the dispersibility of the thermoplastic resin (B) in the gas barrier resin (A) may be reduced, and the transparency, gas barrier property, and oxygen scavenging function may be reduced.

Examples of the block form of the block copolymer include X (YX) _n and (XY) _n . Here, X represents an aromatic vinyl compound block, Y represents a diene compound block, and n is an integer of 1 or more. Among these, a binary block copolymer and a ternary block copolymer are preferable, and a ternary block copolymer is more preferable from the viewpoint of mechanical properties. Especially, it is suitable from a viewpoint of cost and the ease of superposition | polymerization that an aromatic vinyl compound block is a polystyrene block and a diene compound block is a polyisoprene block.

  Although the manufacturing method of the said block copolymer is not specifically limited, An anionic polymerization method is suitable. Specifically, a method of copolymerizing an aromatic vinyl compound and a diene compound using an alkyllithium compound as an initiator and coupling with a coupling agent, a diene compound and an aromatic vinyl compound as an initiator However, it is not limited to these. As the alkyl lithium compound, an alkyl lithium compound having 1 to 10 carbon atoms in the alkyl group, for example, methyl lithium, ethyl lithium, benzyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium and the like are preferable.

  As the coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane or the like is used. Examples of the dilithium compound include naphthalenedilithium, oligostyryldilithium, dilithiohexylbenzene, and the like. As for the usage-amount, 0.01-0.2 weight part of initiator and 0.04-0.8 weight part of coupling agent are suitable with respect to 100 weight part of all monomers used for superposition | polymerization.

  The thermoplastic resin (B) may have a functional group containing a hetero atom. In particular, in the first resin composition and the second resin composition of the present invention, when the morphology of the entire resin composition is stabilized and a multilayer container having a layer made of the resin composition is manufactured, This is preferable because the impact peel resistance of the multilayer structure in the container can be improved. The method for producing the thermoplastic resin (B) having a functional group containing a hetero atom is not particularly limited. Examples thereof include a method in which a polymer containing an alkali metal at at least one end is reacted with a specific end treatment agent capable of reacting with the alkali metal at the end of the polymer.

  Examples of the functional group containing a hetero atom that can be contained in the thermoplastic resin (B) include the following.

[I] active hydrogen-containing polar group _{-SO 3 H, -SO 2 H,} -SOH, -NH 2, -NHR,> C = NH, -CONH 2, -CONHR, -CONH -, - OH, -SH
Polar group _-NR 2 containing no active hydrogen containing [II] nitrogen, -NR -,> C = N -, - CN, -NCO, -OCN, -SCN, -NO, -NO 2, -NCS, -CONR _2, -CONR-
[III] Epoxy group or thioepoxy group-containing polar group [IV] Carbonyl group or thiocarbonyl group-containing polar group -CHO, -COOH, -COOR, -COR,> C = O,> C = S, -CHS, -CSOR , -CSOH
[V] Phosphorus-containing polar groups -P (OR) ₂ , -P (SR) ₂ , -PO (OR) ₂ , -PO (SR) ₂ , -PS (OR) ₂ , -PS (SR) ₂ ,- PO (SR) (OR), -PS (SR) (OR)
[VI] M (M is any one of Si, Ge, Sn, and Pb) -containing polar groups -MX ₃ , -MX ₂ R, -MXR ₂ , -MR ₃
(In the above general formula, R represents an alkyl group, a phenyl group or an alkoxy group, and X represents a halogen atom.)

  As a solvent for producing the thermoplastic resin (B), an organic solvent inert to the above initiator, coupling agent and Lewis base is used. Among these, saturated hydrocarbons having 6 to 12 carbon atoms, cyclic saturated hydrocarbons, and aromatic hydrocarbons are preferable. For example, hexane, heptane, octane, decane, cyclohexane, toluene, benzene, xylene and the like can be mentioned. The polymerization reaction for producing the thermoplastic resin (B) is usually performed at a temperature range of -20 to 80 ° C for 1 to 50 hours.

  For example, after dropping the polymerization reaction solution into a poor solvent such as methanol and precipitating the reaction product, the nuclear reaction product is heated or dried under reduced pressure, or the polymerization reaction solution is dropped into boiling water and the solvent is used together. After boiling and removing, the thermoplastic resin (B) is obtained by heating or drying under reduced pressure. In addition, the double bond which exists after superposition | polymerization may be partially reduced with hydrogen in the range which does not inhibit the effect of the resin composition of this invention.

  The molecular weight of the thermoplastic resin (B) is preferably 1,000 to 500,000, more preferably 10,000 to 250,000, and even more preferably in the range of 40,000 to 200,000. When the molecular weight of the thermoplastic resin (B) is less than 1000, the dispersibility in the gas barrier resin (A) may decrease, and the transparency, gas barrier property, and oxygen scavenging function may decrease. When the molecular weight exceeds 500,000, the processability of the resin composition may be deteriorated in addition to the same problem.

  The thermoplastic resin (B) may be a single resin or a mixture of a plurality of resins. In any case, when it is desired to obtain a molded product having good transparency, the internal haze value is preferably 10% or less in a film having a thickness of 20 μm.

  In the first resin composition and the second resin composition of the present invention, the difference between the refractive index of the thermoplastic resin (B) used in the present invention and the refractive index of the gas barrier resin (A) is 0. It is preferably 01 or less. When the difference in refractive index between the gas barrier resin (A) and the thermoplastic resin (B) exceeds 0.01, the transparency of the resulting resin composition may deteriorate. The difference in refractive index is more preferably 0.007 or less, and further preferably 0.005 or less. However, when the gas barrier resin (A) is composed of two or more types of gas barrier resins (for example, when composed of two different types of EVOH), the refraction calculated from the refractive index and the weight ratio of each gas barrier resin. The average value of the rate is taken as the refractive index of the gas barrier resin (A).

  The thermoplastic resin (B) may contain an antioxidant. Examples of the antioxidant include the following compounds. 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 4,4′-thiobis- (6-tert-butylphenol), 2,2′-methylene-bis- ( 4-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis- (6-tert-butylphenol) 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, pentaerythritol tetrakis (3-laurylthiopropionate), 2,6-di -(Tert-butyl) -4-methylphenol (BHT), 2,2-methylenebis- (6-tert-butyl) -p- cresol), triphenyl phosphite, phosphorous acid tris - (nonylphenyl), dilauryl like thiodipropionate.

  The addition amount of the antioxidant is appropriately determined in consideration of the type and content of each component in the resin composition, the purpose of use of the resin composition, storage conditions, and the like. Usually, the amount of the antioxidant contained in the thermoplastic resin (B) is preferably 0.01 to 1% by weight based on the total weight of the thermoplastic resin (B) and the antioxidant. More preferably, the content is 0.02 to 0.5% by weight. If the amount of the antioxidant is too large, the reaction between the thermoplastic resin (B) and oxygen is hindered, so that the oxygen barrier property and oxygen scavenging function of the resin composition of the present invention may be insufficient. On the other hand, if the amount of the antioxidant is too small, the reaction with oxygen proceeds when the thermoplastic resin (B) is stored or melt kneaded, and the oxygen scavenging function is provided before actual use of the resin composition of the present invention. It may decrease.

  For example, when the thermoplastic resin (B) is stored at a relatively low temperature or in an inert gas atmosphere, or when a resin composition is produced by melt-kneading in a nitrogen-sealed state, the amount of antioxidant is May be less. In addition, when an oxidation catalyst is added during melt mixing to promote oxidation, a resin composition having a good oxygen scavenging function can be obtained even if the thermoplastic resin (B) contains a certain amount of antioxidant. Can be obtained.

  The compatibilizer (C) contained in the resin composition of the present invention improves the compatibility between the gas barrier resin (A) and the thermoplastic resin (B), and has a stable morphology in the resulting resin composition. Is a compound that forms The type of the compatibilizer (C) is not particularly limited, and is appropriately selected depending on the combination of the gas barrier resin (A) and the thermoplastic resin (B) to be used.

  When the gas barrier resin (A) is a highly polar resin such as a polyvinyl alcohol resin, the compatibilizer (C) is preferably a hydrocarbon polymer or EVOH containing a polar group. . For example, in the case of a hydrocarbon-based polymer containing a polar group, the compatibility between the compatibilizer (C) and the thermoplastic resin (B) is increased by the hydrocarbon polymer portion serving as the base of the polymer. It becomes good. At the same time, the affinity between the compatibilizer (C) and the gas barrier resin (A) is improved by the polar group. As a result, a stable morphology can be formed in the obtained resin composition.

  Examples of the monomer that forms the hydrocarbon polymer portion serving as the base of the hydrocarbon polymer containing the polar group include the following compounds: ethylene, propylene, 1-butene, isobutene, and 3-methyl. Α-olefins such as pentene, 1-hexene, 1-octene; styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, tert-butoxy Styrenes such as styrene; 1-vinylnaphthalene, 2 -Vinylnaphthalenes such as vinylnaphthalene; vinylene group-containing aromatic compounds such as indene and acenaphthylene; conjugated diene compounds such as butadiene, isoprene, 2,3-dimethylbutadiene, pentadiene and hexadiene. The hydrocarbon polymer may mainly contain one of these monomers, or may mainly contain two or more.

  As described later, a hydrocarbon-based polymer containing a polar group is prepared using the monomer, and the monomer forms a hydrocarbon polymer portion composed of the following polymer: polyethylene ( Ultra low density, low density, linear low density, medium density, high density), ethylene- (meth) acrylic acid ester (methyl ester, ethyl ester, etc.) copolymer, ethylene-vinyl acetate copolymer, ethylene- Olefin polymers such as vinyl alcohol copolymer, polypropylene, ethylene-propylene copolymer; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-diene block copolymer (styrene- Isoprene-block copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer Styrene polymers such as hydrogenated products thereof; (meth) acrylate polymers such as polymethyl acrylate, polyethyl acrylate and polymethyl methacrylate; vinyl halides such as polyvinyl chloride and vinylidene fluoride Semi-aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate; aliphatic polyesters such as polyvalerolactone, polycaprolactone, polyethylene succinate, and polybutylene succinate. Among these, it is often preferable to contain a monomer constituting the thermoplastic resin (B) as a constituent component. For example, when the thermoplastic resin (B) contains polystyrene, the polymer constituting the hydrocarbon polymer portion of the compatibilizer (C) may be polystyrene, styrene-diene block copolymer (styrene-isoprene-block). Copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer, and the like) and hydrogenated products thereof are preferable.

The polar group contained in the compatibilizer (C) is not particularly limited, but a functional group containing an oxygen atom is preferable. Specifically, polar groups that contain active hydrogen-containing polar groups (such as —SO ₃ H, —SO ₂ H, —SOH, —CONH ₂ , —CONHR, —CONH—, —OH, etc.) and no active hydrogen. Groups (—NCO, —OCN, —NO, —NO ₂ , —CONR ₂ , —CONR—, etc.), epoxy groups, carbonyl group-containing polar groups (—CHO, —COOH, —COOR, —COR,> C═O , -CSOR, -CSOH, etc.), phosphorus-containing polar groups (-P (OR) ₂ , -PO (OR) ₂ , -PO (SR) ₂ , -PS (OR) ₂ , -PO (SR) (OR) , -PS (SR) (OR), etc.), boron-containing polar groups, and the like. (In the above general formula, R represents an alkyl group, a phenyl group or an alkoxy group.)

  The method for producing a hydrocarbon-based polymer containing a polar group is not particularly limited. For example, the following methods can be mentioned: 1) copolymerization of a monomer capable of forming the hydrocarbon polymer part and a monomer containing a polar group (or a group capable of forming the polar group). 2) When the monomer capable of forming the hydrocarbon polymer portion is polymerized, an initiator or a chain transfer agent having the polar group (or a group capable of forming the polar group) is used. Method: 3) Living polymerization of a monomer capable of forming the hydrocarbon polymer portion, and a monomer having the polar group (or a group capable of forming the polar group) as a terminator (terminal treatment agent) And 4) polymerizing a monomer capable of forming the hydrocarbon polymer portion to obtain a polymer, and reacting with a reactive portion in the polymer, for example, a carbon-carbon double bond portion, A monomer having the polar group (or a group capable of forming the polar group) is reacted with How to enter. In the method 1), when copolymerization is performed, any polymerization method of random copolymerization, block copolymerization, and graft copolymerization may be employed.

  When the compatibilizer (C) is a hydrocarbon polymer, particularly preferred polar groups include carboxyl groups and boron-containing polar groups (boronic acid groups and converted to boronic acid groups in the presence of water. Obtained boron-containing groups). Hereinafter, these polar groups and the hydrocarbon-based polymer containing the polar groups will be sequentially described.

  In the present specification, the “carboxyl group” includes a carboxylic acid anhydride group and a carboxylate group in addition to the carboxyl group. Among these, the carboxylate group is one in which all or part of the carboxylic acid is present in the form of a metal salt. Examples of the metal of the metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and transition metals such as zinc, manganese and cobalt. Among these, zinc is preferable from the viewpoint of compatibility.

  A method for preparing a hydrocarbon-based polymer containing a carboxyl group is not particularly limited, but a monomer capable of forming a hydrocarbon polymer portion and a carboxyl group or a carboxylic acid anhydride group by the method of 1) above. It is preferable to copolymerize the monomer to be contained. Among the monomers that can be used in such a method, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, and itaconic acid. Among these, acrylic acid and methacrylic acid are preferable. The content of the carboxyl group in the polymer is preferably 0.5 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 3 to 12 mol%.

  Examples of the monomer having a carboxylic acid anhydride group include itaconic anhydride and maleic anhydride, and maleic anhydride is particularly preferable. The content of the carboxylic acid anhydride group in the polymer is preferably 0.0001 to 5 mol%, more preferably 0.0005 to 3 mol%, and still more preferably 0.001 to 1 mol%.

  The carboxylate group is introduced into the polymer by, for example, a salt exchange reaction between the polymer having a carboxyl group or carboxylic anhydride group prepared by the above method and a low molecular metal salt. The low molecular metal salt at this time may contain one kind of the above-mentioned metals, or may contain two or more kinds.

  Examples of the metal counter ion in the low molecular metal salt include an anion derived from an organic acid or chloride. Examples of the organic acid include acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, resin acid, capric acid, and naphthenic acid. Particularly preferred low molecular metal salts include cobalt 2-ethylhexanoate, cobalt neodecanoate, cobalt stearate and cobalt acetate.

  The degree of neutralization of the resulting carboxylate group is preferably less than 100%, more preferably 90% or less, and even more preferably 70% or less. Further, it is preferably 5% or more, more preferably 10% or more, and further preferably 30% or more. For example, it is preferably 5 to 90%, more preferably 10 to 70%.

  The type of hydrocarbon-based polymer containing a carboxyl group is not particularly limited, but α-olefin is used as a monomer capable of forming a hydrocarbon polymer portion, and the above carboxyl group or carboxylic acid anhydride group is used. A copolymer obtained by copolymerization with a monomer having is preferable. Among these, a random copolymer is preferable from the viewpoint of thermal stability of the obtained resin composition.

  As said random copolymer, ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), and these metal salts are mentioned. Among these, EMAA and its metal salt are preferable.

  A copolymer obtained by grafting a monomer having the above carboxyl group or carboxylic acid anhydride group to polyolefin is also preferably used. Polyolefin (for example, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), etc.), polypropylene, copolymer polypropylene, etc. And ethylene-vinyl acetate copolymers are preferred. As the monomer to be grafted, maleic anhydride is preferred.

  The hydrocarbon polymer containing a carboxyl group may contain the following monomers as a polymerization component: vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate and ethyl acrylate , Isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate, diethyl maleate, and the like; carbon monoxide and the like.

  The melt flow rate (MFR) (under 190 ° C. and 2160 g load) of the polymer containing the carboxyl group is usually 0.01 g / 10 min or more, preferably 0.05 g / min or more, more preferably Is 0.1 g / 10 min or more. The MFR is usually 50 g / 10 minutes or less, preferably 30 g / 10 minutes or less, more preferably 10 g / 10 minutes or less.

  When the polar group contained in the compatibilizer (C) is a boron-containing polar group, as described above, a boronic acid group and a boron-containing group that can be converted to a boronic acid group in the presence of water. Is preferred. The boronic acid group is represented by the following formula (II).

  The boron-containing group that can be converted to a boronic acid group in the presence of water refers to a boron-containing group that can be converted to a boronic acid group represented by the above formula (II) by hydrolysis in the presence of water. More specifically, water alone, a mixture of water and an organic solvent (toluene, xylene, acetone, etc.), or a mixture of a 5% boric acid aqueous solution and an organic solvent is used as a solvent at a temperature of room temperature to 150 ° C. It means a functional group that can be converted to a boronic acid group when hydrolyzed for minutes to 2 hours. Representative examples of such functional groups include boronic acid ester groups represented by the following formula (III), boronic acid anhydride groups represented by the following formula (IV), boronic acid groups represented by the following formula (V), etc. Is mentioned.

{In the formula, X ₁ and X ₂ are a hydrogen atom, an aliphatic hydrocarbon group (a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkenyl group), an alicyclic hydrocarbon group (cycloalkyl Group, a cycloalkenyl group, etc.) and an aromatic hydrocarbon group (phenyl group, biphenyl group, etc.), and X ₁ and X ₂ may be the same or different. However, the case where both X ₁ and X ₂ are hydrogen atoms is excluded. X ₁ and X ₂ may be bonded. R ₇ , R ₈ and R ₉ represent the same hydrogen atom, aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group as those of X ₁ and X _2, and R ₇ , R ₈ and R 9 ₉ may be the same or different. Mt represents an alkali metal. Further, X ₁ , X ₂ , R ₇ , R ₈ and R ₉ may have other groups such as a carboxyl group and a halogen atom. }

  The hydrocarbon polymer having a boron-containing polar group exhibits very excellent performance as a compatibilizer. For example, when a multilayer container in which a layer made of a resin composition containing such a polymer is in direct contact with a PES layer is produced, the impact peel resistance is remarkably improved.

  Specific examples of the boronic acid ester group represented by the general formula (III) include the following groups: boronic acid dimethyl ester group, boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid diisopropyl ester group, Boronic acid dibutyl ester group, boronic acid dihexyl ester group, boronic acid dicyclohexyl ester group, boronic acid ethylene glycol ester group, boronic acid propylene glycol ester group, boronic acid 1,3-propanediol ester group, boronic acid 1,3-butane Diol ester group, boronic acid neopentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group, boronic acid trimethylolethane ester group and the like.

  Examples of the boronic acid base represented by the general formula (V) include an alkali metal base of boronic acid. Specific examples include sodium boronate base and potassium boronate base.

  Although there is no restriction | limiting in particular in content of the said boron containing polar group in the thermoplastic resin (B) which has the said boron containing polar group, 0.0001-1 meq / g (milli equivalent / g) is preferable, 0.001- 0.1 meq / g is more preferable.

  The method for producing the hydrocarbon-based polymer having the boron-containing polar group is not particularly limited. Any of the above methods 1) to 4) can be applied. Among them, representative examples of the methods 1), 2), and 4) will be described below.

  Boron-containing by the method of 1) above (a method of copolymerizing a monomer capable of forming a hydrocarbon polymer portion with a polar group or a monomer containing a group capable of forming the polar group) Boron-containing polarity is obtained by copolymerizing a monomer having a polar group with a monomer capable of forming the above hydrocarbon polymer part (olefin polymer, vinyl polymer, diene polymer, etc.). A hydrocarbon-based polymer having a group is obtained. Examples of the monomer having a boron-containing polar group include 3-acryloylaminobenzeneboronic acid, 3-acryloylaminobenzeneboronic acid ethylene glycol ester, 3-methacryloylaminobenzeneboronic acid, and 3-methacryloylaminobenzeneboronic acid ethylene. Examples include glycol ester, 4-vinylphenylboronic acid, 4-vinylphenylboronic acid ethylene glycol ester, and the like.

  The hydrocarbon polymer having a boron-containing polar group is also a monomer (olefin-based polymer) that can form a hydrocarbon polymer portion by using the thiol having a boron-containing polar group as a chain transfer agent by the method of 2) above. It can be obtained by radical polymerization of monomers capable of forming a polymer, a vinyl polymer, a diene polymer and the like. The obtained polymer has a boron-containing polar group at the terminal.

  The thiol having a boron-containing polar group (for example, a boronic acid group) can be obtained, for example, by reacting a thiol having a double bond with diborane or a borane complex in a nitrogen atmosphere and then adding an alcohol or water. . Examples of the thiol having a double bond as a raw material include 2-propene-1-thiol, 2-methyl-2-propene-1-thiol, 3-butene-1-thiol, and 4-pentene-1-thiol. It is done. Among these, 2-propene-1-thiol and 2-methyl-2-propene-1-thiol are preferable. As the borane complex, borane-tetrahydrofuran complex, borane-dimethylsulfide complex, borane-pyridine complex, borane-trimethylamine complex, borane-triethylamine complex and the like are preferable. Of these, borane-tetrahydrofuran complex and borane-dimethyl sulfide complex are preferable. The amount of diborane or borane complex added is preferably about the same amount as the thiol having a double bond. The reaction temperature is preferably in the range of room temperature to 200 ° C. Examples of the solvent include ether solvents such as tetrahydrofuran (THF) and diglyme; saturated hydrocarbon solvents such as hexane, heptane, ethylcyclohexane, and decalin. Among these, THF is preferable. As alcohols added after the reaction, lower alcohols such as methanol and ethanol are preferable, and methanol is more preferable.

  As polymerization conditions for obtaining a polymer having a boron-containing polar group at the terminal, an azo or peroxide initiator is used, and the polymerization temperature is preferably in the range of room temperature to 150 ° C. The addition amount of the thiol having a boron-containing polar group is preferably about 0.001 to 1 mmol per 1 g of monomer. The method for adding the thiol is not particularly limited, but when using a monomer that easily undergoes chain transfer such as vinyl acetate or styrene, it is preferable to add a thiol during polymerization, such as methyl methacrylate. When using a material that is difficult to chain transfer, it is preferable to add thiol from the beginning.

  The monomer which can form the hydrocarbon polymer part of 4) above is polymerized to obtain a polymer, and the monomer having the polar group (boron-containing polar group) at the reactive part in the polymer The following two methods are mentioned as a method of introducing by reaction.

  Method 4-1): The hydrocarbon-based polymer having a boron-containing polar group is obtained by reacting a borane complex and a boric acid trialkyl ester with a polymer having a carbon-carbon double bond in a nitrogen atmosphere. After obtaining a thermoplastic resin having a boronic acid dialkyl ester group by water, it is obtained by reacting water or alcohols as necessary. In this method, a boron-containing polar group is introduced into the carbon-carbon double bond of the polymer having the carbon-carbon double bond by an addition reaction. In this production method, if a polymer having a double bond at the terminal is used as a raw material, a hydrocarbon-based polymer having a boron-containing polar group at the terminal is obtained, and the side chain or main chain has a double bond as a raw material. If a polymer is used, a hydrocarbon polymer having a boron-containing polar group in the side chain can be obtained.

  Since an ordinary olefin polymer has a slight double bond at its end, it can be used as a raw material for the above-mentioned production method. In addition, as a method for obtaining a polymer having a carbon-carbon double bond, a method for obtaining an olefin polymer having a double bond at the terminal by thermally decomposing a normal olefin polymer under anoxic conditions, an olefin Examples thereof include a method of obtaining these copolymers using a raw material monomer and a diene polymer as raw materials.

  Examples of the borane complex used in the above reaction include the borane complexes described in the method 2). Among these, borane-trimethylamine complex and borane-triethylamine complex are more preferable. The amount of the borane complex charged is preferably in the range of 1/3 to 10 mol with respect to 1 mol of the carbon-carbon double bond of the thermoplastic resin.

  As the boric acid trialkyl ester, boric acid lower alkyl esters such as trimethyl borate, triethyl borate, tripropyl borate and tributyl borate are preferable. The charged amount of the boric acid trialkyl ester is preferably in the range of 1 to 100 mol per 1 mol of the carbon-carbon double bond of the thermoplastic resin. Although it is not necessary to use a solvent in particular, saturated hydrocarbon solvents such as hexane, heptane, octane, decane, dodecane, cyclohexane, ethylcyclohexane and decalin are preferred.

  The reaction temperature is usually in the range of room temperature to 300 ° C., preferably 100 to 250 ° C., and the reaction is preferably performed at a temperature in this range for 1 minute to 10 hours, preferably 5 minutes to 5 hours.

  The boronic acid dialkyl ester group introduced into the thermoplastic resin by the above reaction can be hydrolyzed to a boronic acid group by a method generally used in the art. Further, it can be converted into an arbitrary boronic ester group by an ester exchange reaction with alcohols by a usual method. Furthermore, it can be dehydrated and condensed by heating to form a boronic acid anhydride group. Furthermore, it can be reacted with a metal hydroxide or metal alcoholate by a known method to form a boronate group.

  Such a boron-containing functional group conversion reaction is usually carried out using an organic solvent such as toluene, xylene, acetone, ethyl acetate or the like. Examples of alcohols include monoalcohols such as methanol, ethanol, and butanol; ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, glycerin, trimethylolethane, pentaerythritol, diester Examples thereof include polyhydric alcohols such as pentaerythritol. Examples of the metal hydroxide include hydroxides of alkali metals such as sodium and potassium. Furthermore, examples of the metal alcoholate include metal alcoholates composed of the metal and the alcohol. These are not limited to those exemplified. These amounts are usually 1 to 100 moles per mole of boronic acid dialkyl ester group.

  Method 4-2): A hydrocarbon-based polymer having a boron-containing polar group includes a polymer containing a carboxyl group generally known in the art, m-aminophenylbenzeneboronic acid, and m-aminophenyl. It is obtained by subjecting an amino group-containing boronic acid such as boronic acid ethylene glycol ester or an amino group-containing boronic acid ester to an amidation reaction by an ordinary method. In the reaction, a condensing agent such as carbodiimide may be used.

  Examples of the thermoplastic resin containing a carboxyl group include semi-aromatic polyester resins (PET, etc.), aliphatic polyester resins, etc., a polymer containing a carboxyl group at the terminal, a polyolefin resin, a styrene resin, ) A monomer unit having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, fumaric acid, maleic anhydride is copolymerized with a polymer such as an acrylic ester resin or a vinyl halide resin. Examples thereof include, but are not limited to, a polymer in which maleic anhydride and the like are introduced into the introduced polymer and the above-described thermoplastic resin containing an olefinic double bond by an addition reaction.

  The melt flow rate (MFR) (230 ° C., load 2160 g) of the hydrocarbon-based polymer having a boron-containing polar group is preferably in the range of 0.1 to 100 g / 10 minutes, more preferably 0. The range is 2 to 50 g / 10 minutes.

  As a compatibilizer (C), EVOH can also be used as described above. In particular, when the gas barrier resin (A) is EVOH, the effect as a compatibilizer is sufficiently exhibited. Among these, an ethylene-vinyl alcohol copolymer having an ethylene content of 70 to 99 mol% and a saponification degree of 40% or more is preferable from the viewpoint of improving compatibility. The ethylene content is more preferably 72 to 96 mol%, still more preferably 72 to 94 mol%. When ethylene content is less than 70 mol%, affinity with a thermoplastic resin (B) may fall. Moreover, when ethylene content rate exceeds 99 mol%, affinity with EVOH may fall. The degree of saponification is more preferably 45% or more. The upper limit of the saponification degree is not particularly limited, and those having a saponification degree of 100% can be used. If the degree of saponification is less than 40%, the affinity with EVOH may decrease.

  The EVOH has a melt flow rate (MFR) (210 ° C., load 2160 g) of preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more. Further, it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and further preferably 30 g / 10 min or less.

  The compatibilizer (C) described above may be used alone or in combination of two or more.

  When a multilayer container such as a bottle composed of a multilayer body in which the layer made of the resin composition of the present invention containing the compatibilizer (C) and the PES layer are in direct contact with each other is prepared by co-injection stretch blow molding, for example. In addition, the adhesion between the resin composition and the PES is increased, and a high impact peel resistance is obtained. From this viewpoint, the significance of the present invention is great.

  The second resin composition and the fourth resin composition of the present invention need to contain a transition metal salt (D). The first resin composition and the third resin composition of the present invention preferably contain a transition metal salt (D). The transition metal salt (D) has an effect of improving the oxygen scavenging function of the resin composition by promoting the oxidation reaction of the thermoplastic resin (B). For example, the oxygen present in the packaging material obtained from the resin composition of the present invention and the oxygen to be permeated through the packaging material and the reaction between the thermoplastic resin (B) are promoted, and the oxygen barrier property and oxygen of the packaging material The scavenging function is improved.

  In the first resin composition and the second resin composition of the present invention, the transition metal salt (D) is preferably contained at a ratio of 1 to 5000 ppm in terms of metal element. That is, the transition metal salt (D) is 1 to 5000 parts by weight in terms of metal elements with respect to 1000000 parts by weight of the total amount of the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C). It is contained in the ratio. More preferably, the transition metal salt (D) is contained in the range of 5 to 1000 ppm, more preferably 10 to 500 ppm. When the content of the transition metal salt (D) is less than 1 ppm, the effect of the addition may be insufficient. On the other hand, when the content of the transition metal salt (D) exceeds 5000 ppm, the thermal stability of the resin composition is lowered, and the generation of decomposition gas and the generation of gels and blisters may become remarkable.

  On the other hand, in the third resin composition and the fourth resin composition of the present invention, the transition metal salt is preferably based on the total amount of the thermoplastic resin (B) and the compatibilizer (C). It is contained at a ratio of 1 to 50000 ppm in terms of metal element. More preferably, the transition metal salt (D) is contained in the range of 5 to 10,000 ppm, more preferably 10 to 5000 ppm. When the content of the transition metal salt (D) is less than 1 ppm, the effect of the addition may be insufficient. On the other hand, when the content of the transition metal salt (D) exceeds 50000 ppm, the thermal stability of the resin composition is lowered, and the generation of decomposition gas and the generation of gels and blisters may become remarkable.

  Examples of the transition metal used in the transition metal salt (D) include, but are not limited to, iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium, ruthenium and the like. Among these, iron, nickel, copper, manganese, and cobalt are preferable, manganese and cobalt are more preferable, and cobalt is still more preferable.

  Examples of the counter ion of the metal contained in the transition metal salt (D) include an anion derived from an organic acid or chloride. Examples of the organic acid include acetic acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, resin acid, capric acid, and naphthenic acid. However, it is not limited to these. Particularly preferred salts include cobalt 2-ethylhexanoate, cobalt neodecanoate and cobalt stearate. The metal salt may be a so-called ionomer having a polymeric counter ion.

  In the first resin composition and the second resin composition of the present invention, the gas barrier resin (A) is 40 to 99.8% by weight, the thermoplastic resin (B) is 0.1 to 30% by weight, and It is necessary that the compatibilizer (C) is contained in an amount of 0.1 to 30% by weight. When the content ratio of the gas barrier resin (A) is less than 40% by weight, the transparency of the molded product such as a multilayer container using the resin composition is inferior, and the gas barrier property against oxygen gas, carbon dioxide gas, etc. may be reduced. There is. On the other hand, when the content ratio exceeds 99.8% by weight, the content ratio of the thermoplastic resin (B) and the compatibilizer (C) decreases, so that the oxygen barrier property and the oxygen scavenging function are deteriorated, and the resin The stability of the morphology of the entire composition may be impaired. The content ratio of the gas barrier resin (A) is preferably 60 to 99% by weight, more preferably 80 to 98% by weight, and further preferably 85 to 97% by weight.

  Moreover, the content rate of a thermoplastic resin (B) becomes like this. Preferably it is 1-20 weight%, More preferably, it is 2-15 weight%. Furthermore, the content ratio of the compatibilizer (C) is preferably 0.5 to 20% by weight, and more preferably 1.0 to 10% by weight.

  The third resin composition and the fourth resin composition of the present invention contain 1 to 99% by weight of the thermoplastic resin (B) and 1 to 99% by weight of the compatibilizer (C). Is preferred. The content of the thermoplastic resin (B) is preferably 5 to 95% by weight, more preferably 30 to 90% by weight, and most preferably 50 to 90% by weight. The content of the compatibilizer (C) is preferably 5 to 95% by weight, more preferably 10 to 70% by weight, and most preferably 10 to 50% by weight.

Oxygen absorption rate of the first resin composition of the present invention, must be at 0.001ml ^/ m 2 · day or more, preferably more than ^{0.01ml / m 2 · day, 0.05ml} / m 2 -Day or more is more preferable. When the oxygen absorption rate is less than 0.001 ml / m ² · day, there is a possibility that the oxygen barrier property and the oxygen scavenging effect of the molded product made of the resin composition obtained will be insufficient. Moreover, it is preferable that the 2nd resin composition of this invention also has an oxygen absorption rate more than said numerical value.

The oxygen absorption rate of the third resin composition of the present invention, must be at 0.1ml ^/ m 2 · day or more, 0.5 ml ^/ m is preferably not less than ² · day, 1ml / ^m 2 -More than day is more preferable, and 10 ml / m < ² > -day or more is still more preferable. Moreover, it is preferable that the 4th resin composition of this invention also has an oxygen absorption rate more than said numerical value. The oxygen absorption rate is the volume of oxygen absorbed by the film per unit surface area per unit surface area when the resin composition film is left in a certain volume of air. Specific measurement methods will be described in the examples described later.

  The first resin composition and the second resin composition of the present invention are such that the gas barrier resin (A), the thermoplastic resin (B), and the compatibilizer (C) to the extent that the effects of the present invention are not impaired. Other thermoplastic resins (E) may be contained. In addition, the third resin composition and the fourth resin composition of the present invention are also thermoplastic resins other than the thermoplastic resin (B) and the compatibilizer (C) to the extent that the effects of the present invention are not impaired. E) may be contained. The thermoplastic resin (E) is not particularly limited, and examples thereof include the following compounds: polyethylene, polypropylene, ethylene-propylene copolymer, ethylene or propylene copolymer (ethylene or propylene and the following monomer) Copolymer with at least one of: α-olefin such as 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; itaconic acid, methacrylic acid, acrylic acid, maleic anhydride Unsaturated carboxylic acids such as acids, salts, partial or complete esters thereof, nitriles, amides, anhydrides thereof; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate Carboxylic acid vinyl esters such as vinyl stearate and vinyl arachidonate; Vinyl silane compounds such as rutrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkyl thiols; vinyl pyrrolidones, etc.), polyolefins such as poly-4-methyl-1-pentene, poly-1-butene; Polyester such as polyethylene naphthalate; polystyrene, polycarbonate, polyacrylate and the like.

  When selecting the thermoplastic resin (E) contained in the resin composition of the present invention, the miscibility of the thermoplastic resin (E) with the gas barrier resin (A) and the thermoplastic resin (B) is taken into consideration. It is preferable. The miscibility of these resins can affect the gas barrier properties, cleanliness, effectiveness as oxygen scavengers, mechanical properties, product texture, and the like of the resulting product.

  Various additives may be contained in the resin composition of the present invention as long as the effects of the present invention are not inhibited. Examples of such additives include antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, deodorants, UV absorbers, antistatic agents, lubricants, colorants, fillers, desiccants. , Fillers, pigments, dyes, processing aids, flame retardants, antifogging agents, and other polymer compounds. Among the above, the heat stabilizer will be described below.

  Among the additives, as the heat stabilizer, one or more of hydrotalcite compounds and higher aliphatic carboxylic acid metal salts are used. These compounds can prevent the formation of gels and fish eyes during the production of the resin composition, and can further improve long-term driving stability. These compounds are preferably contained in a proportion of 0.01 to 1% by weight of the entire resin composition.

  The metal salt of a higher aliphatic carboxylic acid is a metal salt of a higher fatty acid having 8 to 22 carbon atoms. Examples of the higher fatty acid having 8 to 22 carbon atoms include lauric acid, stearic acid, myristic acid and the like. Examples of the metal constituting the salt include sodium, potassium, magnesium, calcium, zinc, barium, and aluminum. Of these, alkaline earth metals such as magnesium, calcium and barium are preferred. Of these metal salts of higher aliphatic carboxylic acids, calcium stearate and magnesium stearate are preferred.

  A preferred melt flow rate (MFR) of the resin composition of the present invention (at 210 ° C. under a load of 2160 g, based on JIS K7210) is 0.1 to 100 g / 10 minutes, more preferably 0.5 to 50 g / 10 minutes. More preferably, it is 1 to 30 g / 10 min. When the melt flow rate of the resin composition of the present invention is out of the above range, the workability during melt molding often deteriorates.

  In the first resin composition and the second resin composition of the present invention, it is preferable that the particles made of the thermoplastic resin (B) are dispersed in the matrix made of the gas barrier resin (A). A molded product made of such a resin composition has good transparency, gas barrier properties, and oxygen scavenging function. At this time, it is preferable that the average particle diameter of the particles made of the thermoplastic resin (B) is 10 μm or less. When the average particle diameter exceeds 10 μm, the area of the interface between the thermoplastic resin (B) and the matrix made of the gas barrier resin (A) or the like becomes small, and the oxygen gas barrier property and the oxygen scavenging function may be lowered. is there. The average particle diameter of the thermoplastic resin (B) particles is more preferably 5 μm or less, and further preferably 2 μm or less.

  Each component of the resin composition of the present invention is mixed and processed into a desired product. The method for mixing the components of the resin composition of the present invention is not particularly limited. The order of mixing the components is not particularly limited. For example, when mixing a gas barrier resin (A), a thermoplastic resin (B), a compatibilizer (C) and a transition metal salt (D), these may be mixed simultaneously, or the thermoplastic resin (B ), The compatibilizer (C) and the transition metal salt (D) may be mixed and then mixed with the gas barrier resin (A). Further, after mixing the thermoplastic resin (B) and the compatibilizer (C), it may be mixed with the gas barrier resin (A) and the transition metal salt (D), or the gas barrier resin (A) and the transition may be mixed. After mixing the metal salt (D), it may be mixed with the thermoplastic resin (B) and the compatibilizer (C). Further, after mixing the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C), they may be mixed with the transition metal salt (D), or the compatibilizer (C) and After mixing the transition metal salt (D), it may be mixed with the gas barrier resin (A) and the thermoplastic resin (B). Also obtained by mixing a gas barrier resin (A), a thermoplastic resin (B) and a compatibilizer (C), a gas barrier resin (A), and a transition metal salt (D). The mixture may be mixed.

  As a specific method of mixing, a melt-kneading method is preferable from the viewpoints of process simplicity and cost. At this time, using an apparatus capable of achieving a high degree of kneading and dispersing each component finely and uniformly can improve oxygen absorption performance and transparency, and can prevent the generation and mixing of gels and blisters. This is preferable.

  The equipment with a high degree of kneading includes continuous intensive mixers, kneading type twin-screw extruders (in the same direction or in different directions), continuous kneaders such as mixing rolls and kneaders, high-speed mixers, Banbury mixers, intensive mixers, pressurization A batch type kneader such as a kneader, an apparatus using a rotating disk having a grinding mechanism such as a stone mill, such as a KCK kneading extruder manufactured by KCK Co., Ltd., and a kneading part (Dalmage, CTM, etc.) in a single screw extruder Examples thereof include a simple kneader such as a provided one, a ribbon blender, and a Brabender mixer. Among these, a continuous kneader is preferable. Examples of commercially available continuous intensive mixers include Farrel FCM, Nippon Steel Works CIM, Kobe Steel KCM, LCM, and ACM. It is preferable to employ a device in which a single screw extruder is installed under these kneaders, and kneading and extrusion pelletization are simultaneously performed. Examples of the twin-screw kneading extruder having a kneading disk or a kneading rotor include, for example, TEX manufactured by Nippon Steel Works, ZSK manufactured by Werner & Pfleiderer, TEM manufactured by Toshiba Machine Co., Ltd., PCM manufactured by Ikekai Tekko Co., Ltd. Is mentioned.

  In these continuous kneaders, the shape of the rotor and disk plays an important role. In particular, the gap (chip clearance) between the mixing chamber and the rotor chip or the disk chip is important, and a mixture with good dispersibility cannot be obtained if it is too narrow or too wide. The optimum tip clearance is 1 to 5 mm.

  The rotation speed of the rotor of the kneader is usually 100 to 1200 rpm, preferably 150 to 1000 rpm, and more preferably 200 to 800 rpm. The kneader chamber inner diameter (D) is usually 30 mm or more, and preferably 50 to 400 mm. Furthermore, the ratio L / D between the chamber length (L) and the inner diameter (D) of the kneader is preferably 4-30. One kneader may be used, or two or more kneaders may be connected and used.

  The kneading temperature is usually in the range of 50 to 300 ° C. In order to prevent oxidation of the thermoplastic resin (B), it is preferable that the hopper port is sealed with nitrogen and extruded at a low temperature. The longer the kneading time, the better results can be obtained, but from the viewpoint of antioxidant and production efficiency of the thermoplastic resin (B), it is usually 10 to 600 seconds, preferably 15 to 200 seconds, more preferably 15 to 150 seconds.

  The resin composition of the present invention can be molded into various molded products such as films, sheets, containers, and other packaging materials by appropriately adopting molding methods. At this time, the resin composition of the present invention may be once formed into pellets and then subjected to molding, or each component of the resin composition may be dry blended and directly subjected to molding.

  As a molding method and a molded product, for example, it can be formed into a film, sheet, pipe or the like by melt extrusion molding, into a container shape by injection molding, or into a hollow container such as a bottle shape by hollow molding. The hollow molding is preferably extrusion hollow molding in which a parison is molded by extrusion molding and blown to perform molding, and injection hollow molding in which a preform is molded by injection molding and blown to perform molding.

  In the present invention, the molded product obtained by the above molding may be a single layer, but it is laminated with other layers from the viewpoint of imparting mechanical properties, water vapor barrier properties, further oxygen barrier properties and the like. And preferably used as a multilayer structure.

  As a layer structure of the multilayer structure, x / y, where x is a layer made of a resin other than the resin composition of the present invention, y layer is a resin composition layer of the present invention, and z layer is an adhesive resin layer, x / y / x, x / z / y, x / z / y / z / x, x / y / x / y / x, x / z / y / z / x / z / y / z / x, etc. However, the present invention is not limited to these examples. When a plurality of x layers are provided, the types may be the same or different. Moreover, you may provide separately the layer using collection | recovery resin which consists of scraps, such as a trim generated at the time of shaping | molding, and you may blend collection | recovery resin with the layer which consists of other resin. The thickness structure of each layer of the multilayer structure is not particularly limited, but the thickness ratio of the y layer to the total layer thickness is preferably 2 to 20% from the viewpoint of moldability and cost.

  The resin used for the x layer is preferably a thermoplastic resin from the viewpoint of processability and the like. Such thermoplastic resins include, but are not limited to, the following resins: polyethylene, polypropylene, ethylene-propylene copolymer, ethylene or propylene copolymer (at least one of the following monomers with ethylene or propylene): Copolymer with one type: α-olefin such as 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; non-condensation such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride Saturated carboxylic acid, salt, partial or complete ester thereof, nitrile, amide, anhydride thereof; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate , Vinyl carboxylic acid esters such as vinyl arachidonate; vinyl Vinyl silane compounds such as limethoxysilane; unsaturated sulfonic acids or salts thereof; alkyl thiols; vinyl pyrrolidones, etc.), polyolefins such as poly-4-methyl-1-pentene, poly-1-butene; polyethylene terephthalate, polybutylene terephthalate Polyesters such as polyethylene naphthalate; Polyamides such as poly ε-caprolactam, polyhexamethylene adipamide, polymethaxylylene adipamide; polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylate and the like. Such a thermoplastic resin layer may be unstretched, or may be stretched or rolled uniaxially or biaxially.

  Of these thermoplastic resins, polyolefin is preferable in terms of moisture resistance, mechanical properties, economy, heat sealability, and the like, and polyester is preferable in terms of mechanical properties, heat resistance, and the like.

  On the other hand, the adhesive resin used for the z layer is not particularly limited as long as it can bond the respective layers, and a polyurethane-based or polyester-based one-component or two-component curable adhesive, carboxylic acid-modified polyolefin Resins and the like are preferably used. The carboxylic acid-modified polyolefin resin is an olefin polymer or copolymer containing an unsaturated carboxylic acid or its anhydride (such as maleic anhydride) as a copolymerization component; or an unsaturated carboxylic acid or its anhydride as an olefin polymer. Or it is a graft copolymer obtained by grafting to a copolymer.

  Among these, carboxylic acid-modified polyolefin resin is more preferable. In particular, when the x layer is a polyolefin resin, the adhesion with the y layer is good. Examples of such carboxylic acid-modified polyolefin resins include polyethylene {low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE)}, polypropylene, copolymer polypropylene, ethylene-vinyl acetate. Examples thereof include a copolymer, an ethylene- (meth) acrylic acid ester (methyl ester or ethyl ester) copolymer and the like that are modified with a carboxylic acid.

  Examples of the method for obtaining the multilayer structure include an extrusion laminating method, a dry laminating method, a co-injection molding method, and a co-extrusion molding method, but are not particularly limited. 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.

  The sheet, film, parison, etc. of the multilayer structure thus obtained are reheated at a temperature below the melting point of the contained resin, a thermoforming method such as drawing, a roll stretching method, a pantograph type stretching method, A stretched molded product can also be obtained by uniaxial or biaxial stretching by an inflation stretching method, a blow molding method, or the like.

  The resin composition of the present invention has good transparency by selecting an appropriate resin. Therefore, by selecting a resin having good transparency as the other resin to be laminated, a packaging container in which the contents can be easily seen can be obtained. From this viewpoint, the haze value of the multilayer structure having the resin composition layer of the present invention is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

  Molded articles using the multilayer structure are used for various purposes. In particular, the effect of the multilayer structure of the present invention is greatly exhibited when a multilayer container is used. Furthermore, in the multilayer structure in which layers having a high water vapor barrier property are arranged on both sides or high humidity side of the resin composition layer of the present invention, the duration of the oxygen scavenging function is particularly extended, resulting in extremely high gas barrier properties. Is preferable from the viewpoint of continuing for a longer time. On the other hand, a multilayer container having a resin composition layer as the innermost layer is preferable from the viewpoint that the oxygen scavenging function in the container is rapidly exhibited.

  Furthermore, the resin composition of the present invention has good transparency by selecting an appropriate resin. Therefore, such a resin composition is optimal for use as a packaging container in which the contents are easily visible. Among such packaging containers, the required performance for transparency is strict, and the following two types of modes are mentioned as modes in which the usefulness of using the resin composition of the present invention is great. That is, one is a container made of a multilayer film including a layer made of the resin composition of the present invention and having a total layer thickness of 300 μm or less, and the other is a layer made of the resin composition of the present invention and thermoplasticity. A multilayer container including at least one polyester (PES) layer. Hereinafter, these embodiments will be sequentially described.

  A container composed of a multilayer film including a layer composed of the resin composition of the present invention and having a total layer thickness of 300 μm or less is a flexible container composed of a multilayer structure having a relatively thin total layer thickness, and is usually in the form of a pouch or the like. Has been processed. This container has excellent gas barrier properties, has a continuous oxygen scavenging function, and is easy to manufacture. Therefore, it is extremely useful for packaging products that are highly sensitive to oxygen and easily deteriorate.

  In general, as a container that requires good transparency, a container having a thin overall thickness is manufactured, with each resin layer constituting the multilayer structure being thin. For example, when a crystalline resin such as polyolefin is used, if the thickness is large, the transparency often deteriorates due to scattering by crystals, whereas a thin container is good. Transparency is obtained. In general, even if a resin crystallized unstretched is poor in transparency, a resin crystallized by stretching and orientation has good transparency. Such a uniaxially or biaxially stretched film is usually thin, and in this respect as well, a thin multilayer structure often gives good transparency.

  The resin composition of the present invention has good transparency by selecting an appropriate resin. Therefore, it can be suitably used for a container made of a thin multilayer film that often requires transparency. In such a thin film, even if the transparency deteriorates with time, the degree is small. The thickness of such a multilayer film is not particularly limited, but is preferably 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less from the viewpoint of maintaining transparency and flexibility. . On the other hand, considering the mechanical properties of the container, the total layer thickness is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more.

  When the multilayer container is manufactured from a multilayer film, the method for manufacturing the multilayer film is not particularly limited. For example, the resin composition layer of the present invention and another thermoplastic resin layer may be dry laminated, co-extruded laminated, or the like. A multilayer film can be obtained by laminating by the method.

  In the case of dry lamination, an unstretched film, a uniaxially stretched film, a biaxially stretched film, a rolled film, etc. can be used. Among these, a biaxially stretched polypropylene film, a biaxially stretched polyethylene terephthalate film, and a biaxially stretched polyε-caprolactam film are preferable from the viewpoint of mechanical strength, and a biaxially stretched polypropylene film is particularly preferable in consideration of moisture resistance. When using an unstretched film or a uniaxially stretched film, the multilayer film is reheated after lamination, and uniaxially or biaxially stretched by a thermoforming method such as drawing, a roll stretching method, a pantograph stretching method, an inflation stretching method, or the like. Thus, a stretched multilayer film can be obtained.

  In order to seal the resulting multilayer container, it is also preferable to provide a layer made of a heat-sealable resin on at least one outermost surface in the production stage of the multilayer film. Examples of such a resin include polyolefins such as polyethylene and polypropylene.

  The multilayer film obtained in this way is processed into a bag shape, for example, and can be used as a packaging container for filling the contents. Since it is flexible and simple and has excellent transparency and oxygen scavenging properties, it is extremely useful for packaging contents such as foods that are easily deteriorated by the presence of oxygen.

  A multi-layer container including at least one layer composed of the resin composition of the present invention and a PES layer is excellent in gas barrier properties and oxygen scavenging function, and becomes more transparent by selecting an appropriate resin. Therefore, it is used in various forms such as a bag-shaped container, a cup-shaped container, and a hollow molded container. Among these, hollow molded containers, particularly bottles, are important.

  Bottles made of PES are now widely used as beverage containers. In such applications, it is necessary to prevent deterioration of the contents, and it is required that the consumer can sufficiently visually recognize the beverage that is the contents. In addition, when filling contents such as beer that are very susceptible to the deterioration of flavor due to oxygen, it is desirable to have extremely high gas barrier properties and oxygen scavenging performance.

  A multilayer container comprising at least one layer composed of the resin composition of the present invention and at least one PES layer can obtain high transparency, and the retention performance of the quality of the contents is extremely excellent. Is optimal. As a layer structure of the multilayer container, an adhesive resin layer may be disposed between the resin composition layer and the PES layer, but the PES layer is disposed so as to be in direct contact with both surfaces of the resin composition layer. The multilayer container is particularly preferable from the viewpoint of being able to obtain higher transparency and sufficiently exhibiting the effect of the present invention that is excellent in impact peelability between the resin composition layer and the PES layer.

  As the PES used in the multilayer container of the present invention comprising the layer comprising the resin composition of the present invention and the PES layer, a condensation polymer mainly comprising an aromatic dicarboxylic acid or an alkyl ester thereof and a diol is used. It is done. In particular, in order to achieve the object of the present invention, PES mainly composed of an ethylene terephthalate component is preferable. Specifically, the total ratio (mol%) of terephthalic acid units and ethylene glycol units is preferably 70 mol% or more, based on the total number of moles of all structural units constituting PES, and is 90 mol%. The above is more preferable. When the total proportion of the terephthalic acid unit and the ethylene glycol unit is less than 70 mol%, the resulting PES becomes amorphous, the mechanical strength is insufficient, and the contents are heated and filled after being drawn into a container ( When hot filling is performed, there is a risk that the heat shrinkage is large and it cannot be used. In addition, if solid phase polymerization is performed to reduce the oligomers contained in the resin, the resin is likely to become stuck due to softening of the resin, which may make production difficult.

  The PES can contain a bifunctional compound unit other than the terephthalic acid unit and the ethylene glycol unit as required, as long as the above problem does not occur. The proportion (mol%) is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less with respect to the total number of moles of all structural units constituting PES. Examples of such a bifunctional compound unit include a dicarboxylic acid unit, a diol unit, and a hydroxycarboxylic acid unit, and may be aliphatic, alicyclic, or aromatic. Specific examples include a neopentyl glycol unit, a cyclohexanedimethanol unit, a cyclohexanedicarboxylic acid unit, an isophthalic acid unit, and a naphthalenedicarboxylic acid unit.

  Among these, the isophthalic acid unit has the advantage that when the obtained PES is used, the production conditions under which a good molded product can be obtained are wide and the moldability is excellent, so that the defective product rate is low. It is also preferable from the viewpoint that whitening of the molded product can be prevented by suppressing the crystallization rate. Moreover, the 1, 4- cyclohexane dimethanol unit or the 1, 4- cyclohexane dicarboxylic acid unit is preferable from the point that the intensity | strength at the time of fall of the molded article obtained is further excellent. Furthermore, naphthalenedicarboxylic acid units are preferable because the glass transition temperature of the resulting PES is increased, the heat resistance is improved, and the ability to absorb ultraviolet rays is imparted, and the content tends to be deteriorated by ultraviolet rays. It is particularly useful. For example, it is particularly useful when the contents are easily deteriorated by oxidation or ultraviolet rays, such as beer.

  When a polycondensation catalyst is used in the production of PES, a catalyst usually used in the production of PES can be used. For example, antimony compounds such as antimony trioxide; germanium compounds such as germanium dioxide, germanium tetraethoxide, germanium tetra-n-butoxide; tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra Titanium compounds such as butoxy titanium; tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide, and dibutyltin diacetate can be used. These catalysts may be used alone or in combination of two or more. The amount of the polycondensation catalyst used is preferably in the range of 0.002 to 0.8% by weight based on the weight of the dicarboxylic acid component.

  Among these, an antimony compound is preferable from the viewpoint of catalyst cost, and antimony trioxide is particularly preferable. On the other hand, a germanium compound is preferable and germanium dioxide is particularly preferable from the viewpoint that the color tone of the obtained PES is good. Further, from the viewpoint of moldability, a germanium compound is preferable to an antimony compound. PES obtained by a polymerization reaction using an antimony compound as a catalyst has a faster crystallization rate than PES polymerized using a germanium compound as a catalyst, and crystallization by heating is likely to proceed during injection molding or blow molding. The resulting bottle may be whitened and the transparency may be impaired. In addition, the stretch orientation may be lowered and the shapeability may be deteriorated. As described above, the range of manufacturing conditions under which a good molded product can be obtained is narrowed, and the defective product rate tends to increase.

  In particular, as the PES used in the present invention, when using polyethylene terephthalate which does not contain a copolymer component other than the diethylene glycol unit as a by-product, a germanium compound is used to suppress the crystallization rate when the PES is produced. Is preferably used as a catalyst.

  The method for producing the multilayer container of the present invention comprising at least one layer composed of the resin composition and the PES layer is not particularly limited, but it is preferable to use co-injection blow molding from the viewpoint of productivity and the like. It is. In co-injection blow molding, a container is manufactured by stretch-blow molding a container precursor (parison) obtained by co-injection molding.

  In the co-injection molding, the resin that constitutes each layer of the multilayer structure is usually guided into a concentric nozzle from two or more injection cylinders, and at the same time or alternately at different timings, a single mold Molding is performed by injecting into the mold and performing a single clamping operation. For example, (1) First, a PES layer for inner and outer layers is injected, and then a resin composition as an intermediate layer is injected to obtain a molded container having a three-layer structure of PES / resin composition / PES, (2 ) First, the PES layer for the inner and outer layers is injected, then the resin composition is injected, and at the same time or after that, the PES layer is injected again, and five layers of PES / resin composition / PES / resin composition / PES are injected. Although the parison is manufactured by a method of obtaining a molded container having a configuration, the parison is not limited to these manufacturing methods. Moreover, in the said layer structure, you may arrange | position an adhesive resin layer between a resin composition layer and a PES layer as needed.

  As conditions for injection molding, PES is preferably injected in a temperature range of 250 to 330 ° C, more preferably 270 to 320 ° C, and further preferably 280 to 310 ° C. When the injection temperature of PES is less than 250 ° C., PES is not sufficiently melted, and an unmelted product (fish eye) is mixed into the molded product, resulting in poor appearance, and at the same time, the mechanical strength of the molded product is reduced. There is a risk of becoming. In extreme cases, the screw torque increases, which may cause a failure of the molding machine. On the other hand, when the injection temperature of PES exceeds 330 ° C., the decomposition of PES becomes remarkable, which may cause a decrease in mechanical strength of the molded product due to a decrease in molecular weight. Further, not only the properties of the substance filled in the molded product by the gas such as acetaldehyde generated at the time of decomposition are impaired, but also the oligomers generated at the time of decomposition may cause the mold to become dirty and impair the appearance of the molded product.

  The resin composition is preferably injected in a temperature range of 170 to 250 ° C, more preferably 180 to 240 ° C, and further preferably 190 to 230 ° C. When the injection temperature of the resin composition is less than 170 ° C., the resin composition does not melt sufficiently, and an unmelted product (fish eye) may be mixed into the molded product, resulting in poor appearance. In extreme cases, the screw torque increases, which may cause a failure of the molding machine. On the other hand, when the injection temperature of the resin composition exceeds 250 ° C., the oxidation of the thermoplastic resin (B) proceeds, and the gas barrier property and oxygen scavenging function of the resin composition may be deteriorated. At the same time, the appearance of the molded product may be poor due to coloration or gelation, or the fluidity may be non-uniform or hindered by the decomposition gas or gelation, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to the generation of a gelled product. In order to suppress the progress of oxidation during melting, it is also preferable to seal the raw material supply hopper with nitrogen.

  The resin composition may be supplied to the molding machine in the form of pellets in which raw material components are melt-blended in advance, or each dry-blended raw material component may be supplied to the molding machine.

  The temperature of the hot runner part into which PES and the resin composition flow is preferably in the range of 220 to 300 ° C, more preferably 240 to 280 ° C, and further preferably 250 to 270 ° C. When the temperature of the hot runner portion is less than 220 ° C., PES may crystallize and solidify in the hot runner portion, so that molding may be difficult. On the other hand, when the temperature of the hot runner portion exceeds 300 ° C., the oxidation of the thermoplastic resin (B) proceeds, and the gas barrier property and oxygen scavenging function of the resin composition may be deteriorated. At the same time, the appearance of the molded product may be poor due to coloration or gelation, or the fluidity may be non-uniform or hindered by the decomposition gas or gelation, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to the generation of a gelled product.

  As mold temperature, the range of 0-70 degreeC is preferable, 5-50 degreeC is more preferable, and 10-30 degreeC is further more preferable. As a result, crystallization of the PES of the parison and the resin composition is suppressed, uniform stretchability is ensured, the delamination resistance and transparency of the resulting multilayer container are improved, and a molded product having a stable shape is obtained. be able to. When the mold temperature is less than 0 ° C., the appearance of the parison is impaired due to condensation of the mold, and a good molded product may not be obtained. Further, when the mold temperature exceeds 70 ° C., the crystallization of the parison PES and the resin composition is not suppressed, the extensibility becomes non-uniform, and the delamination resistance and transparency of the obtained molded product are reduced. It becomes difficult to obtain a molded product shaped into the intended shape.

  In the parison thus obtained, the total thickness is preferably 2 to 5 mm, and the total thickness of the resin composition layer is preferably 10 to 500 μm.

  The parison is reheated directly at a high temperature or using a heating element such as a block heater or an infrared heater, and then sent to the stretch blow step. After the heated parison is stretched 1 to 5 times in the longitudinal direction in the stretch blow step, the multilayer injection blow molded container of the present invention is manufactured by stretch blow molding with compressed air or the like 1 to 4 times. Can do. The temperature of the parison is preferably 75 to 150 ° C, more preferably 85 to 140 ° C, still more preferably 90 to 130 ° C, and most preferably 95 to 120 ° C. When the temperature of the parison exceeds 150 ° C., PES tends to be crystallized, and the resulting container may be whitened to deteriorate the appearance or increase the delamination of the container. On the other hand, when the temperature of the parison is less than 75 ° C., crazing occurs in the PES, and the transparency may be impaired due to a pearly tone.

  The total thickness of the trunk portion of the multilayer container thus obtained is generally 100 to 2000 μm, preferably 150 to 1000 μm, and can be properly used depending on the application. The total thickness of the resin composition layer at this time is preferably in the range of 2 to 200 μm, and more preferably 5 to 100 μm.

  In this way, a multilayer container comprising a layer comprising the resin composition of the present invention and a PES layer is obtained. This container can obtain high transparency, and is extremely excellent in gas barrier property and oxygen scavenging function. Therefore, it is useful as a container for contents that easily deteriorate due to the presence of oxygen, such as foods and pharmaceuticals. In particular, it is extremely useful as a container for beverages such as beer.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

  The analysis in this example was performed as follows.

(1) Ethylene content and saponification degree of EVOH:
It was calculated from the spectrum obtained by ¹ H-NMR (nuclear magnetic resonance) measurement (using “JNM-GX-500 type” manufactured by JEOL Ltd.) using deuterated dimethyl sulfoxide as a solvent.

(2) Phosphate content of EVOH:
10 g of the dried chip as a sample was put into 50 ml of 0.01 N hydrochloric acid aqueous solution and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography, and the phosphate radical content was obtained as the phosphate ion (PO ₄ ³⁻ ) content. CIS-A23 manufactured by Yokogawa Electric Corporation was used as the chromatography column, and an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium bicarbonate was used as the eluent. For the determination, a calibration curve prepared with a phosphoric acid aqueous solution was used.

(3) Sodium, potassium and magnesium salt contents of EVOH:
10 g of the dried chip as a sample was put into 50 ml of 0.01 N hydrochloric acid aqueous solution and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography, and the sodium salt, potassium salt, and magnesium salt contents were obtained in metal equivalent amounts as the respective cation contents. As a column for chromatography, ICS-C25 manufactured by Yokogawa Electric Corporation was used, and an aqueous solution containing 5.0 mM tartaric acid and 1.0 mM 2,6-pyridinedicarboxylic acid was used as an eluent. For the determination, a calibration curve prepared with an aqueous solution of each metal chloride was used.

(4) Oxygen permeation rate of EVOH:
Using EVOH pellets, extrusion was performed at an extrusion temperature of 210 ° C. to obtain a film having a thickness of 20 μm. This film was heat-treated at a temperature 20 ° C. lower than the melting point of EVOH for 10 minutes, and then adjusted to a temperature / humidity of 20 ° C.-65% RH, and an oxygen transmission amount measuring device (OX-TRAN-10 / 50A manufactured by Modern Control) Was used to measure the oxygen transmission rate. When a mixture of two kinds of EVOH was used as EVOH, two kinds of EVOH pellets were dry blended in advance, a film was obtained according to the method described above, heat treated, and then the oxygen transmission rate was measured. For the EVOH mixture having two melting points, the heat treatment temperature was 20 ° C. lower than the higher melting point.

(5) Number average molecular weight of copolymer and number average molecular weight of styrene block of copolymer The number average molecular weight of the copolymer was determined as a polystyrene equivalent value using gel permeation chromatography (GPC). The number average molecular weight of the styrene block of the copolymer was determined as a polystyrene equivalent value using GPC in the same manner, using the intermediate sampled after polymerization of the first styrene block as a sample.

(6) Styrene content of copolymer, proportion of structural unit represented by structural formula (I) in isoprene block and carbon-carbon double bond content:
These were all calculated from the spectrum obtained by ¹ H-NMR (nuclear magnetic resonance) measurement using deuterated chloroform as a solvent (“JNM-GX-500 type” manufactured by JEOL Ltd.). Here, the styrene content is a ratio (mol%) of styrene to all monomer units constituting the copolymer. The proportion of the structural unit represented by the structural formula (I) in the isoprene block is the structure with respect to all structural units derived from isoprene (1,4-isoprene unit, 3,4-isoprene unit, and 1,2-isoprene unit). It is the ratio (%) of the structural unit (3,4-isoprene unit and 1,2-isoprene unit) represented by the formula (I). Furthermore, from these results, the carbon-carbon double bond content was calculated as the number of moles of double bonds (eq / g) contained in 1 g of the resin.

(7) Melt flow rate:
A sample of resin or resin composition as a sample is filled into a cylinder having an inner diameter of 9.55 mm and a length of 162 mm of a melt indexer L244 (Takara Industry Co., Ltd.), melted at 210 ° C., and then melted against the molten resin. The load was evenly applied using a plunger having a weight of 2160 g and a diameter of 9.48 mm. The amount of resin extruded per unit time (g / 10 minutes) from an orifice with a diameter of 2.1 mm provided in the center of the cylinder was measured, and this was used as the melt flow rate.

(8) Refractive index:
The resin chip as a sample was subjected to film extrusion at an extrusion temperature of 210 ° C. to obtain an unstretched film having a thickness of 20 μm. The refractive index of this film was measured using an Abbe refractometer (4T type manufactured by Atago Co., Ltd., SL-Na-1 lamp manufactured by Toshiba Corporation).

(9) Haze value (cloudiness value):
A sample of resin or resin composition as a sample was subjected to film extrusion at an extrusion temperature of 210 ° C. to obtain an unstretched film having a thickness of 20 μm. The haze value of this film was measured using a Poic integrating sphere type light transmittance / total light reflectometer (“HR-100 type” manufactured by Murakami Color Research Laboratory) according to ASTM D1003-61. Moreover, the multilayer film was measured similarly. Furthermore, about the multilayer bottle, about four places which divided the center of the bottle trunk | drum into 4 on the circumference, the internal haze value in each location was measured, and the average value was made into the haze value (cloudiness value) of a bottle.

(10) Content of each structural unit of PET:
It was calculated from the spectrum obtained by ¹ H-NMR (nuclear magnetic resonance) measurement (using “JNM-GX-500 type” manufactured by JEOL Ltd.) using deuterated trifluoroacetic acid as a solvent.

(11) Intrinsic viscosity of PET:
A sample film layer was cut out from the PET layer of the multilayer container body and dissolved in an equal weight mixed solvent of phenol and tetrachloroethane. The viscosity of the obtained solution was measured at 30 ° C. using an Ubbelohde viscometer (“HRK-3 type” manufactured by Hayashi Seisakusho).

(12) Melting point and glass transition temperature of PET:
A sample film layer was cut out from the PET layer of the multilayer container body, and measured according to JIS K7121, using a differential scanning calorimeter (DSC) RDC220 / SSC5200H type manufactured by Seiko Electronics Industry. After holding the sample at 280 ° C. for 5 minutes, the temperature was lowered to 30 ° C. at a rate of 100 ° C./minute, held for 5 minutes, and then heated at a rate of 10 ° C./minute for measurement. Indium and lead were used for temperature calibration. From the obtained chart, the melting peak temperature (Tpm) and the midpoint glass transition temperature (Tmg) referred to in the above-mentioned JIS were determined, and these were defined as the melting point and the glass transition temperature, respectively.

  In the examples, EVOH was used as the gas barrier resin (A). The physical properties of EVOH used in the examples are shown in the following table.

  As the thermoplastic resin (B), a triblock copolymer (B-1) prepared by the following method was used.

  In a stirred autoclave purged with dry nitrogen, 600 parts by volume of cyclohexane, 0.16 parts by volume of N, N, N ′, N′-tetramethylethylenediamine (TMEDA), and 0.094 n-butyllithium as an initiator. Volume part was charged. The temperature was raised to 50 ° C., and 4.25 parts by volume of styrene monomer was fed and polymerized for 1.5 hours. Next, the temperature was lowered to 30 ° C., 120 parts by volume of isoprene was fed and polymerized for 2.5 hours. The temperature was raised again to 50 ° C., and 4.25 parts by volume of styrene monomer was fed and polymerized for 1.5 hours.

  To the resulting reaction solution, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and pentaerythritol tetrakis (3-laurylthio) were added as antioxidants. 0.15 parts by weight of propionate) was added to 100 parts by weight of the total amount of styrene and isoprene, respectively. The reaction solution was poured into methanol to precipitate the product, which was separated and dried to obtain a triblock copolymer (B-1) to which an antioxidant was added.

  The number average molecular weight of the obtained styrene-isoprene-styrene triblock copolymer (B-1) was 85000, the molecular weight of the styrene block in the copolymer was 8500, the styrene content was 14 mol%, and the structure in the isoprene block The proportion of the structural unit represented by the formula (I) was 55%. Further, the carbon-carbon double bond content of the copolymer was 0.014 eq / g, and the melt flow rate (210 ° C.-2160 g load) was 7.7 g / 10 min. In the copolymer (B-1), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 0.12% by weight and pentaerythritol Tetrakis (3-lauryl thiopropionate) 0.12 wt% was included. The copolymer (B-1) had a refractive index of 1.531, a haze value (cloudiness value) of 1.0%, and a tan δ main dispersion peak temperature derived from the isoprene block of −3 ° C.

  As the compatibilizer (C), a copolymer prepared by the following method was used.

Production of compatibilizer (C-1):
500 parts by weight of a styrene-hydrogenated butadiene-styrene triblock copolymer (“Tuftec (registered trademark)” H1062 manufactured by Asahi Kasei Co., Ltd.) in a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a cooler, and a distiller; After 1500 parts by weight of decalin was charged and the reaction vessel was purged with nitrogen, the temperature was set at 130 ° C. and stirred to dissolve the copolymer. Further, a mixed solution of 57.5 parts by weight of borane-triethylamine complex and 143 parts by weight of borate 1,3-butanediol ester was added to the reaction vessel. After stirring for 5 minutes, stirring was once stopped and the temperature of the reaction vessel was raised to 200 ° C. After a while after the temperature rise, the entire solution gelled, and then the gel gradually proceeded from the wall surface. Stirring was started again when stirring became possible, and stirring was continued for another hour after the gel in the reaction vessel completely disappeared. The condenser was switched to a distiller, the temperature of the reaction vessel was raised to 220 ° C., distillation was started at normal pressure, and distillation was continued until there was no distillate. The obtained reaction liquid was cooled, poured into acetone, the product was precipitated and separated, and vacuum dried at 120 ° C. overnight to obtain a triblock copolymer (C-1). When this copolymer was dissolved in a mixed solvent at a ratio of heavy paraxylene: deuterochloroform: ethylene glycol = 8: 2: 0.02 and subjected to ¹ H-NMR measurement (500 MHz), The amount of boronic acid 1,3-butanediol ester group was 220 μeq / g.

Production of compatibilizer (C-2):
Styrene-hydrogenated butadiene-styrene triblock copolymer (weight average molecular weight 100400, styrene / hydrogenated butadiene = 18/82 (weight ratio), 1,2-bond / 1,4-bond molar ratio of butadiene units = 47 / 53, 97% hydrogenation rate of butadiene units, double bond amount 430 μeq / g, melt index 5 g / 10 min (230 ° C., 2160 g load), density 0.89 g / cm ³ ), and inlet at 1 L / min While being replaced with nitrogen, it was fed to the twin screw extruder at a rate of 7 kg / hr. Next, a liquid mixture (TEAB / BBD = 29/71, weight ratio) of borane-triethylamine complex (TEAB) and boric acid 1,3-butanediol ester (BBD) is supplied from the liquid feeder 1 at a rate of 0.6 kg / hour. Then, 1,3-butanediol was supplied from the liquid feeder 2 at a rate of 0.4 kg / hour and continuously kneaded. During kneading, the pressure was adjusted so that the gauges of Vent 1 and Vent 2 showed about 20 mmHg. As a result, a triblock copolymer (C-2) containing a boronic acid 1,3-butanediol ester group (BBDE) was obtained at a rate of 7 kg / hour from the discharge port. The amount of boronic acid 1,3-butanediol ester group of this copolymer was 210 μeq / g.

In addition, the structure and operating conditions of the twin screw extruder used for the reaction are as follows.
Same direction twin screw extruder TEM-35B (Toshiba Machine)
Screw diameter: 37mmφ
L / D: 52 (15 blocks)
Liquid feeder: C3 (liquid feeder 1), C11 (liquid feeder 2)
Vent position: C6 (vent 1), C14 (vent 2)
Screw configuration: Use seal rings between C5-C6, C10-C11 and C12 Temperature setting: C1 Water cooling
C2-C3 200 ° C
C4 to C15 250 ° C
Die 250 ℃
Screw rotation speed: 400rpm

  Polyethylene terephthalate (PET) obtained by polymerization using germanium dioxide as a catalyst was used as the thermoplastic polyester. The contents of terephthalic acid units, ethylene glycol units, and diethylene glycol units in the PET were 50.0 mol%, 48.9 mol%, and 1.1 mol%, respectively. The intrinsic viscosity was 0.83 dl / g, and the melting point and glass transition temperature were 252 ° C. and 80 ° C., respectively.

Example 1
71.4 parts by weight of triblock copolymer (B-1), 28.6 parts by weight of compatibilizer (C-1) and 3.0300 parts by weight of cobalt stearate (II) (0.2857 parts by weight as cobalt atoms) Part) was dry blended, and in a cylinder using a 30 mmφ twin-screw extruder (TEX-30SS-30CRW-2V manufactured by Nippon Steel Works) under the conditions of a screw rotation speed of 300 rpm and an extrusion resin amount of 25 kg / hour. Was extruded and pelletized with a nitrogen purge. It dried under reduced pressure at 30 degreeC for 8 hours, and obtained the resin composition pellet which consists of a triblock copolymer (B-1), a compatibilizer (C-1), and a cobalt stearate.

Using the obtained resin composition pellets, extrusion molding was performed at an extrusion temperature of 210 ° C. to obtain a 20 μm-thick film (first single layer film). The haze value of this film was 1.8%. This film 0.9 m ² (0.2 m × 4.5 m; surface area 1.8 m ² ) was wound in a roll shape 5 hours after film formation, and was filled with air at 20 ° C. and 65% RH. Placed in a 375 ml Erlenmeyer flask. The air in the Erlenmeyer flask contained 21:79 oxygen and nitrogen by volume. The mouth of the Erlenmeyer flask was sealed with a multilayer sheet containing an aluminum layer using an epoxy resin, and allowed to stand at 20 ° C. The air inside 2 days, 4 days, and 8 days after encapsulation was sampled with a syringe, and the oxygen concentration of this air was measured using gas chromatography. The pores vacated in the multilayer sheet at the time of measurement were sealed with an epoxy resin each time. The amount of oxygen decrease (oxygen absorption) was calculated from the volume ratio of oxygen and nitrogen obtained by the measurement, and the results shown in FIG. 1 were obtained. The oxygen absorption rate of the film, calculated from the measurement results after 2 days and 8 days, was 67 ml / m ² · day.

  93 parts by weight of EVOH (A-11) shown in Table 2 and 7.2121 parts by weight of the above resin composition were dry blended, and a 30 mmφ twin screw extruder (TEX-30SS-30CRW-2V manufactured by Nippon Steel Works). Was extruded and pelletized at 210 ° C. under conditions of a screw speed of 300 rpm and an extruded resin amount of 25 kg / hour, and dried under reduced pressure at 30 ° C. for 16 hours to obtain resin composition pellets. The melt flow rate (210 ° C., 2160 g load) of this resin composition was 13.1 g / 10 min. When the fracture surface of the resin composition pellet was observed with an electron microscope, particles having a size of 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix made of EVOH.

A 20 μm-thick film (second single-layer film) was obtained from this resin composition in the same manner as described above, and the haze value was measured and found to be 1.3%. Moreover, when the amount of oxygen absorption was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.238 ml / m ² · day.

  Next, a stretched polypropylene film having a thickness of 20 μm (OP- # 20 U-1 manufactured by Tosero Co., Ltd.), a urethane adhesive (manufactured by Toyo Morton, trade name: AD335A) and a curing agent is formed on both surfaces of the obtained film. A multilayer film was obtained by laminating using a toluene / methyl ethyl ketone mixed solution (by weight ratio of 1: 1) manufactured by Toyo Morton (trade name: Cat-10). The haze value of this multilayer film was 2.7%. The temperature and humidity of this multilayer film was adjusted to 20 ° C.-85% RH, and the time when 24 hours passed after film formation was set to 0, using an oxygen transmission amount measuring device (OX-TRAN-10 / 50A, manufactured by Modern Control). When the oxygen transmission rate was measured for 1000 hours, the results shown in FIG. 3 were obtained.

  Next, using the above resin composition pellets and the above-mentioned PET as raw materials, using a Nissei ASB co-injection stretch blow molding machine (ASB-50HT type 500 ml), two types of PET / resin composition / PET 3 Layered parison was molded. At this time, the PET side injection machine temperature is 290 ° C., the resin composition side injection machine temperature is 205 ° C., the temperature of the hot runner block part where the PET and the resin composition merge is 255 ° C., and the injection mold core temperature is 15 ° C. The injection mold cavity temperature was 15 ° C. The cycle time was 40 seconds. Thereafter, using a stretch blow molding machine (LB01) manufactured by CORPOPLAST, the surface temperature of the parison is heated to 105 ° C. and stretch blow molding is performed. The average thickness in the body portion is 100 μm for the inner layer PET, and the intermediate layer resin composition A multi-layer injection blow-molded bottle with 15 μm of the product and 150 μm of the outer layer PET and a bottle bottom portion of the champagne bottle type of two types and three layers was manufactured. The haze value of this bottle was 3.0%.

  Adjust the temperature and humidity of the obtained bottle to 20 ° C-65% RH outside the bottle and 20 ° C-100% RH inside the bottle, and use an oxygen permeation measuring device (OX-TRAN-10 / 50A, manufactured by Modern Control) Then, the oxygen permeation rate per container 10 days after molding was measured and found to be 0.00 ml / container · day · atm.

  Separately, the bottle was filled with water as the contents and sealed under normal pressure. From the height of 50 cm with the bottle body vertical, the bottle was naturally dropped only once onto a horizontal concrete plate with the bottle bottom facing downward. A test of 100 bottles per one bottle was performed, and the delamination occurrence rate Rd (%) was calculated from the number Nd of bottles that caused delamination according to the following formula. As a result, it was 7%.

      Rd = (Nd / 100) × 100

Example 2
71.4 parts by weight of the triblock copolymer (B-1) and 28.6 parts by weight of the compatibilizer (C-1) used in Example 1 were dry blended, and a 30 mmφ twin screw extruder (Corporation) Using TEX-30SS-30CRW-2V) manufactured by Nippon Steel Works, the inside of the cylinder was purged with nitrogen and extruded at 200 ° C. under the conditions of a screw rotation speed of 300 rpm and an extruded resin amount of 25 kg / hour to be pelletized. It dried under reduced pressure at 30 degreeC for 8 hours, and obtained the resin composition pellet which consists of a triblock copolymer (B-1) and a compatibilizer (C-1).

  A film having a thickness of 20 μm was obtained from this resin composition in the same manner as in Example 1, and the haze value was measured and found to be 1.6%.

  74.4 parts by weight of EVOH (A-11) used in Example 1, 18.6 parts by weight of EVOH (A-21) shown in Table 2, compatibilized with the above triblock copolymer (B-1) Resin in the same manner as in Example 1 using 7 parts by weight of the resin composition comprising the agent (C-1) and 0.2121 parts by weight of cobalt stearate (II) (0.0200 parts by weight as cobalt atoms). A composition was obtained. The melt flow rate (210 ° C., 2160 g load) of this resin composition was 12.8 g / 10 min. When the fracture surface of the resin composition pellet was observed with an electron microscope, particles having a size of 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix made of EVOH.

A film having a thickness of 20 μm was obtained from this resin composition in the same manner as in Example 1, and the haze value was measured and found to be 1.2%. Moreover, when the amount of oxygen absorption was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.475 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.5%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Furthermore, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 2.8%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.00 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 1%.

Example 3
In Example 2, a resin composition was obtained in the same manner as in Example 2 except that EVOH (A-12) shown in Table 2 was used instead of EVOH (A-11). The melt flow rate (210 ° C., 2160 g load) of this resin composition was 9.2 g / 10 minutes. When the fracture surface of the resin composition pellet was observed with an electron microscope, particles having a size of 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix made of EVOH.

A film having a thickness of 20 μm was obtained from this resin composition in the same manner as in Example 1, and the haze value was measured and found to be 1.4%. Moreover, when the amount of oxygen absorption was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.938 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.7%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Further, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 2.9%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.00 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 3%.

Example 4
In Example 3, the resin composition was obtained like Example 3 except having used the compatibilizing agent (C-2) instead of the compatibilizing agent (C-1). The melt flow rate (210 ° C., 2160 g load) of this resin composition was 9.2 g / 10 minutes. When the fracture surface of the resin composition pellet was observed with an electron microscope, particles having a size of 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix made of EVOH.

A film having a thickness of 20 μm was obtained from this resin composition in the same manner as in Example 1, and the haze value was measured and found to be 1.4%. Moreover, when the amount of oxygen absorption was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.044 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.8%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Furthermore, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 3.0%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.00 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 2%.

Comparative Example 1
EVOH (A-11) was used alone, and a film having a thickness of 20 μm was obtained in the same manner as in Example 1. When the oxygen absorption amount of this film was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.000 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.1%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Furthermore, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 2.1%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.03 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 10%.

Comparative Example 2
95 parts by weight of EVOH (A-11) used in Example 1, 5 parts by weight of triblock copolymer (B-1), and 0.2121 parts by weight of cobalt stearate (II) (0.0200 parts by weight as cobalt atoms) ) Was used in the same manner as in Example 1 to obtain a resin composition. The melt flow rate (210 ° C., 2160 g load) of this resin composition was 13.5 g / 10 minutes. When the fracture surface of the resin composition pellet was observed with an electron microscope, particles of about 1 to 2 μm of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.

A film having a thickness of 20 μm was obtained from this resin composition in the same manner as in Example 1, and the haze value was measured and found to be 1.5%. Moreover, when the amount of oxygen absorption was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.117 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.9%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Furthermore, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 3.3%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.00 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 52%.

Comparative Example 3
A film having a thickness of 20 μm was obtained in the same manner as in Comparative Example 1 except that EVOH (A-12) was used alone instead of EVOH (A-11). When the oxygen absorption amount of this film was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.000 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.0%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Furthermore, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 2.0%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.02 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 11%.

Comparative Example 4
A resin composition was obtained in the same manner as in Comparative Example 2 except that EVOH (A-12) was used instead of EVOH (A-11). The melt flow rate (210 ° C., 2160 g load) of this resin composition was 10.0 g / 10 minutes. When the fracture surface of the resin composition pellet was observed with an electron microscope, particles of about 1 to 2 μm of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.

A film having a thickness of 20 μm was obtained from this resin composition in the same manner as in Example 1, and the haze value was measured and found to be 1.4%. Moreover, when the amount of oxygen absorption was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.700 ml / m ² · day. Next, a multilayer film was produced in the same manner as in Example 1, and the haze value was measured and found to be 2.9%. Further, when the oxygen transmission rate was measured over time, the result shown in FIG. 3 was obtained.

  Further, when a bottle was produced in the same manner as in Example 1 and the haze value was measured, it was 3.4%. When the oxygen transmission rate of this bottle was measured in the same manner as in Example 1, it was 0.00 ml / container · day · atm. When a drop test was performed in the same manner as in Example 1, the delamination occurrence rate was 85%.

  The composition of the above resin composition is summarized in Table 3, and the results of various evaluations are summarized in Table 4.

Effect of the invention

  According to the present invention, a resin composition having an excellent oxygen scavenging function can be obtained. The resin composition is easy to handle and can be molded into any shape. In particular, the container made of the resin composition not only has excellent gas barrier properties, moisture proofing properties, fragrance retention properties, and flavor barrier properties, but also has excellent impact peel resistance, and also has an appearance and particularly high transparency. Therefore, it is useful as a container for products that are highly sensitive to oxygen and easily deteriorate, particularly foods, beverages, pharmaceuticals, and cosmetics.

  2 is a graph plotting oxygen absorption of the first single-layer film of Example 1 against time.   It is the graph which plotted the oxygen absorption amount of the single layer film of Examples 1-4 and Comparative Examples 1-4 with respect to time. However, Example 1 is the result of the second monolayer film.   It is the graph which plotted the oxygen transmission rate of the multilayer film of Examples 1-4 and Comparative Examples 1-4 with respect to time.

Claims (9)

Gas barrier resin (A) having an oxygen transmission rate of 500 ml · 20 μm / m ² · day · atm (20 ° C., 65% RH) or less, 40 to 99.8 wt%, thermoplastic resin other than the gas barrier resin (A) (B) A resin composition containing 0.1 to 30% by weight, a compatibilizer (C) 0.1 to 30% by weight, and a transition metal salt (D),
The gas barrier resin (A) is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more,
The thermoplastic resin (B) has the following structural formula (I)
[Chemical 1]

(Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or a methyl group, and R ₃ and R ₄ are hydrogen atoms)
A block copolymer having a diene compound unit and an aromatic vinyl compound unit containing a unit represented by:
The compatibilizer (C) is a styrene-diene block block having at least one functional group selected from the group consisting of boronic acid groups and boron-containing groups that can be converted to boronic acid groups in the presence of water. Coalesced ,
The transition metal salt (D) is an organic acid cobalt;
A resin composition in which particles comprising the thermoplastic resin (B) are dispersed in a matrix of the gas barrier resin (A).
The transition metal salt (D) is contained at a ratio of 1 to 5000 ppm in terms of metal element, based on the total weight of the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C). 2. The resin composition according to 1.
The resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) contains a carbon-carbon double bond at a rate of 0.0001 eq / g or more.
The resin composition according to any one of claims 1 to 3 carbon-average molecular weight of the thermoplastic resin (B) is 1,000 to 500,000.
The resin composition according to any one of claims 1 to 4 , wherein a difference in refractive index between the gas barrier resin (A) and the thermoplastic resin (B) is 0.01 or less.
The resin composition according to claim 1 , wherein the diene compound unit is at least one selected from the group consisting of isoprene units and butadiene units.
The resin composition according to claim 1 , wherein the aromatic vinyl compound unit is a styrene unit.
A layer of the resin composition according to any one of claims 1 to 7 multilayer structure comprising at least one layer.
A multilayer container comprising at least one layer comprising the resin composition according to any one of claims 1 to 7 and a thermoplastic polyester layer.

Images