JP7149882B2 - Resin composition, molded article, secondary processed product, method for producing resin composition, and method for producing molded article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, a molded article, a secondary processed product, a method for producing a resin composition, and a method for producing a molded article.

Ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as “EVOH”) is a resin having excellent barrier properties against oxygen, odors, flavors and the like. Therefore, EVOH is suitably used as a packaging material for foods and the like.

However, since EVOH has low stretchability, voids and cracks tend to occur during processing and molding. Therefore, in order to improve stretchability and the like, a resin composition in which EVOH is mixed with polyamide (hereinafter sometimes abbreviated as "PA") is used depending on the application (see Patent Documents 1 and 2). ).

On the other hand, the packaging material is often subjected to heat treatment (retort treatment or boiling treatment) with hot water or steam after being filled with contents such as food. However, when EVOH is heat-treated with hot water or steam for a long period of time, whitening streaks and partial opacity (whitening, etc.) occur, resulting in a deterioration in appearance. In order to improve such whitening and the like, a resin composition in which EVOH and PA are blended in an appropriate ratio is used as a packaging material for heat treatment (see Patent Document 3).

JP-A-58-129035 JP-A-04-202549 WO2015/174396

Such packaging materials as described above are generally required to have high gas barrier properties for long-term storage stability of foods and the like. However, when EVOH and PA are blended, the gas barrier properties of the packaging material tend to deteriorate, so packaging materials with higher barrier performance and good resistance to heat treatment are desired.

In addition, the required appearance performance required for packaging materials is increasing, and the whitening phenomenon described above is seen when packaging materials having a layer of a resin composition containing EVOH are subjected to retort treatment (heat treatment for a long time). There is a need for further suppression of Therefore, the resin composition is required to have excellent retort resistance, such as suppression of whitening caused by long-term retort treatment.

However, in the techniques of Patent Documents 1 and 2, retort resistance is not taken into consideration at all, and both good gas barrier properties and retort resistance cannot be achieved. Also, in the technique of Patent Document 3, there is still a demand for a higher level of both gas barrier performance and retort resistance.

The present invention has been made based on the above circumstances, and an object of the present invention is to provide a resin composition having both good gas barrier properties and retort resistance, a molded article molded from this resin composition, and secondary processing. The object of the present invention is to provide a product, a method for producing this resin composition, and a molded product.

In order to solve the above problems, the present invention provides a resin composition, a molded article, a secondary processed product, a method for producing a resin composition, and a method for producing a molded article, which are described below.
That is, the present invention
[1] An ethylene-vinyl alcohol copolymer (A), an ethylene-vinyl alcohol copolymer (B) having a melting point TmB lower than the melting point TmA of the ethylene-vinyl alcohol copolymer (A), and a polyamide ( C), and the difference (TmA−TmB) between the melting point TmA of the ethylene-vinyl alcohol copolymer (A) and the melting point TmB of the ethylene-vinyl alcohol copolymer (B) is 10° C. or more, and the gel A resin composition having a fraction of 0.5% or more and 20% or less;
[2] The mixing ratio (A/B) based on mass of the ethylene-vinyl alcohol copolymer (A) and the ethylene-vinyl alcohol copolymer (B) is 1.0 or more and 20 or less, resin composition;
[3] The mass-based mixing ratio ((A+B)/C) of the sum of the ethylene-vinyl alcohol copolymer (A) and the ethylene-vinyl alcohol copolymer (B) and the polyamide (C) is 0.67 or more. 99 or less, the resin composition of [1] or [2];
[4] Any one of [1] to [3], wherein the mass-based mixing ratio (B/C) of the ethylene-vinyl alcohol copolymer (B) and the polyamide (C) is 0.053 or more and 19 or less The resin composition of;
[5] The resin composition of any one of [1] to [4], wherein the polyamide (C) has a melting point TmC of 190°C or higher;
[6] Further containing fatty acid divalent metal salt (D), ethylene-vinyl alcohol copolymer (A), ethylene-vinyl alcohol copolymer (B) and fatty acid with respect to total amount of 100 parts by mass of polyamide (C) The resin composition according to any one of [1] to [5], wherein the content of the divalent metal salt (D) in terms of metal ions is 0.001 parts by mass or more and 0.05 parts by mass or less;
[7] The resin composition of [6], wherein the amount (D/C) of the fatty acid divalent metal salt (D) in terms of metal ions with respect to the mass of the polyamide (C) is 3 μmol/g or more and 250 μmol/g or less;
[8] The resin composition of any one of [1] to [7], which is in the form of pellets;
[9] Molded article made of the resin composition of any one of [1] to [8];
[10] An ethylene-vinyl alcohol copolymer (A), an ethylene-vinyl alcohol copolymer (B) having a melting point TmB lower than the melting point TmA of the ethylene-vinyl alcohol copolymer (A), and a polyamide ( C), and the difference (TmA−TmB) between the melting point TmA of the ethylene-vinyl alcohol copolymer (A) and the melting point TmB of the ethylene-vinyl alcohol copolymer (B) is 10° C. or more, and the gel Molded body with a fraction of 0.5% or more and 20% or less;
[11] The molded article of [9] or [10], which is a film;
[12] The compact according to any one of [9] to [11], which is a retort packaging material or a boiling packaging material;
[13] A secondary processed product of any of [9] to [12];
[14] A step of dry-blending an ethylene-vinyl alcohol copolymer (A), an ethylene-vinyl alcohol copolymer (B) and a polyamide (C), and melt-kneading the mixture obtained in the dry-blending step. A method for producing a resin composition according to any one of [1] to [8], comprising the steps;
[15] A method for producing a molded body, comprising the step of melt-molding the resin composition of any one of [1] to [8];
is.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition having both good gas barrier properties and retort resistance, a molded article and a secondary processed product made of the resin composition, and a method for producing the resin composition and the molded article.

It is a mimetic diagram showing a phase separation structure of a resin composition concerning one embodiment of the present invention. 1 is a transmission electron micrograph of the monolayer film obtained in Example 1, which is stained with phosphotungsten. 4 is a transmission electron micrograph of the monolayer film obtained in Comparative Example 4, which was dyed with phosphotungsten.

Hereinafter, the resin composition and its manufacturing method, the molded article and its manufacturing method, and the secondary processed product of the present invention will be described in detail. In the present invention, the gas barrier properties are evaluated based on the measurement results of the oxygen barrier properties.

<Resin composition>
The resin composition of the present invention comprises an ethylene-vinyl alcohol copolymer (A) (hereinafter sometimes abbreviated as "EVOH (A)") and a melting point TmB lower than the melting point TmA of EVOH (A). Ethylene-vinyl alcohol copolymer (B) (hereinafter sometimes abbreviated as "EVOH (B)") and polyamide (C) (hereinafter sometimes abbreviated as "PA (C)") wherein the difference (TmA−TmB) between the melting point TmA of EVOH (A) and the melting point TmB of EVOH (B) is 10° C. or more, and the resin has a gel fraction of 0.5% or more and 20% or less. composition.

The melting points of EVOH (A), EVOH (B) and PA (C) are measured by differential thermal analysis, and the peak top of melting measured according to ISO11357:2013 is defined as the melting point.

The resin composition of the present invention has both good gas barrier properties and retort resistance due to the above composition and gel fraction. Further, the resin composition of the present invention preferably further contains a predetermined amount of fatty acid divalent metal salt (D), so that it can have good thermal stability, trim recoverability and retort resistance.

In the resin composition of the present invention, PA (C) has a melting point TmC of 190° C. or higher, further contains a fatty acid divalent metal salt (D), and contains EVOH (A), EVOH (B) and PA (C). The content of the fatty acid divalent metal salt (D) in terms of metal ions is preferably 0.001 parts by mass or more and 0.05 parts by mass or less per 100 parts by mass of the total amount of . In such cases, the resin composition of the present invention can combine good thermal stability, trim stability and retort resistance. Although the details of the reason why such an effect is produced are unknown, for example, the following conjecture is conceivable. Good thermal stability is exhibited by containing a predetermined amount of fatty acid divalent metal salt (D). Also, by using the low melting point EVOH (B) and the fatty acid divalent metal salt (D) in combination, excellent trim recoverability is exhibited. Furthermore, good retort resistance is exhibited by using PA (C) having a high melting point and two types of EVOH having different melting points.

(EVOH (A))
EVOH (A) is an EVOH whose melting point TmA is higher than the melting point TmB of EVOH (B).

EVOH (A) can usually be obtained by saponifying an ethylene-vinyl ester copolymer. That is, EVOH (A) is usually a saponified ethylene-vinyl ester copolymer. Copolymerization of ethylene and vinyl ester and saponification of ethylene-vinyl ester copolymer can be carried out by known methods. Vinyl esters are typically vinyl acetate, but other vinyl esters such as fatty acid vinyl esters (vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatate, etc.).

The lower limit of the degree of saponification of the vinyl ester component of EVOH (A) is preferably 85 mol%, more preferably 90 mol%, still more preferably 96 mol%, particularly preferably 98 mol%, most preferably 99 mol%. By making the degree of saponification equal to or higher than the above lower limit, it is possible to improve the gas barrier properties of the molded product. Moreover, the upper limit of the degree of saponification may be 100 mol % or 99.99 mol %.

The lower limit of the ethylene unit content in EVOH (A) is preferably 5 mol%, more preferably 10 mol%, even more preferably 20 mol%, and particularly preferably 25 mol%. The upper limit of the ethylene unit content is preferably 70 mol%, more preferably 50 mol%, still more preferably 40 mol%, still more preferably 35 mol%, and particularly preferably 30 mol%. By setting the ethylene unit content to the above lower limit or more, it is possible to improve the gas barrier properties of the film or the like under high humidity conditions and the appearance after heat treatment. On the other hand, by setting the ethylene unit content to the above upper limit or less, the gas barrier properties of the film or the like can be enhanced. Further, by setting the ethylene unit content of EVOH (A) within the above range, the desired melting point TmA can be relatively easily adjusted.

In addition, EVOH (A) may have units derived from monomers other than ethylene, vinyl esters and saponified products thereof as long as the object of the present invention is not hindered. When EVOH (A) has a unit derived from the other monomer, the content of the other monomer unit is preferably 30 mol% or less, more preferably 20 mol% or less, relative to the total structural units of EVOH (A). More preferably, it is 10 mol % or less, and particularly preferably 5 mol % or less. When EVOH (A) contains the above-mentioned other monomer units, it is also possible to adjust the melting point by adjusting the content. When EVOH (A) contains units derived from the other monomers, the lower limit may be 0.05 mol % or 0.10 mol %. Examples of the other monomers include unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid, or their anhydrides, salts, mono- or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; acrylamide; , amides such as methacrylamide; vinylsulfonic acid, allylsulfonic acid, olefinsulfonic acid such as methallylsulfonic acid or salts thereof; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, γ- Vinylsilane compounds such as methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like.

Further, the unit derived from the other monomer is a structural unit (I) represented by the following general formula (I), a structural unit (II) represented by the following general formula (II), and the following general formula (III ) may be at least one of the structural units (III) represented by When EVOH (A) has such a structural unit, it is possible to further improve the bending resistance and the like of the resulting film.

In general formula (I) above, R ¹ , R ² and R ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, It represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or a hydroxyl group. Also, one pair of R ¹ , R ² and R ³ may be bonded. In addition, some or all of the hydrogen atoms of the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms are It may be substituted with a hydroxyl group, a carboxyl group or a halogen atom.

In general formula (II) above, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an alicyclic carbonized group having 3 to 10 carbon atoms. It represents a hydrogen group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a hydroxyl group. Also, ^R4 and ^R5 or ^R6 and ^R7 may be bonded. In addition, some or all of the hydrogen atoms of the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms are It may be substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom.

In general formula (III) above, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an alicyclic carbonized group having 3 to 10 carbon atoms. It represents a hydrogen group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a hydroxyl group. In addition, some or all of the hydrogen atoms of the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms are It may be substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom. R ¹² and R ¹³ each independently represent a hydrogen atom, a formyl group or an alkanoyl group having 2 to 10 carbon atoms.

In the structural unit (I), (II) or (III), the aliphatic hydrocarbon group having 1 to 10 carbon atoms includes an alkyl group, an alkenyl group, and the like. Hydrogen groups include cycloalkyl groups, cycloalkenyl groups and the like, and aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl groups and the like.

In the structural unit (I), R ¹ , R ² and R ³ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a hydroxymethyl group and a hydroxyethyl group. From the viewpoint of further improving the stretchability and thermoformability of the resin composition of (1), it is more preferable that they are each independently a hydrogen atom, a methyl group, a hydroxyl group and a hydroxymethyl group.

The method of incorporating the structural unit (I) into EVOH (A) is not particularly limited, but for example, a method of copolymerizing a monomer derived from the structural unit (I) in the polymerization of ethylene and vinyl ester. is mentioned. Such monomers include alkenes such as propylene, butylene, pentene, hexene; 4-diacyloxy-1-butene, 3-acyloxy-4-hydroxy-1-butene, 4-acyloxy-3-hydroxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2- methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4-hydroxy-1-pentene, 5-hydroxy-1-pentene, 4, 5-dihydroxy-1-pentene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-hydroxy-3-methyl-1-pentene, 5-hydroxy- 3-methyl-1-pentene, 4,5-dihydroxy-3-methyl-1-pentene, 5,6-dihydroxy-1-hexene, 4-hydroxy-1-hexene, 5-hydroxy-1-hexene, 6- Alkenes having a hydroxyl group or an ester group such as hydroxy-1-hexene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene, etc. be done. Among them, propylene, 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4- Diacyloxy-1-butene is preferred. Acyloxy is preferably acetoxy, specifically 3-acetoxy-1-propene, 3-acetoxy-1-butene, 4-acetoxy-1-butene and 3,4-diacetoxy-1-butene. In the case of an alkene having an ester, it is derived to the structural unit (I) during the saponification reaction.

In structural unit (II) above, both R ⁴ and R ⁵ are preferably hydrogen atoms. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, one of R ⁶ and R ⁷ is a C 1-10 aliphatic hydrocarbon group, and the other is a hydrogen atom. This aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group. From the viewpoint of placing particular importance on the gas barrier properties of the resulting film, etc., it is particularly preferred that one of R ⁶ and R ⁷ is a methyl group or an ethyl group, and the other is a hydrogen atom. It is also particularly preferred that one of R ⁶ and R ⁷ is a substituent represented by (CH ₂ ) _h OH (where h is an integer of 1 to 8) and the other is a hydrogen atom. In the substituent represented by (CH ₂ ) _h OH, h is preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1.

The method for incorporating the structural unit (II) into EVOH (A) is not particularly limited. For example, a method of reacting EVOH (A) obtained by a saponification reaction with a monovalent epoxy compound represented by the following general formulas (IV) to (X) to contain the compound is preferably used.

In the general formulas (IV) to (X), R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (alkyl group, alkenyl group, etc.), an alicyclic hydrocarbon group having 3 to 10 carbon atoms (cycloalkyl group, cycloalkenyl group, etc.), or an aliphatic hydrocarbon group having 6 to 10 carbon atoms (phenyl group, etc.). i, j, k, p and q each independently represents an integer of 1 to 8; However, when R ¹⁷ is a hydrogen atom, R ¹⁸ has a substituent other than a hydrogen atom.

Examples of the monovalent epoxy compound represented by the general formula (IV) include epoxyethane (ethylene oxide), epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 3-methyl-1,2- Epoxybutane, 1,2-epoxypentane, 3-methyl-1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2- Epoxyhexane, 3-methyl-1,2-epoxyheptane, 4-methyl-1,2-epoxyheptane, 1,2-epoxyoctane, 2,3-epoxyoctane, 1,2-epoxynonane, 2,3- Epoxynonane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxyethylbenzene, 1-phenyl-1,2-epoxypropane, 3-phenyl-1,2-epoxypropane and the like.

Examples of the monovalent epoxy compound represented by the general formula (V) include various alkyl glycidyl ethers. Examples of the monovalent epoxy compound represented by the general formula (VI) include various alkylene glycol monoglycidyl ethers. Examples of the monovalent epoxy compound represented by the general formula (VII) include various alkenyl glycidyl ethers. Examples of the monovalent epoxy compound represented by the general formula (VIII) include various epoxyalkanols such as glycidol. Examples of the monovalent epoxy compound represented by the general formula (IX) include various epoxycycloalkanes. Examples of the monovalent epoxy compound represented by the general formula (X) include various epoxycycloalkenes.

Among the above monovalent epoxy compounds, epoxy compounds having 2 to 8 carbon atoms are preferred. In particular, the number of carbon atoms in the monovalent epoxy compound is more preferably 2 to 6, more preferably 2 to 4, from the viewpoints of ease of handling and reactivity of the compound. Among the above general formulas, the monovalent epoxy compound is particularly preferably the compound represented by the general formula (IV) or the compound represented by the general formula (V). Specifically, 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane and glycidol are preferred from the viewpoint of reactivity with EVOH (A) and gas barrier properties of the resulting film. Among them, epoxypropane and glycidol are particularly preferred.

In the structural unit (III), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl groups are preferred.

Although the method for incorporating the structural unit (III) in EVOH (A) is not particularly limited, examples thereof include the method described in JP-A-2014-034647.

The lower limit of the melting point TmA of EVOH (A) is preferably 160°C, more preferably 170°C, still more preferably 180°C, and particularly preferably 185°C. On the other hand, the upper limit of the melting point TmA is preferably 210°C, more preferably 200°C, and even more preferably 195°C. By setting the melting point TmA of EVOH (A) within the above range, melt moldability, thermal stability, gas barrier properties, retort resistance, etc. can be further enhanced.

As for the melt viscosity of EVOH (A), the lower limit of MFR is preferably 1 g/10 min, more preferably 3 g/10 min under conditions of 210° C. and 2160 g load. On the other hand, the upper limit is preferably 15 g/10 minutes, more preferably 10 g/10 minutes, even more preferably 6 g/10 minutes. By using EVOH (A) having such a melt viscosity, melt moldability, retort resistance, and the like can be further enhanced. In addition, the value of MFR in this specification can be measured according to ASTM D1238.

The lower limit of the content of EVOH (A) is preferably 30 parts by mass, more preferably 50 parts by mass, and 60 parts by mass with respect to 100 parts by mass of the total amount of EVOH (A), EVOH (B) and PA (C). is more preferred. On the other hand, the upper limit of this content is preferably 95 parts by mass, more preferably 90 parts by mass, still more preferably 85 parts by mass, and even more preferably 80 parts by mass. By setting the content of EVOH (A) within the above range, thermal stability, gas barrier properties, retort resistance, etc. can be improved in a well-balanced manner.

(EVOH (B))
EVOH (B) in the resin composition according to one embodiment of the present invention is preferably EVOH having a melting point TmB lower than the melting point TmA of EVOH (A) by 10° C. or more. EVOH (B) in the resin composition according to another embodiment of the present invention has a melting point TmB lower than the melting point TmA of EVOH (A) by 10° C. or more. By containing EVOH (B) having such a low melting point, the resin composition of the present invention can improve gas barrier properties, retort resistance, trim recoverability, and the like.

The lower limit of the difference (TmA-TmB) between the melting point TmA of EVOH (A) and the melting point TmB of EVOH (B) is preferably 15°C, more preferably 20°C. When the difference (TmA-TmB) between the melting point TmA and the melting point TmB is 10° C. or more, gas barrier properties, retort resistance, trim recoverability and the like can be enhanced. On the other hand, the upper limit of this difference (TmA-TmB) may be, for example, 50°C, 40°C, or 30°C.

The method for producing EVOH (B), the specific examples and preferred examples of the constituent monomers and the degree of saponification are the same as those for EVOH (A).

The lower limit of the ethylene unit content in EVOH (B) is preferably 20 mol%, more preferably 30 mol%, still more preferably 36 mol%, and particularly preferably 40 mol%. The upper limit of the ethylene unit content is preferably 70 mol%, more preferably 60 mol%, even more preferably 50 mol%. By setting the ethylene unit content to the above lower limit or more, it is possible to improve gas barrier properties, retort resistance, etc. under high humidity in films and the like. On the other hand, by setting the ethylene unit content to the above upper limit or less, the gas barrier properties of the film or the like can be enhanced. Further, by setting the ethylene unit content of EVOH (B) within the above range, the desired melting point TmB can be relatively easily adjusted.

The lower limit of the melting point TmB of EVOH (B) is preferably 150°C, more preferably 160°C. On the other hand, the upper limit of the melting point TmB is preferably 190°C, more preferably 180°C, still more preferably 175°C, and particularly preferably 170°C. By setting the melting point TmB of EVOH (B) within the above range, retort resistance and the like can be further enhanced.

As for the melt viscosity of EVOH (B), the lower limit of MFR is preferably 1 g/10 min, more preferably 3 g/10 min under conditions of 210° C. and 2160 g load. On the other hand, the upper limit is preferably 30 g/10 minutes, more preferably 20 g/10 minutes, even more preferably 15 g/10 minutes. By using EVOH (B) having such a melt viscosity, melt moldability, retort resistance, etc. can be further improved.

The lower limit of the content of EVOH (B) is preferably 1 part by mass, more preferably 3 parts by mass, and 5 parts by mass with respect to 100 parts by mass of the total amount of EVOH (A), EVOH (B) and PA (C). is more preferred. On the other hand, the upper limit of the content is preferably 50 parts by mass, more preferably 40 parts by mass, and even more preferably 30 parts by mass. By setting the content of EVOH (B) within the above range, gas barrier properties, retort resistance, thermal stability, trim recoverability, etc. can be improved in a well-balanced manner.

(PA (C))
PA(C) is a polymer obtained by polymerizing monomers through amide bonds. Examples of PA (C) include polycaproamide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryl Lactam (nylon 12), polyethylenediamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), poly Hexamethylenedodecamide (nylon 612), polyoctamethyleneadipamide (nylon 86), polydecamethyleneadipamide (nylon 106), caprolactam/lauryllactam copolymer (nylon 6/12), caprolactam/ω-aminononane Acid copolymer (nylon 6/9), caprolactam/hexamethylenediammonium adipate copolymer (nylon 6/66), lauryllactam/hexamethylenediammonium adipate copolymer (nylon 12/66), ethylenediammonium adipate / hexamethylenediammonium adipate copolymer (nylon 26/66), caprolactam / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon 6/66/610), ethylenediammonium adipate / hexamethylene di Ammonium adipate/hexamethylenediammonium sebacate copolymer (nylon 26/66/610), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (nylon 6T), hexamethylene isophthalamide/hexamethylene terephthalamide Copolymer (nylon 6I/6T), 11-aminoundecaneamide/hexamethylene terephthalamide copolymer, polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyhexamethylenecyclohexylamide, Examples thereof include polynonamethylenecyclohexylamide and those obtained by modifying these polyamides with aromatic amines such as methylenebenzylamine and meta-xylenediamine. In addition, meta-xylylene diammonium adipate and the like are also included.

Among them, from the viewpoint of gas barrier properties, retort resistance, thermal stability, trim recoverability, etc., it is preferable to use a polyamide mainly composed of caproamide. Specifically, 75 mol% or more of the constituent units of the polyamide are caproamide units. is preferably Among them, nylon 6 is preferable from the viewpoint of compatibility with EVOH (A) and EVOH (B).

As a method for polymerizing PA (C), melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, or a combination thereof can be employed.

The lower limit of the melting point TmC of PA(C) is preferably 190°C, more preferably 200°C, still more preferably 205°C, and particularly preferably 210°C. By making the melting point TmC of PA(C) equal to or higher than the above lower limit, retort resistance and the like can be further enhanced. On the other hand, the upper limit of the melting point TmC is preferably 250°C, more preferably 230°C, and even more preferably 225°C. By setting the melting point TmC of PA(C) to the above upper limit or less, melt moldability, thermal stability, trim recoverability, etc. can be further enhanced.

The lower limit of the content of PA (C) is preferably 1 part by mass, more preferably 4 parts by mass, and 7 parts by mass with respect to 100 parts by mass of the total amount of EVOH (A), EVOH (B) and PA (C). is more preferred. Retort resistance etc. can be improved by making content of PA (C) more than the said minimum. On the other hand, the upper limit of this content is preferably 60 parts by mass, more preferably 40 parts by mass, still more preferably 30 parts by mass, particularly preferably 20 parts by mass, and most preferably 15 parts by mass. By making the content of PA (C) equal to or less than the above upper limit, it is possible to further improve the gas barrier property while improving the thermal stability, trim recoverability and retort resistance.

(Fatty acid divalent metal salt (D))
The resin composition of the present invention preferably contains a fatty acid divalent metal salt (D). By containing a predetermined amount of fatty acid divalent metal salt (D), the thermal stability, trim recoverability, hue, etc. of the resin composition of the present invention can be further improved. The fatty acid constituting the fatty acid divalent metal salt (D) is a monocarboxylic acid composed of one aliphatic hydrocarbon group or hydrogen atom and one carboxy group. Examples of such fatty acids include higher fatty acids having 7 or more carbon atoms and lower fatty acids having 1 to 6 carbon atoms, and lower fatty acids are preferred from the viewpoint of long-term thermal stability. Examples of higher fatty acids include lauric acid, stearic acid, and myristic acid, with stearic acid being preferred from the viewpoint of compatibility with EVOH (A) and EVOH (B). Examples of lower fatty acids include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid and caproic acid; and unsaturated fatty acids such as acrylic acid and methacrylic acid. For these reasons, saturated fatty acids having 1 to 3 carbon atoms are preferred, and acetic acid is more preferred.

Metals constituting the fatty acid divalent metal salt (D) include alkaline earth metals such as magnesium and calcium, manganese (II), iron (II), cobalt (II), nickel (II) and copper (II). , zinc (II) and other divalent transition metals, preferably alkaline earth metals, and more preferably magnesium, from the viewpoint of thermal stability and the like.

In the resin composition of the present invention, the metal that constitutes the fatty acid divalent metal salt (D) may form a salt as a counter cation of the fatty acid ion that constitutes the fatty acid divalent metal salt (D). A salt may be formed as a counter cation of the alkoxide of (A) and/or EVOH (B).

When the resin composition of the present invention contains a fatty acid divalent metal salt (D), the lower limit of its content is In terms of metal ions, it may be, for example, 0.0001 parts by mass, preferably 0.001 parts by mass, and more preferably 0.002 parts by mass. By setting the content of the fatty acid divalent metal salt (D) to the above lower limit or more, thermal stability, trim recoverability, etc. can be enhanced, and a predetermined phase separation structure or gel fraction can be stably adjusted. In addition, trim recoverability can be enhanced by setting the content of the fatty acid divalent metal salt (D) to the above lower limit or more. On the other hand, the upper limit of the content may be, for example, 0.1 parts by mass, but is preferably 0.05 parts by mass, more preferably 0.03 parts by mass, and still more preferably 0.02 parts by mass. By setting the content of the fatty acid divalent metal salt (D) to the above upper limit or less, the thermal stability can be improved, and a predetermined phase separation structure or gel fraction can be stably adjusted. Moreover, by setting the content of the fatty acid divalent metal salt (D) to the above upper limit or less, the hue of the resin composition of the present invention and the resulting molded article can be improved, and yellowing can be suppressed.

When the resin composition of the present invention contains the fatty acid divalent metal salt (D), the fatty acid divalent metal salt (D) is preferably dispersed uniformly throughout the resin composition of the present invention.

(Mixing ratio)
The lower limit of the mass-based mixing ratio (A/B) of EVOH (A) and EVOH (B) may be, for example, 1.0, preferably 2.0, and more preferably 3.0. On the other hand, the upper limit of the mixing ratio (A/B) may be, for example, 20, preferably 11, more preferably 7. By setting the mixing ratio (A/B) of EVOH (A) and EVOH (B) within the above range, gas barrier properties, retort resistance, and the like can be further enhanced.

The lower limit of the mass-based mixing ratio ((A+B)/C) of the sum of EVOH (A) and EVOH (B) and PA (C) may be, for example, 0.67, preferably 1.5, and 2 .33 is more preferred, 4 is particularly preferred, and 5.67 is most preferred. By setting the mixing ratio ((A+B)/C) to the above lower limit or higher, it becomes easier to adjust the phase separation structure or the gel fraction to a predetermined one, and gas barrier properties, retort resistance, trim recoverability, etc. can be improved. . On the other hand, the upper limit of the mixing ratio ((A+B)/C) is preferably 99, more preferably 49, still more preferably 24, and particularly preferably 13.29. By setting the mixing ratio ((A+B)/C) to the above upper limit or less, the content ratio of PA (C) having a high melting point increases, and retort resistance can be further improved.

The lower limit of the mass-based mixing ratio (B/C) of EVOH (B) and PA (C) is preferably 0.053, more preferably 0.25. By setting the mixing ratio (B/C) to the above lower limit or higher, gas barrier properties, trim recoverability, and the like can be further enhanced. On the other hand, the upper limit of the mixing ratio (B/C) is preferably 19, more preferably 5.67. By making the mixing ratio (B/C) equal to or less than the above upper limit, retort resistance can be further enhanced.

Metal ion conversion substance amount (D/C) of fatty acid divalent metal salt (D) with respect to mass of PA (C), i.e., metal ion conversion substance amount of fatty acid divalent metal salt (D) per 1 g of PA (C) is preferably 3 μmol/g, more preferably 8 μmol/g, and even more preferably 12 μmol/g. By making the content ratio equal to or higher than the above lower limit, thermal stability and trim recoverability can be further enhanced. On the other hand, the upper limit of the content ratio (D/C) may be, for example, 250 μmol/g, preferably 150 μmol/g, more preferably 50 μmol/g, and even more preferably 35 μmol/g. By setting the content ratio (D/C) to the above upper limit or less, the thermal stability and hue can be improved.

(other ingredients)
The resin composition of the present invention further contains resins other than EVOH (A), EVOH (B) and PA (C) and additives other than fatty acid divalent metal salt (D) as other components. may

Examples of other resins include polyolefins. However, the lower limit of the ratio of the total amount of EVOH (A), EVOH (B) and PA (C) to all resin components in the resin composition of the present invention is preferably 90% by mass, more preferably 97% by mass, and 99% by mass. % by mass is more preferred. In this way, the resin component is substantially composed of only EVOH (A), EVOH (B) and PA (C), so that thermal stability, gas barrier properties, trim recoverability and retort resistance are improved. can be done.

Examples of the additives include known additives such as plasticizers, fillers, antiblocking agents, antioxidants, coloring agents, antistatic agents, ultraviolet absorbers, lubricants and desiccants. However, the content of the additive is preferably 2 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of the total amount of EVOH (A), EVOH (B) and PA (C). By reducing the content of the additive, thermal stability, gas barrier properties, trim recoverability and retort resistance can be improved.

Moreover, the resin composition of the present invention may contain a metal salt other than the fatty acid divalent metal salt (D). Examples of other metal salts include fatty acid monovalent metal salts and carboxylic acid metal salts other than fatty acid salts. As the fatty acid monovalent metal salt, a fatty acid alkali metal salt is preferably used, and as the fatty acid constituting the fatty acid monovalent metal salt, the fatty acid constituting the above-mentioned fatty acid divalent metal salt (D) is preferably used. Carboxylic acids constituting carboxylic acid metal salts other than fatty acid salts include aromatic carboxylic acids and polyvalent carboxylic acids, for example, aromatic carboxylic acids such as benzoic acid and 2-naphthoic acid; oxalic acid and malonic acid. , succinic acid, maleic acid, fumaric acid, malic acid, glutaric acid, adipic acid, pimelic acid and other aliphatic dicarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids; citric acid, isocitric acid, aconite tricarboxylic acids such as acids; tetravalent carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid and ethylenediaminetetraacetic acid; citric acid, isocitric acid, tartaric acid, malic acid, mucic acid, tartronic acid, citramaric acid hydroxycarboxylic acids; ketodicarboxylic acids such as oxaloacetic acid, mesooxalic acid, 2-ketoglutaric acid and 3-ketoglutaric acid; and amino acids such as glutamic acid, aspartic acid and 2-aminoadipic acid. When the resin composition of the present invention contains a metal salt other than the fatty acid divalent metal salt (D), the metal salt is preferably a fatty acid monovalent metal salt. When the resin composition of the present invention contains a metal salt other than the fatty acid divalent metal salt (D), the upper limit of the content is EVOH (A), EVOH (B) and PA (C) in the resin composition of the present invention. ) is preferably 0.03 parts by mass, more preferably 0.02 parts by mass, and still more preferably 0.018 parts by mass with respect to 100 parts by mass of the total amount of In addition, the total content of EVOH (A), EVOH (B), PA (C) and metal salt in the resin composition of the present invention in a dry state is preferably 99% by mass or more, and is 99.9% by mass. % or more may be more preferable, and 99.99% by mass or more may be even more preferable. When the resin composition of the present invention has such a composition, gas barrier properties and retort resistance can be improved by making it easier to achieve a good gel fraction, which will be described later.

(Phase separation structure, etc.)
The resin composition of the present invention, as shown in FIG. 1, has a phase separation structure having a sea phase 11, an island phase 12, and a third phase 13 surrounded by the island phase 12. The sea phase 11 is It is preferable that the resin composition contains EVOH (A), the island phase 12 contains EVOH (B), and the third phase 13 contains PA (C). By having such a phase separation structure, good retort resistance can be exhibited while maintaining good gas barrier properties.

The island phase is a phase that is dispersed and exists in the form of islands. The third phase is a phase that further exists in the form of islands within the island phase. One third phase may be present in one island phase, or a plurality of third phases may be present. Moreover, the third phase may not be completely surrounded by the island phase, and there may be an island phase that does not surround the third phase.

The shapes of the island phase and the third phase are not particularly limited, and may be circular, elliptical, or other irregular shapes. Among them, a circular shape and an elliptical shape are preferable, and an elliptical shape is particularly preferable. When the resin composition is extrusion molded, injection molded, or the like, the island phase and the third phase are presumed to form an elliptical shape extending in the extrusion direction or the like.

In the resin composition of the present invention, the proportion of EVOH (A) in the sea phase is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. It may be 100% by mass. The proportion of EVOH (B) in the island phase is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. good too. Note that the third phase is not taken into account in calculating the proportion of the island phase component. Furthermore, the proportion of PA (C) in the third phase is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. may When the ratio of EVOH (A), EVOH (B), and PA (C) in each phase is within the above range, good gas barrier properties and retort resistance can be exhibited when the above-described phase separation structure is formed. Therefore, it is preferable. For example, if the above range is satisfied, the sea phase and the island phase may contain PA (C), and the third phase may contain EVOH (A) or EVOH (B), The ratio can be measured by Nano-IR analysis or TEM observation described in Examples.

In the resin composition of the present invention, the lower limit of the average dispersed particle size of the third phase is preferably 0.05 μm. On the other hand, the upper limit is preferably 1 μm, more preferably 0.5 μm or less, even more preferably 0.3 μm or less. Here, the average dispersed particle size is calculated by averaging the sizes of 100 third phases in the field of view when observing an arbitrary cut surface of the resin composition of the present invention with an electron microscope. Point. When the third phase has a shape other than a circle such as an ellipse, the value of the minor axis is used for calculation. When the average dispersed particle size is within the above range, good retort resistance is exhibited while maintaining high barrier properties, which is preferable.

(Gel fraction)
The gel in the gel fraction defined in another embodiment of the present invention is presumed to be a reaction product of EVOH and PA (C), the resin composition is dissolved in a good solvent for EVOH, PA (C ) is dissolved in the good solvent. However, this insoluble matter does not include inorganic insoluble matter such as fillers. Here, a good solvent for EVOH means a solvent in which EVOH is completely dissolved under predetermined conditions, and a good solvent for PA(C) means a solvent in which PA(C) is completely dissolved under predetermined conditions. . A good solvent for EVOH is a mixed solvent of water (45% by mass)/propanol (55% by mass). Good solvents for PA(C) include 2,2,2-trifluoroethanol. The gel fraction is measured after completely dissolving EVOH and PA(C), and for example, the conditions described in Examples are applied. The conditions described in the examples can be suitably adopted, for example, when the content of insoluble inorganic matter in the resin composition in a dry state is less than 0.1% by mass. When the insoluble content of inorganic substances in the resin composition is 0.1% by mass or more, for example, by obtaining the mass of inorganic substances in the insoluble content obtained by the method described in the examples, the insoluble content other than inorganic substances can be obtained to calculate the gel fraction. The gel fraction is calculated by the following formula (1).
Gel fraction (%) = 100 x mass of insoluble matter / mass of resin composition (1)

The lower limit of the gel fraction in the present invention is 0.5%, preferably 0.75%, more preferably 1%. On the other hand, the upper limit of the gel fraction is 20%, preferably 15%, more preferably 10%. By setting the gel fraction within the above range, gas barrier properties and retort resistance can be improved. Further, by setting the gel fraction to 0.5% or more, the ratio of the reaction product of EVOH and PA(C) becomes sufficient, and appearance defects (voids, etc.) after heat treatment tend to be reduced. On the other hand, by setting the gel fraction to 20% or less, problems in the production process such as adhesion of the reaction product of EVOH and PA (C) to the screw, and deterioration of thermal stability during film formation can be suppressed. can be done.

(Means for adjusting phase separation structure or gel fraction)
The phase separation structure or gel fraction can be adjusted, for example, by adjusting the mixing ratio and kneading conditions of EVOH (A), EVOH (B) and PA (C). Specific methods for adjusting the kneading conditions include, for example, when using a single-screw extruder, adjusting the resin residence time by adjusting the shape and groove depth of the screw, adjusting the shear viscosity, and the like. be done. As the screw shape, for example, a full flight screw, a barrier screw, or the like can be used. In order to adjust the kneading strength, a screw having a Maddock or Dulmage shape may be used. Additionally, the screw speed may be adjusted to increase the shear rate. Moreover, a twin-screw extruder may be used from the viewpoint of easily changing the screw shape. In the case of using a twin-screw extruder, a method of adjusting the length of the kneading disk can be used to adjust the kneading strength.

When a single-screw extruder is used, as a specific kneading condition, for example, the lower limit of the shear rate r in the weighing section in the melt extruder calculated from the following formula (2) is preferably 10 sec ^-1 , and 15 sec ^-1 . More preferably, 20 sec ⁻¹ is particularly preferred. Further, the upper limit of the shear rate r is preferably 100 sec ^-1 , more preferably 95 sec ^-1 , and particularly preferably 90 sec ^-1 . If kneading is performed below the above lower limit, the mixing state of EVOH (A), EVOH (B) and PA (C) is poor, and it tends to become difficult to form the above-mentioned phase separation structure, and the gel fraction tends to decrease. Retortability may deteriorate. If kneading is performed above the above upper limit, EVOH (A), EVOH (B), and PA (C) will be mixed too much, making it difficult to form the above-described phase separation structure, and the gel fraction will tend to increase. Stability may deteriorate.

In formula (2), D is the cylinder diameter (cm), N is the screw rotation speed (rpm), h is the groove depth of the metering portion (cm), and r is the shear rate (sec ⁻¹ ).

Although the shape of the resin composition of the present invention is not particularly limited, it is usually in the form of pellets. Moreover, the resin composition of the present invention is usually a dry product. The water content of the resin composition of the present invention may be, for example, 10% by mass or less, 1% by mass or less, or 0.1% by mass or less. The resin composition of the present invention can be suitably used as a melt molding material such as a packaging material.

<Method for producing resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and known apparatuses and methods may be applied. For example, a production method comprising a step of dry blending EVOH (A), EVOH (B) and PA (C) and a step of melt-kneading the mixture obtained by the dry blending; or EVOH (A) and EVOH (B ) and a step of melt-kneading the resulting mixture of EVOH (A) and EVOH (B) with PA (C). Among them, in order to achieve the above-mentioned phase separation structure or gel fraction and further improve thermal stability, gas barrier property and retort resistance, EVOH (A), EVOH (B) and PA (C) are dry blended. and a step of melt-kneading the mixture obtained by the above dry blending is preferred.

The EVOH (A), EVOH (B) and PA (C) used in the dry blending step and the melt-kneading step are usually pellets. When the fatty acid divalent metal salt (D) is contained in these pellets, the pellets are immersed in or brought into contact with a pre-prepared aqueous solution containing the fatty acid divalent metal salt (D) for a sufficient time, for example, 1 second to 1 day. be able to. Moreover, in the melt-kneading step, melt-kneading can also be performed together with a preliminarily prepared fatty acid divalent metal salt (D) or an aqueous solution containing it.

In addition, melt-kneading can be performed by well-known apparatuses, such as a single-screw extruder and a twin-screw extruder. Moreover, in each melt-kneading step, the resin composition of the present invention can be obtained as pellets by melt-extrusion and pelletizing with a single-screw extruder, a twin-screw extruder, or the like.

<Method for producing molded article, etc. and molded article>
The molded article of the present invention comprises the resin composition of the present invention described above. The molded article of the present invention is usually a melt-molded article of the resin composition of the present invention. Further, it contains EVOH (A), EVOH (B) having a melting point TmB lower than the melting point TmA of EVOH (A), and PA (C). A molded article having a difference (TmA-TmB) from the melting point TmB of 10°C or more and a gel fraction of 0.5% or more and 20% or less is also the molded article of the present invention. Further, the method for producing a molded article of the present invention comprises the step of melt-molding the resin composition of the present invention.

That is, the resin composition of the present invention described above can be formed into molded articles such as films, containers, and other packaging materials (for foods, pharmaceuticals, etc.) by melt molding. When performing melt molding, the resin composition of the present invention may be melt molded, or EVOH (A), EVOH (B) and PA (C) may be dry blended and directly melt molded. The resin composition of the present invention has both good gas barrier properties and retort resistance, as well as good thermal stability and trim recoverability. For this reason, a molded article such as a film, which is a melt-molded article of the resin composition of the present invention, is suitable for use as a retort packaging material or a boiling packaging material. Note that the term "film" does not particularly limit the thickness, but is a concept that also includes what is called a "sheet".

Moreover, it is good also as a molded article which secondary-processed the molded object (film etc.) of this invention. Examples of secondary processed products of such films include retort pouches, thermoformed containers, lids for thermoformed containers, food packaging containers such as shrink containers, and other packaging containers. When the molded article of the present invention is a film, the film may be a single layer or multiple layers, and contains a hydrophobic thermoplastic resin for the purpose of preventing deterioration of the gas barrier performance of the resin composition due to moisture. It is preferably used as a multilayer structure with layers.

Examples of the hydrophobic thermoplastic resin include polyolefin resins (polyethylene resin, polypropylene resin, etc.), grafted polyolefin resins graft-modified with unsaturated carboxylic acids or their esters, halogenated polyolefin resins, and ethylene-vinyl acetate copolymer resins. , ethylene-acrylic acid copolymer resin, ethylene-acrylate copolymer resin, polyester resin, polyamide resin, polyvinyl chloride resin, polyvinylidene chloride resin, acrylic resin, polystyrene resin, vinyl ester resin, ionomer, polyester elastomer , polyurethane elastomers, aromatic or aliphatic polyketones, and the like. Among them, polyolefin resins are preferable, and polyethylene resins and polypropylene resins are more preferable in terms of mechanical strength and moldability.

In addition to these resins, paper, metal foil, woven fabric, non-woven fabric, metallic cotton strips, wooden surfaces, and multilayer structures combined with aluminum or silica vapor deposition may also be used.

As the layer structure of the multilayer structure, the layer obtained from the resin composition of the present invention is F, the layer made of a hydrophobic thermoplastic resin is A, and the hydrophobic thermoplastic resin is modified with an unsaturated carboxylic acid or a derivative thereof. When a layer composed of is represented by MA, the following layer configurations can be exemplified. In the layer structure, the layer on the left side is the outer layer (the side exposed to the external environment). The layer MA, which consists of a hydrophobic thermoplastic resin modified with an unsaturated carboxylic acid or a derivative thereof, is used both as an adhesive resin layer and as an outer layer.
2 layers MA/F
3 layers A/MA/F, MA/F/MA, F/MA/F, A/F/A
4 layers A/MA/F/MA, MA/F/MA/F
5 layers F/MA/A/MA/F, A/MA/F/MA/A
MA/F/MA/F/MA, A/MA/F/MA/F
A/F/A/MA/A
6 layers A/MA/F/MA/A/MA
7 layers A/MA/F/MA/F/MA/A

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples shown below. In addition, the methods of measurement, calculation and evaluation were in accordance with the following methods.

(1) Melting point Using a differential scanning calorimeter "Q2000" manufactured by TA Instruments, the melting point was determined from the peak temperature measured by heating from 30°C to 250°C at a rate of 10°C/min.

(2) Amount of divalent metal ions 0.5 g of dry EVOH pellets was added to a Teflon (registered trademark) pressure vessel manufactured by Actac, and 5 mL of nitric acid for precision analysis manufactured by Wako Pure Chemical Industries, Ltd. was added. After left for 30 minutes, the container was covered with a cap lip with a rupture disk, and decomposed at 150°C for 10 minutes and then at 180°C for 10 minutes in a microwave high-speed decomposition system "Speedwave MWS-2" manufactured by Actac. processed. If the dry EVOH pellets were insufficiently decomposed, the processing conditions were adjusted accordingly. After diluting with 10 mL of ion-exchanged water, all the liquid was transferred to a 50 mL volumetric flask, and ion-exchanged water was added to a constant volume to obtain a decomposition solution.
The above decomposed solution was quantitatively analyzed at each observation wavelength shown below using an ICP emission spectrometer "Optima 4300 DV" manufactured by PerkinElmer Japan Co., Ltd. to quantify the amount of each divalent metal ion.
Mg: 285.213 nm
Ca: 317.933 nm

(3) TEM Observation A resin composition (pellet) and a monolayer film were embedded in an epoxy resin, and transverse sections were prepared with an ultramicrotome. The obtained cross section was brought into contact with a 5% phosphotungstic acid aqueous solution for 5 minutes, dried, and then observed with a transmission electron microscope (TEM) "JEM2100" manufactured by JEOL Ltd. at a magnification of 5000 times. From the TEM image, a sea-island structure is observed if it has the above-described phase separation structure having a sea phase, an island phase and a third phase, and the observed particle diameter (short diameter of the third phase) is 0.05 μm or more. Those having a particle size of less than 0.05 μm were regarded as finely dispersed. Incidentally, the "sea-island structure" in this embodiment means that it has the above-described phase separation structure and includes EVOH (A) as the sea phase, EVOH (B) as the island phase, and PA (C) as the third phase. represents something. In the "finely dispersed" ones, no additional phase was observed within the dispersed phase. A TEM image of the single layer film obtained in Example 1 is shown in FIG. 2, and a TEM image of the single layer film obtained in Comparative Example 4 is shown in FIG.

(4) Gel fraction Using a single-screw extruder (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight), A monolayer film having a thickness of 20 μm was produced from the resin composition pellets obtained in the comparative example. Extrusion conditions are as shown below.
Extrusion temperature: 240°C
Dice width: 30cm
Take-up roll temperature: 80°C
Screw rotation speed: 45 rpm
Take-up roll speed: 3.4 m/min The prepared monolayer film having a thickness of 20 μm was dried in a vacuum dryer at 60° C. for 12 hours, cut out, and the mass was measured (W1). 1 part by mass of the single layer film was immersed in 100 parts by mass of a mixed solvent of water (45% by mass) / propanol (55% by mass), dissolved by heating at 75 ° C. for 8 hours, and then applied to a metal mesh (mesh number: 100). The insoluble matter was collected with a filter to obtain a filter cake. The resulting filter cake was dried in a vacuum dryer at 60° C. for 12 hours. Then, 1 part by mass of the filter cake was immersed in 100 parts by mass of 2,2,2-trifluoroethanol and dissolved at 50° C. for 8 hours. , The obtained insoluble matter was dried in a vacuum dryer at 60°C for 12 hours, and then the mass was measured (W2). A gel fraction (G) (%) was calculated by the following formula.
Gel fraction (G) (%) = 100 × mass of insoluble matter after drying (W2) / mass of 20 µm monolayer film after drying (W1)

(5) OTR (oxygen transmission rate)
Monolayer films having a thickness of 20 μm obtained in Examples and Comparative Examples were manufactured by MOCON INC. JIS K 7126 under the conditions of temperature 20 ° C. and humidity 65% RH using an oxygen transmission rate measuring device "OX-TRAN 2/20 type" (detection limit value 0.01 mL / 20 μm / m ² / day / atm) manufactured by It was measured according to the method described in (isobaric method). The oxygen barrier properties were determined according to the following criteria. If the judgment is A to B, the gas barrier property is good.
Judgment: Criteria A: less than 0.25 B: 0.25 or more and less than 0.45 C: 0.45 or more (unit: mL 20 µm/m ² day atm)

(6) Retort resistance Monolayer films with a thickness of 20 μm obtained in Examples and Comparative Examples, biaxially oriented nylon 6 films (“Emblem ONBC” manufactured by Unitika, thickness 15 μm) and unoriented polypropylene films (Mitsui Chemicals Tocello Co., Ltd.) "Tohcello CP" (thickness 50 μm) manufactured by the company was cut into A4 size, and a dry lamination adhesive was applied to both sides of the single-layer film. Lamination was performed and dried at 80° C. for 3 minutes to obtain a transparent laminate film consisting of 3 layers. As the adhesive for dry laminating, an adhesive using "Takelac A-520" manufactured by Mitsui Chemicals, Inc. as a main agent, "Takenate A-50" manufactured by Mitsui Chemicals, Inc. as a curing agent, and ethyl acetate as a diluent was used. The adhesive was applied in an amount of 4.0 g/m ² and cured at 40° C. for 3 days after lamination.

Using the laminate film obtained above, a pouch having internal dimensions of 12 cm×12 cm and having its four sides sealed was produced. The content was water. This was subjected to retort treatment at 120° C. for 120 minutes using a retort device (High temperature and high pressure cooking sterilization tester “RCS-40RTGN” manufactured by Hisaka Seisakusho Co., Ltd.). After the retort treatment, surface water was wiped off and the film was allowed to stand for one day in a room of constant temperature and humidity at 20°C and 65% RH, and then the appearance characteristics were evaluated as evaluation of retort resistance. When the evaluation is from A to C, the retort resistance is good.
Judgment: Criteria A: No whitening B: Striped whitening observed C: Slightly whitened D: Whitened

(7) Thermal stability 1 (long-run property, viscosity stability)
Using a single-screw extruder (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight), resins obtained in Examples and Comparative Examples A film was made from the composition for 8 hours continuously. Extrusion conditions are as shown below.
Extrusion temperature: 240°C
Dice width: 30cm
Take-up roll temperature: 80°C
Screw rotation speed: 40 rpm
Take-up roll speed: 3.1 m/min

After 8 hours from the start of film production, a film of 10 cm×10 cm was sampled, and the number of particles having a size of 100 μm or more was visually counted. Based on the number of spots, thermal stability was determined as follows.
Judgment: Criteria A: 50 pieces/100 cm ² or less B: More than 50 pieces/100 cm ² and 100 pieces/100 cm ² or less C: More than 100 pieces/100 cm ²

(8) Thermal stability 2 (long-run property, viscosity stability)
Torque change was measured when 6.5 g of the resin compositions obtained in Examples and Comparative Examples were kneaded at 100 rpm and 230° C. using “Thermo HAAKE MiniLab Rheomex CTW5” manufactured by Thermo Fisher Scientific. The torque was measured 5 minutes after the start of kneading, and the time until the torque value became 1.5 times or 0.5 times was measured. A longer time indicates less change in viscosity and better thermal stability. Thermal stability was determined according to the following criteria. The thermal stability is good when the judgment is from A to D.
Judgment: Criteria A: 40 minutes or more B: 30 minutes or more and less than 40 minutes C: 20 minutes or more and less than 30 minutes D: 10 minutes or more and less than 20 minutes E: Less than 10 minutes

(9) Trim recoverability A recovered material was produced and pelletized repeatedly by the following method, and the amount of adhering to the screw was measured as the trim recoverability.
(Manufacturing of Collected Materials)
Using PP "Novatec EA7AD" manufactured by Japan Polypropylene Corporation as the outermost layer, resin compositions obtained in Examples and Comparative Examples as the innermost layer, and "Modic AP P604V" manufactured by Mitsubishi Chemical Corporation as the adhesive resin layer, feed Polyolefin layer/adhesive resin layer/resin composition layer/adhesive resin layer/polyolefin layer=200 μm/20 μm/20 μm/20 μm/200 μm were co-extruded using a block die to produce a multi-layer film. Each resin was supplied to the feed block using a 32 mmφ extruder for the polyolefin layer, a 20 mmφ extruder for the adhesive resin layer, and a 20 mmφ extruder for the resin composition layer, and the extrusion temperature was 240°C for each resin. , the die section, and the feed block section were also performed at 230°C. Subsequently, the obtained multilayer film was pulverized with a pulverizer having a mesh diameter of 8 mmφ to obtain a recovered material. The mass ratio of the obtained recovered material was PP/EVOH/adhesive resin=85.9/5.5/8.6.
(repeated pelletization)
Using the masterbatch 1 (MB1) described in the example of International Publication No. 2011/136287 as a recovery aid, the mixture of 10.3 kg obtained by dry blending at a mass ratio of recovered material/recovery aid = 100/3 was melt-kneaded at an extrusion temperature of 230° C. and a discharge rate of 6 kg/h using a 25 mmφ co-rotating twin-screw extruder (“Laboplastomill” manufactured by Toyo Seiki Seisakusho Co., Ltd.) and then pelletized. Subsequently, the obtained pellets were dried in a hot air dryer at 80° C. for 1 hour, and then extruded at a temperature of 230° C. using a 25 mmφ co-rotating twin-screw extruder (“Laboplastomill” manufactured by Toyo Seiki Seisakusho Co., Ltd.). , and pelletized after melt-kneading at a discharge rate of 6 kg/h. Further, drying and pelletization in the same manner as described above were repeated three times.
(Measurement of screw adhesion amount)
After pelletizing a total of 5 times repeatedly as described above, 0.5 kg of LDPE ("Novatec LD LA320" manufactured by Japan Polyethylene Co., Ltd.) was subsequently added and pelletized. After the LDPE had completely flowed, the operation was stopped, the screw was taken out, the screw deposits were recovered, and the mass of the obtained screw deposits was weighed. The screw deposits increase as the resin composition deteriorates, and form gels and pimples that degrade the appearance of the molded product. The recoverability of the trim was determined according to the following criteria. The grades A to C indicate good trim recoverability.
Judgment: Criteria A: 200 g or less B: More than 200 g and less than 400 g C: More than 400 g and less than 600 g D: More than 600 g

(10) Hue The multilayer film produced by the method described in (6) Retort resistance was wound around a paper tube, and the degree of coloration of the film end surface was visually evaluated according to the following criteria.
Judgment: Standard A: No coloring B: Slightly yellowed C: Yellowed

[Example 1]
72 parts by mass of "L171B" (ethylene unit content 27 mol%, MFR 4.0 g/10 min, melting point 191 ° C.) manufactured by Kuraray Co., Ltd. as EVOH (A), and "E105B" (ethylene 18 parts by mass of a unit content of 44 mol%, MFR 13 g/10 min, melting point of 165 ° C.), and 10 parts by mass of nylon 6 ("UBE NYLON SF1018A" manufactured by Ube Industries, Ltd., melting point of 220 ° C.) as PA (C). After each pellet was dry-blended so as to form a mixture, it was supplied to a twin-screw extruder “TEX30α” (screw diameter: 30 mm) manufactured by The Japan Steel Works, Ltd. Further, in the twin-screw extruder, an aqueous magnesium acetate solution having a concentration of 1.5 g / L is added as an aqueous solution of fatty acid divalent metal salt (D) with a liquid addition pump, and downstream of the addition, a screw configuration Using a screw whose forward kneading disk has L (screw length) / D (screw diameter) = 3, melt extrusion is performed under the conditions of a melt temperature of 220 to 230 ° C. and an extrusion rate of 20 kg / hr. rice field. Then, the extruded strand was cooled and solidified in a cooling bath, and then cut to obtain resin composition pellets of Example 1.

Using a single screw extruder (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight), a thickness of 20 μm is extruded from the resin composition pellets. A monolayer film was produced. Extrusion conditions are as shown below.
Extrusion temperature: 240°C
Dice width: 30cm
Take-up roll temperature: 80°C
Screw rotation speed: 45 rpm
Take-up roll speed: 3.4 m/min

[Examples 2 to 27]
The types and blending amounts of EVOH (A), EVOH (B) and PA (C) and the type of fatty acid divalent metal salt (D) are as shown in Table 1, and the fatty acid divalent metal salt ( Resin composition pellets and monolayer films of Examples 2 to 27 were prepared in the same manner as in Example 1, except that the concentration of the aqueous solution of the fatty acid divalent metal salt (D) was adjusted so that the content of D) was obtained. obtained respectively.

[Example 28]
As EVOH (A), 72 parts by mass of "L171B" (ethylene unit content 27 mol%, MFR 4.0 g/10 min, melting point 191 ° C.) manufactured by Kuraray Co., Ltd., and as EVOH (B), "E105B" manufactured by Kuraray Co., Ltd. 18 parts by mass of (ethylene unit content 44 mol%, MFR 13 g/10 min, melting point 165 ° C.), and 10 mass parts of nylon 6 ("UBE NYLON SF1018A" manufactured by Ube Industries, Ltd., melting point 220 ° C.) as PA (C) Part, magnesium acetate tetrahydrate as fatty acid divalent metal salt (D) is 2.08 μmol / g in terms of metal atom with respect to the total amount of EVOH (A), EVOH (B) and PA (C) After dry blending each pellet, a single screw extruder (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: Maddock and Dharmage A single layer film having a thickness of 20 μm was produced using a screw. Extrusion conditions are as shown below.
Extrusion temperature: 240°C
Dice width: 30cm
Take-up roll temperature: 80°C
Screw rotation speed: 45 rpm
Take-up roll speed: 3.4 m/min

[Example 29]
In Example 1, the screw during the production of resin composition pellets was changed to a screw having a forward kneading disk having L (screw length) / D (screw diameter) = 1.5. A resin composition pellet was obtained in the same manner as in Example 1. Then, using a single-screw extruder (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: screw with Maddock and Dalmage), a thickness of 20 μm A monolayer film was produced. Extrusion conditions are as shown below.
Extrusion temperature: 240°C
Dice width: 30cm
Take-up roll temperature: 80°C
Screw rotation speed: 45 rpm
Take-up roll speed: 3.4 m/min

[Comparative Example 1]
Resin composition pellets and a single layer film were obtained in the same manner as in Example 1, except that the extrusion conditions during the single layer film formation in Example 1 were as follows.
Extrusion temperature: 240°C
Dice width: 30cm
Take-up roll temperature: 80°C
Screw rotation speed: 90 rpm
Take-up roll speed: 6.8m/min

[Comparative Example 2]
In Example 1, the screw during the production of resin composition pellets was changed to a screw having a forward kneading disk having L (screw length) / D (screw diameter) = 6. A resin composition pellet and a monolayer film were obtained in the same manner as above.

[Comparative Examples 3 to 5, 7]
The types and blending amounts of EVOH (A), EVOH (B) and PA (C) and the type of fatty acid divalent metal salt (D) are as shown in Table 1, and the fatty acid divalent metal salt ( Resin composition pellets and monolayers of Comparative Examples 3 to 5 and 7 were prepared in the same manner as in Example 1 except that the concentration of the aqueous solution of fatty acid divalent metal salt (D) was adjusted so that the content of D) was adjusted. A film was obtained for each.

[Comparative Example 6]
A single layer film was produced in the same manner as in Example 28, except that a full flight was used as the screw of the single screw extruder for molding the single layer film.

[Comparative Example 8]
An autoclave was charged with 60 kg of ε-caprolactam, 1.2 kg of water, and octadecylamine in an amount of 6.78 meq per mol of ε-caprolactam. After the reaction was carried out under pressure for 1 hour, the pressure was released and the pressure was reduced to 180 Torr, and the reaction was carried out for 2 hours. Then, nitrogen was introduced to return the pressure to normal pressure. The unreacted monomer was removed by extraction with boiling water and dried to obtain PA(C). The resulting PA(C) had an MFR (load of 2160 g at 230°C) of 2.5 g/10 minutes and a melting point of 220°C.
As EVOH (A), 49 parts by mass of "F171B" (ethylene unit content 32 mol%, MFR 3.7 g/10 min, melting point 183 ° C.) manufactured by Kuraray Co., Ltd., and as EVOH (B), "E105B" manufactured by Kuraray Co., Ltd. 21 parts by mass of (ethylene unit content 44 mol%, MFR 13 g/10 min, melting point 165 ° C.), 30 parts by mass of PA (C) produced above, and magnesium acetate tetrahydrate as fatty acid divalent metal salt (D) After dry blending each pellet so that the total amount of EVOH (A), EVOH (B) and PA (C) is 2.0 μmol / g in terms of metal atoms, Toyo Seiki Seisakusho Co., Ltd. Supply to a screw extruder (screw diameter (D) 40 mm, L / D = 26, screw configuration: full flight, screw rotation speed 40 rpm), extruder temperature 230 ° C., die temperature 250 ° C., resin temperature 245 ° C. After melt extrusion, the strand was cooled and solidified in a cooling bath and then cut to obtain resin composition pellets. The resin composition pellets were supplied to a single-screw extruder manufactured by Toyo Seiki Seisakusho Co., Ltd. (screw diameter (D) 40 mm, L/D = 26, screw configuration: full flight, screw rotation speed 40 rpm) equipped with a T die. , an extruder temperature of 230°C, a die temperature of 250°C, and a resin temperature of 245°C to prepare a single-layer film.

[Comparative Example 9]
In the compounding ratio of Comparative Example 8, 68 parts by mass of "F171B" manufactured by Kuraray Co., Ltd. as EVOH (A), 17 parts by mass of "E105B" manufactured by Kuraray Co., Ltd. as EVOH (B), and PA synthesized above (C ) is 15 parts by mass, and magnesium acetate tetrahydrate as a fatty acid divalent metal salt (D) is 2.3 μmol in terms of a metal atom with respect to the total amount of EVOH (A), EVOH (B) and PA (C). /g was used, but the same evaluation was performed.

In Table 1, "F171B" in EVOH (A), and "E171B", "H171B" and "C109B" in EVOH (B) are all EVOH of Kuraray Co., Ltd. The ethylene unit content, MFR (210° C., 2160 g load) and melting point of each EVOH are as described below.
・L171B
Ethylene unit content 27 mol%, MFR 4.0 g/10 min, melting point 191°C
・F171B
Ethylene unit content 32 mol%, MFR 3.7 g/10 min, melting point 183°C
・E105B
Ethylene unit content 44 mol%, MFR 13 g/10 min, melting point 165°C
・E171B
Ethylene unit content 44 mol%, MFR 3.3 g/10 minutes, melting point 165°C
・H171B
Ethylene unit content 38 mol%, MFR 3.4 g/10 min, melting point 172°C
・C109B
Ethylene unit content 35 mol%, MFR 21 g/10 min, melting point 177°C

"UBE NYLON 1024B", "UBE NYLON 1030B" and "UBE NYLON 7024B" in PA (C) in Table 1 are PAs manufactured by Ube Industries, Ltd. "Ny6" in Table 1 represents nylon 6, and "Ny6,12" represents nylon 6/12.

Each resin composition pellet and monolayer film obtained were evaluated by the above-described method. Table 2 shows the evaluation results. Table 2 also shows the mixing ratio (A/B, (A+B)/C, B/C, and D/C) of each component. In addition, in the columns of TEM observation and each evaluation in Table 2, "-" indicates that observation or evaluation was not performed.

As shown in Table 2, it can be seen that Examples 1 to 29 all have good gas barrier properties and retort resistance. On the other hand, none of Comparative Examples 1 to 9 had good gas barrier properties and retort resistance. Comparative Example 1 in which the number of screw revolutions was high and Comparative Example 2 in which a screw with high kneading strength was used were excessively kneaded, resulting in a high gel fraction and poor gas barrier properties and retort resistance. Comparative Example 3 containing no PA (C) is inferior in retort resistance. Comparative Example 4 containing no EVOH (B) and Comparative Example 5 using EVOH (B) having a small difference in melting point from EVOH (A) are inferior in gas barrier properties and retort resistance. In Comparative Example 6 in which a monolayer film was directly formed by dry blending and the kneading strength of the screw was not adjusted (not increased), kneading was insufficient, so the gel fraction was low and the gas barrier gas barrier Inferior in durability and retort resistance. Comparative Example 7, in which the PA (C) content is relatively high, has a high gel fraction and is inferior in gas barrier properties. Further, in Comparative Examples 8 and 9, since the degree of kneading was low, the gel fraction was a low value and the retort resistance was poor.

Among the examples, Example 21 in which the content of the fatty acid divalent metal salt (D) is low and Example 26 in which the content of the fatty acid divalent metal salt (D) is high are somewhat evaluated for thermal stability 2. Inferior. Example 27, in which the higher fatty acid divalent metal salt was used instead of the lower fatty acid divalent metal salt, was slightly inferior in trim recovery. In addition, Examples 25 and 26, in which the content of the fatty acid divalent metal salt (D) is high, have relatively low hue evaluations. That is, by containing a predetermined amount of the fatty acid divalent metal salt (D) and further containing a predetermined amount of the lower fatty acid divalent metal salt as the fatty acid divalent metal salt (D), thermal stability, trim recovery, and It can be seen that the hue is improved.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used as packaging materials, particularly retort packaging materials and boiling packaging materials.

11 Sea phase 12 Island phase 13 Third phase

Claims (15)

An ethylene-vinyl alcohol copolymer (A), an ethylene-vinyl alcohol copolymer (B) having a melting point TmB lower than the melting point TmA of the ethylene-vinyl alcohol copolymer (A), and a polyamide (C) and the difference (TmA-TmB) between the melting point TmA of the ethylene-vinyl alcohol copolymer (A) and the melting point TmB of the ethylene-vinyl alcohol copolymer (B) is 10° C. or more, and the gel fraction is A resin composition having a content of 0.5% or more and 20% or less. 2. The resin according to claim 1, wherein the mass-based mixing ratio (A/B) of the ethylene-vinyl alcohol copolymer (A) and the ethylene-vinyl alcohol copolymer (B) is 1.0 or more and 20 or less. Composition. Ethylene-vinyl alcohol copolymer (A) and ethylene-vinyl alcohol copolymer (B) total and polyamide (C) mixing ratio ((A + B) / C) based on mass is 0.67 or more and 99 or less A resin composition according to claim 1 or 2. 4. The ethylene-vinyl alcohol copolymer (B) and the polyamide (C) according to any one of claims 1 to 3, wherein the mass-based mixing ratio (B/C) is 0.053 or more and 19 or less. Resin composition. The resin composition according to any one of claims 1 to 4, wherein the polyamide (C) has a melting point TmC of 190°C or higher. Further containing a fatty acid divalent metal salt (D), the fatty acid divalent metal relative to the total amount of 100 parts by mass of the ethylene-vinyl alcohol copolymer (A), the ethylene-vinyl alcohol copolymer (B) and the polyamide (C) The resin composition according to any one of claims 1 to 5, wherein the content of the salt (D) in terms of metal ions is 0.001 parts by mass or more and 0.05 parts by mass or less. 7. The resin composition according to claim 6, wherein the amount (D/C) of the fatty acid divalent metal salt (D) in terms of metal ions with respect to the mass of the polyamide (C) is 3 μmol/g or more and 250 μmol/g or less. The resin composition according to any one of claims 1 to 7, which is in the form of pellets. A molded article made of the resin composition according to any one of claims 1 to 8. An ethylene-vinyl alcohol copolymer (A), an ethylene-vinyl alcohol copolymer (B) having a melting point TmB lower than the melting point TmA of the ethylene-vinyl alcohol copolymer (A), and a polyamide (C) and the difference (TmA-TmB) between the melting point TmA of the ethylene-vinyl alcohol copolymer (A) and the melting point TmB of the ethylene-vinyl alcohol copolymer (B) is 10° C. or more, and the gel fraction is A molded article having a content of 0.5% or more and 20% or less. The molded article according to claim 9 or 10, which is a film. 12. The molded article according to any one of claims 9 to 11, which is a retort packaging material or a boiling packaging material. A secondary processed product of the molded article according to any one of claims 9 to 12. A step of dry-blending an ethylene-vinyl alcohol copolymer (A), an ethylene-vinyl alcohol copolymer (B) and a polyamide (C), and a step of melt-kneading the mixture obtained in the dry-blending step. A method for producing a resin composition according to any one of claims 1 to 8. A method for producing a molded article, comprising the step of melt-molding the resin composition according to any one of claims 1 to 8.

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