DE102019002404A1 - PLASTIC COMPOSITION, FORM BODY, SECONDARY PRODUCT, METHOD FOR PRODUCING A PLASTIC COMPOSITION, AND METHOD FOR PRODUCING A MOLDED BODY - Google Patents

Abstract

The object is to provide a plastic composition having both good gas barrier properties and good resistance to prolonged heating, a molded article formed from this plastic composition, and a method for producing this plastic composition and the molded article. There is provided a plastic composition comprising: an ethylene-vinyl alcohol copolymer (A); an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and a polyamide (C); wherein the plastic composition has a phase separated structure having a sea phase, an island phase, and a third phase surrounded by the island phase; and wherein the sea phase comprises the ethylene-vinyl alcohol copolymer (A), the island phase comprises the ethylene-vinyl alcohol copolymer (B), and the third phase comprises the polyamide (C).

Description

TECHNICAL AREA

The present invention relates to a plastic composition, a molded article, a secondary article, a process for producing a plastic composition and a process for producing a molded article.

BACKGROUND OF THE INVENTION

Ethylene-vinyl alcohol copolymer (hereinafter abbreviated to "EVOH") is a plastic having excellent barrier properties against oxygen, odors and aromas. For this reason, EVOH is often used as packaging material of foods and the like.

However, EVOH has a low stretchability, so that it has the property that in its processing, gaps and cracks and the like easily occur. Therefore, in order to improve the extensibility, plastic compositions are used in which polyamide (hereinafter also abbreviated to "PA") is added to the EVOH depending on the application (see Patent Documents 1 and 2).

Furthermore, such packaging materials, after filling with contents such as e.g. Food, sometimes subjected to heating by hot water or steam (prolonged heating or boiling). However, if EVOH is heated with hot water or steam for a long time, there is the problem of white streaks or partial clouding (fading) that affects the appearance. In order to improve such fading, a plastic composition in which EVOH and PA are mixed in an appropriate ratio is used as a packaging material for heating (see Patent Document 3).

PREVIOUS TECHNICAL DOCUMENTS

TECHNICAL DOCUMENTS

• Patent Document 1: JP S58-129035A
• Patent Document 2: JP H04-202549A
• Patent Document 3: WO 2015/174396

OVERVIEW OF THE INVENTION

PROBLEM TO BE SOLVED BY THE INVENTION

Of the packaging material described above, good gas barrier properties are usually required to be able to store foods and the like for a long and safe time. However, when EVOH and PA are mixed, the gas barrier properties of the packaging material deteriorate, so that a packaging material is required which has better gas barrier properties and is also resistant to heating.

Furthermore, the demands placed on the appearance of packaging material also increase, and it is necessary to avoid the above-described fading, the retorting or prolonged heating (heating for a long time) packaging materials, the layers of plastic compositions with EVOH can be observed. Consequently, there is a need for plastic compositions that are resistant to retorting or prolonged heating, and in which the phenomenon of bleaching can be suppressed even with prolonged heating.

However, in the technology of the above-mentioned Patent Documents 1 and 2, the resistance to prolonged heating is not taken into consideration, so that good gas barrier properties and good resistance to prolonged heating can not be simultaneously attained. Further, also in the technology of the above-mentioned Patent Document 3, a higher level of both gas barrier properties and resistance to prolonged heating is required.

In view of this situation, it is an object of the present invention to provide a plastic composition as well as a molded article and a secondary product formed from this plastic composition, a process for producing this plastic composition and a process for producing the molded article with which both good gas barrier properties can be achieved a good resistance to prolonged heating can be achieved.

MEDIUM TO SOLVE THE PROBLEM

1. (1) Kunststoffzusammensetzung, aufweisend:
   • ein Ethylen-Vinylalkohol-Copolymer (A);
   • ein Ethylen-Vinylalkohol-Copolymer (B) mit einem Schmelzpunkt TmB unter dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymers (A); und
   • ein Polyamid (C);
   • wobei die Kunststoffzusammensetzung eine phasengetrennte Struktur mit einer Meerphase, einer Inselphase sowie einer von der Inselphase umgebene dritten Phase aufweist; und
   • wobei die Meerphase das Ethylen-Vinylalkohol-Copolymer (A) aufweist, die Inselphase das Ethylen-Vinylalkohol-Copolymer (B) aufweist, und die dritte Phase das Polyamid (C) aufweist;
2. (2) Kunststoffzusammensetzung gemäß (1), wobei die Differenz (TmA - TmB) zwischen dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymers (A) und dem Schmelzpunkt TmB des Ethylen-Vinylalkohol-Copolymers (B) mindestens 10°C beträgt;
3. (3) Kunststoffzusammensetzung, aufweisend:
   • ein Ethylen-Vinylalkohol-Copolymer (A);
   • ein Ethylen-Vinylalkohol-Copolymer (B) mit einem Schmelzpunkt TmB unter dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymers (A); und
   • ein Polyamid (C);
   • wobei die Differenz (TmA - TmB) zwischen dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymers (A) und dem Schmelzpunkt TmB des Ethylen-Vinylalkohol-Copolymers (B) mindestens 10°C beträgt; und
   • ein Gelanteil mindestens 0,5% und höchstens 20% beträgt;
4. (4) Kunststoffzusammensetzung gemäß einem von (1) bis (3), wobei das Mischungsverhältnis (A/B) des Ethylen-Vinylalkohol-Copolymers (A) und des Ethylen-Vinylalkohol-Copolymers (B), bezogen auf die Masse, mindestens 1,0 und höchstens 20 beträgt;
5. (5) Kunststoffzusammensetzung gemäß einem von (1) bis (4), wobei das Mischungsverhältnis ((A/B) / C) des Polyamid (C) zur Gesamtheit von Ethylen-Vinylalkohol-Copolymer (A) und Ethylen-Vinylalkohol-Copolymer (B), bezogen auf die Masse, mindestens 0,67 und höchstens 99 beträgt;
6. (6) Kunststoffzusammensetzung gemäß einem von (1) bis (5), wobei das Mischungsverhältnis (B/C) des Ethylen-Vinylalkohol-Copolymer (B) und des Polyamids (C), bezogen auf die Masse, mindestens 0,053 und höchstens 19 beträgt;
7. (7) Kunststoffzusammensetzung gemäß einem von (1) bis (6), wobei der Schmelzpunkt TmC des Polyamids (C) mindestens 190°C beträgt;
8. (8) Kunststoffzusammensetzung gemäß einem von (1) bis (7), ferner aufweisend ein fettsäurebasiertes zweiwertiges Metallsalz (D); wobei die auf Metallionen umgerechnete Inhaltsmenge des fettsäurebasierten zweiwertigen Metallsalz (D) relativ zur 100 Masseteilen der Gesamtmenge an Ethylen-Vinylalkohol-Copolymer (A), Ethylen-Vinylalkohol-Copolymer (B) und Polyamid (C) mindestens 0,001 Masseteile und höchstens 0,05 Masseteile beträgt;
9. (9) Kunststoffzusammensetzung gemäß (8), wobei die auf Metallionen umgerechnete Menge (D/C) des fettsäurebasierten zweiwertigen Metallsalzes (D) relativ zur Masse des Polyamids (C) mindestens 3 µmol / g und höchstens 250 µmol / g beträgt;
10. (10) Kunststoffzusammensetzung gemäß einem von (1) bis (9), wobei die Kunststoffzusammensetzung in Pelletform ist;
11. (11) Formkörper aus einer Kunststoffzusammensetzung gemäß einem von (1) bis (10);
12. (12) Formkörper, aufweisend:
    • ein Ethylen-Vinylalkohol-Copolymer (A);
    • ein Ethylen-Vinylalkohol-Copolymer (B) mit einem Schmelzpunkt TmB unter dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymer (A); und
    • ein Polyamid (C);
    • wobei der Formkörper eine phasengetrennte Struktur mit einer Meerphase, einer Inselphase sowie einer von der Inselphase umgebene dritten Phase aufweist; und
    • wobei die Meerphase das Ethylen-Vinylalkohol-Copolymer (A) aufweist, die Inselphase das Ethylen-Vinylalkohol-Copolymer (B) aufweist, und die dritte Phase das Polyamid (C) aufweist;
13. (13) Formkörper, aufweisend:
    • ein Ethylen-Vinylalkohol-Copolymer (A);
    • ein Ethylen-Vinylalkohol-Copolymer (B) mit einem Schmelzpunkt TmB unter dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymer (A); und
    • ein Polyamid (C);
    • wobei die Differenz (TmA - TmB) zwischen dem Schmelzpunkt TmA des Ethylen-Vinylalkohol-Copolymers (A) und dem Schmelzpunkt TmB des Ethylen-Vinylalkohol-Copolymers (B) mindestens 10°C beträgt; und
    • ein Gelanteil mindestens 0,5% und höchstens 20% beträgt;
14. (14) Formkörper gemäß einem von (11) bis (13), wobei der Formkörper eine Folie ist;
15. (15) Formkörper gemäß einem von (11) bis (14), wobei der Formkörper ein Verpackungsmaterial zum längeren Erhitzen oder ein Verpackungsmaterial zum Aufkochen ist;
16. (16) Sekundärerzeugnis eines Formkörpers gemäß einem von (11) bis (15);
17. (17) Verfahren zum Herstellen einer Kunststoffzusammensetzung gemäß einem von (1) bis (10), mit:
    • einem Schritt des Trockenmischens des Ethylen-Vinylalkohol-Copolymer (A), des Ethylen-Vinylalkohol-Copolymer (B) und des Polyamids (C), und
    • einem Schritt des Schmelzknetens der im Trockenmischschritt erhaltenen Mischung.
18. (18) Verfahren zum Herstellen eines Formkörpers, mit einem Schritt der Schmelzverformung der Kunststoffzusammensetzung gemäß einem von (1) bis (10).

In order to solve this problem, the present invention provides the below-described plastic composition, molded article, secondary product, and process for producing a plastic composition and process for producing a molded article:

1. (1) A plastic composition comprising:
   • an ethylene-vinyl alcohol copolymer (A);
   • an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and
   • a polyamide (C);
   • wherein the plastic composition has a phase separated structure having a sea phase, an island phase, and a third phase surrounded by the island phase; and
   • wherein the sea phase comprises the ethylene-vinyl alcohol copolymer (A), the island phase comprises the ethylene-vinyl alcohol copolymer (B), and the third phase comprises the polyamide (C);
2. (2) The plastic composition according to (1), wherein 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 at least 10 ° C;
3. (3) A plastic composition comprising:
   • an ethylene-vinyl alcohol copolymer (A);
   • an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and
   • a polyamide (C);
   • wherein 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 at least 10 ° C; and
   • a gel content is at least 0.5% and at most 20%;
4. (4) The plastic composition according to any one of (1) to (3), wherein the mixing ratio (A / B) of the ethylene-vinyl alcohol copolymer (A) and the ethylene-vinyl alcohol copolymer (B) by mass is at least 1 , 0 and at most 20;
5. (5) The plastic composition according to any one of (1) to (4), wherein the mixing ratio ((A / B) / C) of the polyamide (C) to the entirety of ethylene-vinyl alcohol copolymer (A) and ethylene-vinyl alcohol copolymer ( B), based on the mass, is at least 0.67 and at most 99;
6. (6) The plastic composition according to any one of (1) to (5), wherein the mixing ratio (B / C) of the ethylene-vinyl alcohol copolymer (B) and the polyamide (C) by mass is at least 0.053 and at most 19 ;
7. (7) The plastic composition according to any one of (1) to (6), wherein the melting point TmC of the polyamide (C) is at least 190 ° C;
8. (8) The plastic composition according to any one of (1) to (7), further comprising a fatty acid-based divalent metal salt (D); wherein the metal ion-converted content amount of the fatty acid-based divalent metal salt (D) relative to 100 parts by mass of the total of ethylene-vinyl alcohol copolymer (A), ethylene-vinyl alcohol copolymer (B) and polyamide (C) is at least 0.001 part by weight and at most 0.05 Mass parts is;
9. (9) The plastic composition according to (8), wherein the metal ion-converted amount (D / C) of the fatty acid-based divalent metal salt (D) relative to the bulk of the polyamide (C) is at least 3 μmol / g and at most 250 μmol / g;
10. (10) The plastic composition according to any one of (1) to (9), wherein the plastic composition is in pellet form;
11. (11) molded articles of a plastic composition according to any one of (1) to (10);
12. (12) Shaped body comprising:
    • an ethylene-vinyl alcohol copolymer (A);
    • an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and
    • a polyamide (C);
    • wherein the shaped body has a phase-separated structure having a sea phase, an island phase, and a third phase surrounded by the island phase; and
    • wherein the sea phase comprises the ethylene-vinyl alcohol copolymer (A), the island phase comprises the ethylene-vinyl alcohol copolymer (B), and the third phase comprises the polyamide (C);
13. (13) Shaped body comprising:
    • an ethylene-vinyl alcohol copolymer (A);
    • an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and
    • a polyamide (C);
    • wherein 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 at least 10 ° C; and
    • a gel content is at least 0.5% and at most 20%;
14. (14) The molded article according to any one of (11) to (13), wherein the molded article is a film;
15. (15) The molded article according to any one of (11) to (14), wherein the molded article is a prolonged heating packaging material or a packaging material for boiling;
16. (16) Secondary product of a molded article according to any one of (11) to (15);
17. (17) A process for producing a plastic composition according to any one of (1) to (10), comprising:
    • a step of dry blending the ethylene-vinyl alcohol copolymer (A), the ethylene-vinyl alcohol copolymer (B) and the polyamide (C), and
    • a step of melt-kneading the mixture obtained in the dry-mixing step.
18. (18) A method of producing a molded article, comprising a step of melt-molding the plastic composition according to any one of (1) to (10).

EFFECT OF THE INVENTION

The present invention provides a plastic composition as well as a molded article and a secondary article formed from this plastic composition, a process for producing the plastic composition, and a process for producing the molded article having both good gas barrier properties and good resistance to prolonged heating can be achieved.

list of figures

• 1 Fig. 3 is a diagram showing the separated phase structure of a plastic composition according to an embodiment of the invention.
• 2 Fig. 10 shows a TEM image of a single-layer film obtained with Embodiment 1 with phosphor tungsten dyeing.
• 3 Fig. 10 shows a TEM image of a single layer film obtained with Comparative Example 4 with phosphorus tungsten dyeing.

EMBODIMENTS OF THE INVENTION

Hereinafter, a plastic composition and a method for producing the same, a molded article and a method for producing the same, and a secondary article according to the present invention will be explained in detail. It should be noted that in the present invention, the gas barrier properties are judged by the oxygen barrier properties.

Plastic composition

A plastic composition according to one embodiment of the invention comprises an ethylene-vinyl alcohol copolymer (A) (hereinafter also abbreviated to "EVOH (A)"); an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of EVOH (A) (hereinafter also abbreviated as "EVOH (B)"); and a polyamide (C) (hereinafter abbreviated as "PA (C)"); wherein the plastic composition has a phase separated structure having a sea phase, an island phase, and a third phase surrounded by the island phase (hereinafter also abbreviated as "the phase separated structure"); and wherein the sea phase has the EVOH (A), the island phase has the EVOH (B), and the third phase has the PA (C).

Further, a plastic composition according to another embodiment of the invention comprises an EVOH (A), an EVOH (B) having a melting point TmB below the melting point TmA of the EVOH (A), and a polyamide (C); wherein the difference (TmA - TmB) between the melting point TmA of the EVOH (A) and the melting point TmB of the EVOH (B) is not more than 10 ° C, and a gel content is at least 0.5% and at most 20%.

Here, the melting points of the EVOH (A), the EVOH (B) and the PA (C) are measured values according to differential thermal analysis, with the melting peaks measured according to ISO 11357: 2013 being taken as melting points.

A plastic composition according to the one embodiment of the invention has both good gas barrier properties and resistance to prolonged heating because of the above-described composition and the phase-separated structure. Furthermore, with a plastic composition according to the invention, which preferably further comprises a certain amount of fatty acid-based divalent metal salt (D), good heat resistance, trim recoverability and resistance to prolonged heating can be achieved.

Further, the plastic composition according to the other embodiment of the invention achieves good gas barrier properties and resistance to prolonged heating at the same time due to the above-described composition and gel content. Furthermore, by preferably containing a certain amount of fatty acid-based divalent metal salt (D) in the plastic composition of the present invention, good stability, trim recoverability and resistance to prolonged heating can be attained at the same time.

Preferably, the plastic composition according to the invention has a melting point TmC of PA (C) of at least 190 ° C, and further comprises a fatty acid-based divalent metal salt (D), wherein the content of fatty acid-based divalent metal salt (D) is converted into metal ions relative to the total amount of EVOH ( A), EVOH (B) and PA (C) is at least 0.001 part by mass and at most 0.05 part by mass. In this case, the plastic composition of the present invention simultaneously has good stability, trim recoverability, and resistance to prolonged heating. The exact reason why this effect can be achieved is unclear, but the following is conceivable. By containing a certain amount of fatty acid-based divalent metal salt (D), good heat resistance is achieved. Further, by using both low melting point EVOH (B) and fatty acid based divalent metal salt (D), good trim recoverability is achieved. Further, by using high melting point PA (C) and two types of different melting point EVOH, good resistance to prolonged heating is achieved.

EVOH (A)

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

The EVOH (A) can usually be obtained by saponification of an ethylene-vinyl ester copolymer. In other words, the EVOH (A) is the product of saponification of a common ethylene-vinyl ester copolymer. The copolymerization of ethylene and vinyl ester and the saponification of ethylene-vinyl ester copolymers can be carried out by the known methods. A typical example of vinyl ester is vinyl acetate, however, another vinyl ester such as a vinyl ester of a fatty acid (eg, vinyl formate, vinyl propoxide, vinyl valiate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, and vinyl versatate) may be used.

The lower limit of the degree of saponification of the vinyl ester portion of the EVOH (A) is preferably 85 mol%, more preferably 90 mol%, still more preferably 96 mol%, particularly preferably 98 mol%, and most preferably 99 mol%. The fact that the degree of saponification is above this lower limit, for example, the gas barrier properties of the molding can be improved. Further, the upper limit of the degree of saponification may be 100 mol% or even 99.99 mol%.

The lower limit of the content of ethylene units in the EVOH (A) is preferably 5 mol%, more preferably 10 mol%, still more preferably 20 mol%, and most preferably 25 mol%. The upper limit of the content of ethylene units is preferably 70 mol%, more preferably 50 mol%, even more preferably 40 mol%, still more preferably 35 mol%, and most preferably 30 mol%. By having the content of ethylene units above this lower limit, the film or the like at high humidity can achieve good gas barrier properties as well as a good external appearance after heating. On the other hand, if the content of ethylene units is below the above upper limit, better gas barrier properties can be obtained with the film or the like. Further, with a content of ethylene units of the EVOH (A) in this range, the desired melting point TmA can also be set relatively easily.

To the extent not in contravention of the object of the present invention, the EVOH (A) may include units derived from other monomers besides ethylene, vinyl esters and saponification products thereof. If the EVOH (A) has such units derived from other monomers, then the content of these units derived from other monomers relative to the units of the whole structure is preferably not more than 30 mol%, more preferably not more than 20 mol%, still more preferably not more than 10 mol%, and more preferably not more than 5 mol%. If the EVOH (A) contains such units derived from other monomers, then its melting point can be adjusted by adjusting the content amount thereof. If the EVOH (A) contains such units derived from other monomers, then the lower limit thereof may be 0.05 mol% or even 0.10 mol%. Examples of such other monomers are unsaturated acids, e.g. Acrylic acid, methacrylic acid, crotonic acid and itaconic acid, and their anhydrides, salts and mono- or dialkyl esters; Nitriles, e.g. Acrylonitrile and methacrylonitrile; Amides, e.g. Acrylamide and methacrylamide; Olefin sulfonic acids such as e.g. Vinylsulfonic acid, arylsulfonic acid, methacrylic sulfonic acid and their salts; Vinylsilane compounds such as e.g. Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, and γ-methacryloxypropylmethoxysilane; Alkyl vinyl ether, vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like.

Further, the units derived from other monomers may also contain at least one of the structural units (I) indicated in the following general formula (I), the structural units (II) given in the following general formula (II), and structural Units (III) given in general formula (III) below. By having the EVOH (A) having such a structural unit, for example, a higher bending fatigue strength can be obtained in the obtained film or the like.

In the above general formula (I), R ¹ , R ² and R ³ independently denote a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having a carbon number of 3 to 10, or an aromatic hydrocarbon group having a carbon number from 6 to 10 or one hydroxyl group. Further, a pair of R ¹ , R ² and R ^{3 may} be connected to each other. In addition, a part or all of hydrogen atoms in the aliphatic hydrocarbon group having a carbon number of 1-10, the alicyclic hydrocarbon group having a carbon number of 3-10, and the aromatic hydrocarbon group having a Carbon number of 6 - 10 are replaced by a hydroxyl group, a carboxy group or a halogen atom.

In the above general formula (II), R ⁴ , R ⁵ , R ⁶ and R ⁷ independently denote a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having a carbon number of 3 to 10, an aromatic hydrocarbon group a carbon number of 6-10 or a hydroxyl group. Further, a pair of R ⁴ , R ⁵ , R ⁶ and R ^{7 may} be connected to each other. Further, a part or all of hydrogen atoms in the aliphatic hydrocarbon group having a carbon number of 1-10, the alicyclic hydrocarbon group having a carbon number of 3-10, and the aromatic hydrocarbon group having a carbon number of 6-10 may also be represented by a hydroxyl group, an alkoxy group , a carboxy group or a halogen atom.

In the above general formula (III), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently denote a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having a carbon number of 3 to 10, an aromatic hydrocarbon group a carbon number of 6-10 or a hydroxyl group. Further, a part or all of hydrogen atoms in the aliphatic hydrocarbon group having a carbon number of 1-10, the alicyclic hydrocarbon group having a carbon number of 3-10, and the aromatic hydrocarbon group having a carbon number of 6-10 may also be represented by a hydroxyl group, an alkoxy group , a carboxy group or a halogen atom. R ¹² and R ¹³ independently denote a hydrogen atom, a formyl group or an alkanoyl group having a carbon number of 2-10.

In the structural units (I), (II) and (III), as examples of the aliphatic hydrocarbon group having a carbon number of 1-10, alkyl groups and alkenyl groups can be cited, as examples of the alicyclic hydrocarbon group having a carbon number of 3-10, cycloalkyl groups and cycloalkenyl groups, and as examples of the aromatic hydrocarbon group having a carbon number of 6 to 10, there may be mentioned phenyl groups and the like.

In the structural unit (I), R ¹ , R ² and R ^{3 are} independently preferably hydrogen, methyl, ethyl, hydroxyl, hydroxymethyl and / or hydroxyethyl. Among them, in view of improving the ductility and the heat deformability of the plastic composition of the present invention independently, a hydrogen atom, a methyl group, a hydroxyl group and / or a hydroxymethyl group are preferable.

There is no limitation on the method by which the EVOH (A) is provided with the structural unit (I), and an example is a method of copolymerizing a monomer from which the structural unit (I) can be derived in the polymerization of ethylene with the vinylester. Examples of such monomers are alkenes such as propylene, butylene, pentene and hexene; and alkenes having an ester group or a hydroxyl group, such as 3-hydroxy-1-propene, 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-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-hydroxy-1 Hexene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene. Among them, in view of the copolymerization reaction and the gas barrier properties of the resulting film are propylene, 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, and 3,4-diacyloxy-1-butene preferable. It is preferable that the acyloxy is an acetoxy, and more specifically, 3-acetoxy-1-propene, 3-acetoxy-1-butene, 4-acetoxy-1-butene and 3,4-diacetoxy-1-butene are preferable. In the case of alkene with ester, in the saponification reaction, the above structural unit (I) is derived.

In the structural unit (II), R ⁴ and R ^{5 are} both preferably hydrogen atoms. In particular, it is preferred that R ⁴ and R ^{5 are} both hydrogen atoms, and one of R ⁶ and R ^{7 is} an aliphatic hydrocarbon group having a carbon number of 1-10 and the other is also a hydrogen atom. The aliphatic hydrocarbon group is preferably an alkyl group or alkenyl group. If the gas barrier properties of the obtained film or the like are of particular importance, it is particularly preferable that one of R ⁶ and R ^{7 is} a methyl group or ethyl group and the other is a hydrogen atom. Further, it is particularly preferable that one of R ⁶ and R ^{7 is} a substituent group expressible as (CH ₂ ) _h OH (wherein h is an integer of 1 to 8), and the other is a hydrogen atom. It is particularly advantageous if in the substituent group h expressible as (CH ₂ ) _h OH an integer of 1 to 4, and more advantageously if this is 1 or 2 and especially advantageous if h is 1.

There is no limitation on the method with which the EVOH (A) is provided with the structural unit (II). For example, there can be advantageously used a method in which a monovalent epoxy compound represented by one of the following general formulas (IV) to (X) is reacted with the EVOH (A) obtained by saponification.

In the above general formulas (IV) to (X), R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently denote a hydrogen atom, an aliphatic hydrocarbon group (alkyl group, alkenyl group or the like) having a carbon number of 1-10 alicyclic hydrocarbon group having a carbon number of 3 to 10 (cycloalkyl group, cycloalkenyl group or the like), or an aromatic hydrocarbon group (phenyl group or the like) having a carbon number of 6 to 10. Further, i, j, k, p and q independently denote an integer of However, when R ^{17 is} a hydrogen atom, R ¹⁸ contains a substituent group other than a hydrogen atom.

Examples of the monovalent epoxy compound expressible by the general formula (IV) are epoxyethane (ethylene oxide), epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 3-methyl-1,2-epoxybutane, 1,2-epoxy pentane, 3 Methyl 1,2-epoxy pentane, 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, epoxy-ethylbenzene, 1-phenyl-1,2-epoxypropane, 3-phenyl-1,2-epoxypropane and the like.

Examples of the monovalent epoxy compound expressible by the general formula (V) are any kinds of alkyl glycidyl ether. Examples of the monovalent epoxy compound expressible by the general formula (VI) are any kinds of alkylene glycol monoglycidyl ether. Examples of the monovalent epoxy compound expressible by the general formula (VII) are any kinds of alkenyl glycidyl ether. Examples of the monovalent epoxy compound expressible by the general formula (VIII) are any types of epoxyalkanol, e.g. Glycidol. Examples of the monovalent epoxy compound expressible by general formula (IX) are any types of epoxycycloalkanes. Examples of the monovalent epoxy compound expressible by the general formula (X) are any types of epoxycycloalkenes.

Among the monovalent epoxy compounds, epoxy compounds having a carbon number of 2 to 8 are preferred. Particularly, in view of the handleability and the reactivity of the compound, monovalent epoxy compounds having a carbon number of 2 to 6 are preferable, and a carbon number of 2 to 4 is more preferable. Further preferred monohydric epoxy compounds are the compounds expressable with the general formal (IV) and the compounds expressable with the general formula (V). More specifically, with respect to e.g. the reactivity with EVOH (A) and the gas barrier properties of a obtained film or the like 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane and glycidol are preferable, and of these, epoxypropane and glycidol are preferable.

In the structural unit (III), R ⁸ , R ⁹ , R ¹⁰ and R ^{11 are} preferably hydrogen atoms or aliphatic hydrocarbon groups having a carbon number of 1 to 5, and as aliphatic hydrocarbon groups are methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, Isobutyl groups, tert-butyl groups and n-pentyl groups are preferred.

There is no particular limitation on the method with which the EVOH (A) is provided with the structural unit (III), and an example is that in U.S.P. JP 2014-034647A disclosed methods.

The lower limit of the melting point TmA of the EVOH (A) is preferably 160 ° C, more preferably 170 ° C, even more preferably 180 ° C, and particularly preferably 185 ° C. On the other hand, the upper limit of the melting point TmA of the EVOH (A) is preferably 210 ° C, preferably 200 ° C, and particularly preferably 195 ° C. By setting the melting point TmA of the EVOH (A) in this range, the melt moldability, the heat resistance, the gas barrier properties and the resistance to prolonged heating can be improved.

As for the melt viscosity of EVOH (A), the lower limit of MFR at 210 ° C and 2160 g load is preferably 1g / 10min, and more preferably 3g / 10min. On the other hand, the upper limit thereof is preferably 15g / 10min, more preferably 10g / 10min, and even more preferably 6g / 10min. When an EVOH (A) having such a melt viscosity is used, the melt moldability and the resistance to prolonged heating can be improved. It should be noted that the value of the MFR in this specification can be measured according to the specifications of ASTM D1238.

The lower limit of the content amount of EVOH (A) is preferably 30 parts by mass based on a total amount of 100 parts by mass of EVOH (A), EVOH (B) and PA (C) in total, more preferably 50 parts by mass, and still more preferably 60 parts by mass. On the other hand, the upper limit of this content amount is preferably 95 parts by mass, more preferably 90 parts by mass, still more preferably 85 parts by mass, and still more preferably 80 parts by mass. By keeping the content of EVOH (A) in this range, the heat resistance, the gas barrier properties and the resistance to prolonged heating can be well matched and improved.

EVOH (B)

The EVOH (B) in the plastic composition according to an embodiment of the present invention is preferably an EVOH having a melting point TmB which is at least 10 ° C lower than the melting point TmA of the EVOH (A). Further, the EVOH (B) in the plastic composition according to another embodiment of the present invention is an EVOH having a melting point TmB which is at least 10 ° C lower than the melting point TmA of the EVOH (A). By virtue of the fact that the plastic composition of the present invention contains such a low melting point EVOH (B) the gas barrier properties, the resistance to prolonged heating and the trim recoverability are improved.

The lower limit of the difference (TmA - TmB) between the melting point TmA of the EVOH (A) and the melting point TmB of the EVOH (B) is preferably 15 ° C, and more preferably 20 ° C. If the difference (TmA - TmB) between the melting point TmA and the melting point TmB is at least 10 ° C, then e.g. the gas barrier properties, the resistance to prolonged heating and the trim recoverability are improved. The upper limit for this difference (TmA - TmB), on the other hand, may e.g. 50 ° C, 40 ° C or even 30 ° C.

Concrete examples and preferred examples of the process for producing the EVOH (B) and the constituent monomers are as for the EVOH (A).

The lower limit of the content of ethylene units in the EVOH (B) is preferably 20 mol%, more preferably 30 mol%, more preferably 36 mol%, and particularly preferably 40 mol%. The upper limit of the content of ethylene units is preferably 70 mol%, more preferably 60 mol%, and particularly preferably 50 mol%. By having the content of ethylene units above this lower limit, in a film or the like, e.g. the gas barrier properties at high humidity and the resistance to prolonged heating even better. On the other hand, if the content of ethylene units is below the above upper limit, the gas barrier properties of a film or the like can be improved. And if the content of ethylene units of the EVOH (B) is in the above range, then the desired melting point TmB can be set comparatively easily.

The lower limit of the melting point TmB of the EVOH (B) is preferably 150 ° C, and more preferably 160 ° C. On the other hand, the upper limit of the melting point is preferably 190 ° C, more preferably 180 ° C, even more preferably 175 ° C, and particularly preferably 170 ° C. By having the melting point TmB of the EVOH (B) in this range, e.g. the resistance to prolonged heating can be improved.

As for the melt viscosity of EVOH (B), the lower limit of MFR at 210 ° C and 2160 g load is preferably 1g / 10min, and more preferably 3g / 10min. On the other hand, the upper limit is preferably 30 g / 10 min, more preferably 20 g / 10 min, and even more preferably 15 g / 10 min. When an EVOH (B) having such a melt viscosity is used, the melt moldability and the resistance to prolonged heating can be improved.

The lower limit of the content amount of EVOH (B) is preferably 1 part by mass based on a total amount of 100 parts by mass of EVOH (A), EVOH (B) and PA (C) in total, more preferably 3 parts by mass, and still more preferably 5 parts by mass. On the other hand, the upper limit of this content amount is preferably 50 parts by mass, more preferably 40 parts by mass, and still more preferably 30 parts by mass. By having the content amount of EVOH (B) in this range, gas barrier properties, resistance to prolonged heating, heat resistance, and trim recoverability can be well balanced and improved.

PA (C)

The PA (C) is a macromolecule in which a monomer is polymerized by an amide bond. Examples of the PA (C) are polycaproamide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylauryllactam (nylon 12), polyethylene-diaminadipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 106), caprolactam / lauryl lactam copolymer (nylon 6/12) , Caprolactam / ω-aminononanoic acid copolymer (nylon 6/9), caprolactam / hexamethylene-diammonium adipate copolymer (nylon 6/66), lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/66), ethylenediammonium adipate / hexamethylene diammonium adipate copolymer (nylon 26 / 66), caprolactam / hexamethylenediammonium adipate / hexamethylene-diammonium sebacate copolymer (nylon 6/66/610), ethylenediammonium adipate / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon-26/66/610), Pol yhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (nylon 6T), hexamethylene isophthalamide / hexamethylene terephthalamide copolymer (nylon 61 / 6T), 11-aminoundecanediamine / hexamethylene terephthalamide copolymer, polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyhexamethylenecyclohexylamide, polynonamethylenecyclohexylamide, or those the by modifying these polyamides with an aromatic amine such as methylenebenzylamine or metaxylenediamine. Also, metaxylylenediammonium adipate and the like can be cited as an example.

Of these, in view of gas barrier properties, resistance to prolonged heating, heat resistance and trim recoverability, polyamides which are mainly caproamide are preferable, and concretely, caproamide units in which the polyamide structural units are at least 75 mol% are preferred. Of these, with respect to e.g. for compatibility with EVOH (A) and EVOH (B) nylon 6 is preferred.

As the method for the polymerization of PA (C), melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization and solid state polymerization or combinations of these can be employed.

The lower limit of the melting point TmC of PA (C) is preferably 190 ° C, more preferably 200 ° C, even more preferably 205 ° C, and particularly preferably 210 ° C. For example, by setting the melting point TmC of PA (C) above this lower limit, the resistance to prolonged heating can be improved. On the other hand, the upper limit of the melting point TmC of PA (C) is preferably 250 ° C, more preferably 230 ° C, and still more preferably 225 ° C. By keeping the melting point TmC of PA (C) below this upper limit, for example, melt moldability, heat resistance and trim recoverability can be improved.

The lower limit of the content amount of PA (C) is preferably 1 part by mass based on a total amount of 100 parts by mass of EVOH (A), EVOH (B) and PA (C) in total, more preferably 4 parts by mass, and still more preferably 7 parts by mass. If the content amount of PA (C) is above this lower limit, then e.g. the resistance to prolonged heating can be improved. On the other hand, the upper limit of this content amount 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 keeping the content amount of PA (C) below this upper limit, the gas barrier properties can be improved while achieving good heat resistance, trim recoverability and resistance to prolonged heating.

Fatty Acid Based Divalent Metal Salt (D)

It is advantageous if the plastic composition of the present invention contains a fatty acid-based divalent metal salt (D). By containing a certain amount of fatty acid-based divalent metal salt (D), the heat resistance, the trim recoverability and the hue of the plastic composition of the present invention can be further improved. The fatty acid in this fatty acid-based divalent metal salt (D) is a monocarboxylic acid composed of an aliphatic hydrocarbon group or a hydrogen atom and a carboxy group. Examples of such fatty acids are higher fatty acids having at least 7 carbon atoms and lower fatty acids having 1 to 6 carbon atoms, and lower fatty acids are preferred in view of long-term heat resistance. Examples of higher fatty acids include lauric acid, stearic acid and myristic acid. From the viewpoint of compatibility with EVOH (A) and EVOH (B), stearic acid is preferable. Examples of lower fatty acids are 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. From the viewpoint of compatibility with EVOH (A) and EVOH (B), a saturated fatty acid having 1 to 3 carbon atoms is preferable, and acetic acid is particularly preferable.

Examples of the metal in the fatty acid-based divalent metal salt (D) are alkaline earth metals such as magnesium and calcium; and divalent transition metals such as manganese (II), iron (II), cobalt (II), nickel (II), copper (II) and zinc (II.) With respect to e.g. the heat resistance is alkaline earth metals and magnesium is particularly preferred.

In the plastic composition of the present invention, the salt may be formed by reacting the metal in the fatty acid-based divalent metal salt (D) as a counter cation to the fatty acid ions in the fatty acid-based divalent metal salt (D) or as a counter cation to the alkoxide in the EVOH (A) and / or EVOH (B ) serves.

If the plastic composition of the present invention contains a fatty acid-based divalent metal salt (D), the lower limit of its content amount converted to the metal ions, for example, 0.0001 parts by mass relative to a total of 100 parts by mass of EVOH (A), EVOH (B ) and PA (C) in total, preferably 0.001 part by mass, and more preferably 0.002 part by mass. For example, when the content of the fatty acid-based divalent metal salt (D) is above this lower limit, heat resistance and trim recoverability can be improved, and the plastic composition can be stably adjusted to a particular phase-separated structure and gel fraction. Further, by keeping the content amount of the fatty acid-based divalent metal salt (D) below the upper limit mentioned above, the trim recoverability can be improved. By contrast, the upper limit for this content amount may, for example, also be 0.1 parts by weight, 0.05 parts by weight being preferred, 0.03 parts by weight more preferably and 0.02 parts by weight being particularly preferred. By keeping the content of the fatty acid-based divalent metal salt (D) below this upper limit, even better heat resistance can be obtained, and the plastic composition can be stably adjusted to a certain phase-separated structure and gel fraction. By keeping the content of the fatty acid-based divalent metal salt (D) below the upper limit mentioned above, the hue of the plastic composition of the present invention can be improved and yellowing can be avoided.

If the plastic composition according to the invention contains a fatty acid-based divalent metal salt (D), it is advantageous if this fatty acid-based divalent metal salt (D) is distributed uniformly throughout the plastic composition according to the invention.

mixing ratio

The lower limit of the mixing ratio (A / B) of the EVOH (A) and the EVOH (B) by mass may be e.g. 1.0, with 2.0 being preferred and 3.0 being particularly preferred. The upper limit for this mixing ratio (A / B) may be e.g. 20, with 11 being preferred and 7 being particularly preferred. By keeping the mixing ratio (A / B) of the EVOH (A) and the EVOH (B) in this range, e.g. the gas barrier properties and the resistance to prolonged heating are improved.

The lower limit of the mixing ratio ((A / B) / C) of the PA (C) to the entirety of EVOH (A) and EVOH (B) by mass may be e.g. 0.67, with 1.5 being preferred, 2.33 being most preferred, 4 being most preferred and 5.67 being most preferred. By having the mixing ratio ((A / B) / C) above this lower limit, the plastic composition can be easily adjusted to a particular phase-separated structure and gel fraction, and e.g. the gas barrier properties, the resistance to prolonged heating and the trim recoverability are improved. In contrast, the upper limit for the mixing ratio ((A / B) / C) is advantageously 99, with 49 being preferred, 24 being particularly preferred, and 13.29 being particularly preferred. By keeping the mixing ratio ((A / B) / C) below this upper limit, the proportion of PA (C) having a high melting point can be increased, and the resistance to prolonged heating can be increased.

The lower limit of the mixing ratio (B / C) of the EVOH (B) and the PA (C) by mass is preferably 0.053, with 0.25 being particularly preferable. Since the mixing ratio (B / C) is above this lower limit, e.g. the gas barrier properties and trim recoverability are improved even more. On the other hand, the upper limit of the mixing ratio (B / C) is preferably 19, and more preferably 5.67. By keeping the mixing ratio (B / C) below this upper limit, e.g. the resistance to prolonged heating can be improved even more.

The lower limit for the amount (D / C) of the fatty acid-based divalent metal salt (D) relative to the amount of PA (C), ie the object mass of the fatty acid-based divalent metal salt (D) converted to the metal ions (D) per 1 g PA (C ) is preferably 3 μmol / g, more preferably 8 μmol / g and particularly preferably 12 μmol / g. By keeping the content ratio above this lower limit, heat resistance and trim recoverability can be improved even more. The upper limit of the content ratio (D / C), on the other hand, may be e.g. 250 μmol / g, and is preferably 150 μmol / g, more preferably 50 μmol / g, and particularly preferably 35 μmol / g. By keeping the content ratio (D / C) below this upper limit, better heat resistance and color tone can be achieved.

Other components

In addition to the EVOH (A), the EVOH (B) and the PA (C), the plastic composition according to the invention may also contain other plastics or resins and, in addition to the fatty acid-based divalent metal salt (D), other additives or additives as further components.

Examples of other plastics are polyolefins. In this case, the lower limit for the ratio of the total amount of EVOH (A), EVOH (B) and PA (C) to all plastic components in the plastic composition according to the invention is preferably 90% by mass, more preferably 97% by mass and particularly preferably 99% by mass. %. With the plastic components consisting essentially of EVOH (A), EVOH (B), and PA (C) in this manner, even better heat resistance, gas barrier properties, trim recoverability and resistance to prolonged heating can be obtained.

Examples of additives are plasticizers, fillers, antiblocking agents, antioxidants, dyes, antistatic agents, UV absorbers, lubricants, desiccants and other known additives. Incidentally, the content amount of the additives is preferably not more than 2 parts by mass based on a total of 100 parts by mass of EVOH (A), EVOH (B) and PA (C) in total, and preferably not more than 1 part by mass. By keeping the content of the additives low, better heat resistance, barrier properties, trim recoverability and resistance to prolonged heating can be achieved.

The plastic composition according to the invention may also contain other metal salts in addition to the fatty acid-based divalent metal salt (D). Examples of other metal salts are fatty acid-based monovalent metal salts, and carboxylic acid metal salts, excluding fatty acid salts. As the monovalent fatty acid metal salt, a fatty acid alkali metal salt is preferably used, and as the fatty acid in the monovalent fatty acid metal salt, the above-mentioned fatty acid constituting the fatty acid-based divalent metal salt (D) is preferably used. Examples of carboxylic acids which form carboxylic acid metal salts other than fatty acid salts are aromatic carboxylic acids and polybasic carboxylic acids, for example, aromatic carboxylic acids such as benzoic acid and 2-naphthoic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, malic acid, glutaric acid, adipic acid and pimelic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Tricarboxylic acids such as citric acid, isocitric acid and aconitic acid; tetravalent carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid and ethylenediaminetetraacetic acid; Hydroxycarboxylic acids such as citric acid, isocitric acid, tartaric acid, malic acid, mucic acid, tartronic acid, and citramalic acid; 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. If the plastic composition according to the invention has yet another metal salt in addition to the fatty acid-based divalent metal salt (D), then this metal salt is preferably a fatty acid-based monovalent metal salt. If the plastic composition of the present invention has another metal salt besides the fatty acid-based divalent metal salt, then the upper limit of the content amount thereof is preferably 0.03 part by mass based on a total of 100 parts by mass of EVOH (A), EVOH (B) and PA (C). in total in the plastic composition of the present invention, more preferably 0.02 part by mass, and still more preferably 0.018 part by mass. Further, the total content of EVOH (A), EVOH (B), PA (C) and metal salt in the dried resinous composition of the present invention is preferably at least 99% by mass, more preferably at least 99.9% by mass, and still more preferably at least 99% , 99% by mass. If the plastic composition according to the invention has such a composition, then the favorable gel content described below can be achieved in a simple manner, whereby even better gas barrier properties and resistance to prolonged heating can be achieved.

Separate phase structure

The plastic composition according to one embodiment of the invention has, as in 1 show a separate phase structure, with a sea phase 11 , an island phase 12 as well as one of the island phase 12 surrounded third phase 13 , The sea phase 11 contains the EVOH (A), the island phase 12 contains the EVOH (B) and the third phase 13 contains the PA (C). By virtue of the plastic composition having this separate phase structure, good resistance to prolonged heating can be achieved and, at the same time, good gas barrier properties can be maintained.

The island phase is a phase that is distributed and island-shaped. The third phase is a phase that is island-shaped in turn within the island phase. There may be a third phase each within an island phase, but it is also possible that several third phases within an island phase available. Furthermore, the third phase may also be incompletely surrounded by the island phase, and there may also be island phases that do not surround a third phase.

There is no particular limitation on the shape of the island phase and the third phase, and these may be e.g. be circular or elliptical or have other irregular shapes. Of these, a circular shape and an ellipse shape are advantageous, and an ellipse shape is particularly advantageous. If the resin composition is extruded or injection molded, it is considered that the island phase and the third phase form an ellipse shape stretched in the extrusion direction or the like.

In the plastic composition according to an embodiment of the present invention, the proportion of EVOH (A) in the sea phase is preferably at least 50% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass, particularly preferably at least 90% by mass. %, and most preferably 100% by mass. Further, the proportion of EVOH (B) in the island phase is preferably at least 50% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass, more preferably at least 90% by mass, and may be 100% by mass. %. The calculation of the proportion of components in the island phase does not take into account the third phase. The proportion of PA (C) in the third phase is preferably at least 50% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass, particularly preferably at least 90% by mass, but may also be 100% by mass. %. That the proportion of EVOH (A), EVOH (B) and PA (C) in each phase is in the above-mentioned ranges is advantageous, because thus good gas barrier properties and resistance to prolonged heating can be obtained when the above-described phase-separated structure is formed. For example, as long as the above-mentioned ranges are satisfied, the PA (C) may be contained in the sea phase and in the island phase, and EVOH (A) and EVOH (B) may also be contained in the third phase. The ratio can be measured by nano-IR analysis or TEM observation as described in the embodiments.

In the plastic composition according to one embodiment 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 thereof is preferably 1 μm, more preferably 0.5 μm, and still more preferably 0.3 μm. Here, the average dispersed particle size means the value calculated by averaging the sizes of 100 third phases in the visual field when examining any sectional area of the plastic composition of the present invention with an electron microscope. If the third phase is not circular but elliptical or the like, then the calculation is performed using the short diameter. The fact that the average dispersed particle size falls within the above range is advantageous, because thus a good resistance to prolonged heating can be obtained while maintaining good gas barrier properties.

gel

The gel present in the gel portion according to another embodiment of the invention is taken as the reaction product of EVOH and PA (C) and refers to the insoluble matter remaining after the plastic composition is dissolved in a good solvent for EVOH and further the PA (C) was dissolved in a good solvent for it. In this case, this insoluble matter does not include the inorganic insoluble matter of fillers and the like. Here, a good solvent for EVOH means a solvent in which EVOH can be completely dissolved under certain conditions, and a good solvent for PA (C) means a solvent in which PA (C) can be completely dissolved under certain conditions. An example of a good solvent for EVOH is a mixed solvent of water (45% by weight) / propanol (55% by weight). An example of a good solvent for PA (C) is 2,2,2-trifluoroethanol. The gel content is measured after the EVOH and the PA (C) are completely dissolved, and, for example, the conditions described in the embodiments are applied. The conditions described in the exemplary embodiments can be advantageously used if, for example, the proportion of inorganic insoluble matter in the dried resinous composition is less than 0.1% by mass. If the content of the inorganic insoluble matter in the plastic composition is 0.1 mass% or more, the gel content can be calculated by determining the inorganic mass in the insoluble matter obtained by the methods described in the working examples, and FIGS Mass of insoluble matter is determined except this inorganic mass. The gel content can be determined by the following equation (1): $$\text{gel}\left(\%\right)=100\times \text{Mass of insoluble matter / mass of plastic composite}\left(1\right)$$

The lower limit of the gel content in the other embodiment of the present invention is preferably 0.5%, more preferably 0.75%, and still more preferably 1%. By contrast, the upper limit for the gel fraction is preferably 20%, more preferably 15% and even more preferably 10%. By having the gel content in this range, good gas barrier properties and good resistance to prolonged warm-up can be achieved. And, because the gel content is at least 0.5%, the proportion of the reaction product of EVOH and PA (C) is sufficient, and defects (voids and the like) in appearance after heating may tend to be reduced. If, on the other hand, the gel content is not more than 20%, then problems in the manufacturing process, e.g. Sticking of the reaction product of EVOH and PA (C) on the screw as well as a deterioration of the heat stability in the film production can be avoided.

Means for adjusting the phase-separated structure and the gel fraction

The phase-separated structure and the gel content may be e.g. can be adjusted by adjusting the mixing ratio of EVOH (A), EVOH (B) and PA (C), and the kneading conditions. Examples of concrete methods for adjusting the kneading conditions are when e.g. a single screw extruder is used, adjusting the time that the resin remains in the extruder with the shape of the screw or thread depth, or also adjusting the shear viscosity. As a helical form, e.g. However, it is also possible to use screws with Maddock or Dulmage form to use the "fully flighted screws" or barrier screws to adjust the kneading strength. Furthermore, it is also possible to adjust the number of revolutions of the screws in order to increase the shear rate. Further, in view of that the screw shape can be easily changed, sometimes a twin-screw extruder is used. If a twin-screw extruder is used, adjusting the length of the kneading disc is an example of a method for adjusting the kneading strength.

If a single-screw extruder is used, the lower limit of the shear rate r in the total amount in the melt extruder calculated as the concrete kneading condition with the following equation (2) is preferably 10 sec ^-1 , more preferably 15 sec ^-1 , and most preferably 20 sec ^-1 . 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 . When kneading below this lower limit, the mixing state of EVOH (A), EVOH (B) and PA (C) deteriorates, the phase-separated structure described above tends to be more difficult to form, and also the gel content tends to be lower, so that can worsen the resistance to prolonged heating. When kneading above the above upper limit, the EVOH (A), the EVOH (B) and the PA (C) are mixed too much so that the separated phase structure tends to be more difficult to form, and also the gel content tends to be too high so that the heat stability may deteriorate.
[Mathematical Expression 1] $$\text{r}=\frac{\mathrm{\pi }·\text{DN}}{60·\text{H}}$$

In the equation (2), D denotes the cylinder diameter (cm), N denotes the screw speed (rpm), h denotes the thread depth in the weight reduced portion (cm), and r denotes the shear rate (sec ^-1 ).

There is no particular limitation on the shape of the plastic composition of the present invention, but it is usually in pellet form. Furthermore, the plastic composition according to the invention is normally a dry product. The proportion of water relative to all plastic components in the plastic composition according to the invention may be up to 10% by mass, it may also be up to 1% by mass or up to 0.1% by mass. The plastic composition according to the invention may advantageously be used as a shaped article such as e.g. be used as packaging material.

Process for producing the plastic compound

There is no particular limitation on the method for producing the plastic compound of the present invention, and it is possible to use a generally known device as well as a general one to use known method. Examples thereof are a production method comprising a step of dry blending the EVOH (A), the EVOH (B) and the polyamide (C), and a step of melt kneading the mixture obtained in the dry blending step; or also a production method comprising a step of melt-kneading the EVOH (A) and the EVOH (B), and a step of melt-kneading PA (C) with the obtained mixture of EVOH (A) and EVOH (B). Of these methods, the production method comprising a step of dry blending the EVOH (A), the EVOH (B) and the polyamide (C), and a step of melt-kneading the mixture obtained in the dry blending step is preferable because the above-mentioned phase-separated structure and above gel content can be achieved, and heat resistance, gas barrier properties and resistance to prolonged heating can be improved.

The EVOH (A), the EVOH (B) and the PA (C) added to the above-mentioned steps of dry blending and melt kneading are usually pellets. If these pellets contain a fatty acid-based divalent metal salt (D), pellets may be used in a previously prepared aqueous solution containing the fatty acid-based divalent metal salt (D) for a sufficient time, e.g. Soaked for 1 second to 1 day. Further, in the step of melt-kneading, the previously prepared fatty acid-based divalent metal salt (D) or an aqueous solution thereof may be melt-kneaded together.

The melt-kneading can be carried out with a conventional device, e.g. a single-screw extruder or a twin-screw extruder. Further, in the respective melt-kneading step, melt extrusion and pelletization with a single-screw extruder or a twin-screw extruder can obtain the plastic composition of the present invention in the form of pellets.

Shaped body and method for producing the shaped body

An inventive molding is made of the plastic composition of the invention. The shaped article according to the invention is generally a melt-molded product of the inventive plastic composition. Also, a molded article of an EVOH (A), an EVOH (B) having a melting point TmB below the melting point TmA of the EVOH (A), and a polyamide (C) having a phase-separated structure having a sea phase, an island phase and one of the Is island phase surrounded third phase, and wherein the sea phase comprises the ethylene-vinyl alcohol copolymer (A), the island phase, the ethylene-vinyl alcohol copolymer (B), and the third phase, the polyamide (C), as well as a molding, from an EVOH (A); an EVOH (B) having a melting point TmB below the melting point TmA of EVOH (A), and a polyamide (C), 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 at least 10 ° C, and a gel content is at least 0.5% and at most 20% are molded articles in the sense of the present invention. Furthermore, the method for producing the shaped article according to the invention comprises a step of melt-molding the plastic composition according to the invention.

That is, with the above-described plastic composition of the present invention, by melt molding, a molded article such as a film, a vessel, or other packaging material (e.g., for food or medicine) or the like can be molded. In melt molding, the plastic composition of the present invention may be melt-molded, but also EVOH (A), EVOH (B) and PA (C) may be dry blended and directly melt molded. The plastic composition of the present invention has both good gas barrier properties and good resistance to prolonged heating, and further has good heat resistance and trim recoverability. For this reason, a molded article such as e.g. a film which is a melt-molded product of the plastic composition of the invention, suitable for use as a packaging material for prolonged heating or for boiling. There is no particular restriction on the thickness of foils, and here they also refer to objects that can be referred to as films or webs.

Furthermore, the shaped body according to the invention (film or the like) can also be provided as a secondarily produced molded product. Examples of such secondary products of films are reheat bags, thermoformed containers, thermoformed container caps, food packaging containers such as shrink containers and other food packaging containers, and the like. If the molded article according to the invention is a film, this film may be single-layered or multi-layered, and it is preferable to have a multi-layered structure with layers comprising a hydrophobic thermoplastic resin in order to prevent the gas barrier properties of the plastic composition from being adversely affected by moisture , to use.

Examples of hydrophobic thermoplastics are polyolefin plastic (polyethylene plastic, polypropylene plastic, etc.), grafted polyolefin plastic modified with unsaturated carboxylic acid or an ester thereof, halogenated polyolefin plastic, ethylene-vinyl acetate copolymer plastic, ethylene-acrylic acid copolymer plastic, ethylene-acrylic ester copolymer plastic, Polyester plastic, polyamide plastic, polyvinyl chloride plastic, polyvinylidene chloride plastic, acrylic plastic, polystyrene plastic, vinyl ester plastic, ionomer, polyester elastomer, polyurethane elastomer, aromatic or aliphatic polyketone, and the like. Among these, preferred are polyolefin plastics from the viewpoint of mechanical strength and ductility, with polyethylene plastic and polypropylene plastics being particularly preferred.

It is also possible to provide a multi-layered structure which, instead of these plastics, is combined with paper, gold foil, a woven fabric, a non-woven fabric, metallic cotton strips, a wooden surface, aluminum or silicon dioxide coatings.

As a layered structure for such a multi-layered structure, the following examples of layer arrangements may be given, wherein F denotes a layer obtained from the plastic composition of the present invention, A denotes a layer consisting of a hydrophobic thermoplastic resin, and MA denotes a layer consisting of a hydrophobic thermoplastic plastic modified with an unsaturated carboxylic acid or a derivative thereof. In the layer arrangement, the layers to the left are arranged farther outward (ie to the side which is exposed to external influences). The hydrophobic thermoplastic layer MA modified with an unsaturated carboxylic acid or a derivative thereof may be used as an adhesive resin layer or 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

embodiments

In the following, embodiments of the present invention and comparative examples will be described in detail, and the present invention is not limited to the following embodiments. The procedures for measurement, calculation and evaluation were carried out as follows.

melting point

Using a TA Instruments Differential Scanning Calorimeter "Q2000", the temperature was raised from 30 ° C to 250 ° C at a rate of 10 ° C / min, and the melting point was determined by the measured peak temperature.

Amount of divalent metal ions

0.5 g of dried EVOH pellets were placed in a Tef-Ion ™ pressure vessel made by Actac, and 5 ml of nitric acid for precision analysis, manufactured by Wako Pure Chemical Industries, Ltd., was added thereto. After standing for 30 minutes, the container was covered by a rupture disc sealing lip and split for 10 minutes at 150 ° C and then for 10 minutes at 180 ° C with Actac's "Speedwave MWS-2" microwave high speed analysis system. When the decomposition of the dried EVOH pellets was insufficient, the processing conditions were adjusted accordingly. The whole was diluted with 10 ml of ion exchange water, and all the liquid was transferred to a 50 ml volumetric flask, followed by adjusting a constant volume with deionized water to obtain a decomposing solution.

This decomposition solution was measured using an Optima 4300 DV ICP emission spectrophotometer from PerkinElmer Japan Ltd. was quantitatively analyzed at the following observation wavelengths, whereby the amount of divalent metal ions was measured. mg: 285.213 nm Ca: 317.933 nm

TEM measurement

The plastic composition (pellets) and a monolayer film were embedded in epoxy resin, and segments were made in the cross-sectional direction with an ultramicrotome. The obtained cross-sectional segments were contacted with a 5% aqueous solution of phosophenic tungstic acid for 5 minutes, dried, and thereafter, using a transmission electron microscope (TEM) "JEM 2100" manufactured by Nippon Denshi Co., Ltd. observed under 5000x magnification. From the TEM images, the above-described phase-separated structure of sea phase, island phase and third phase was recognizable, with particles having an observed particle size (short diameter of the third phase) of at least 0.05 .mu.m as a sea-island structure, and particles with a observed particle size of less than 0.05 microns were adopted as a fine distribution. A "sea-island structure" according to the present embodiment means a structure having the above-described phase-separated structure, containing as the sea phase EVOH (A), island phase EVOH (B), and third phase PA (C). In the "fine distribution" the presence of further phases within the distributed phases could not be recognized. 2 shows a TEM image of a single-layer film obtained with the embodiment 1, and 3 Fig. 12 shows a TEM image of a single layer film obtained with Comparative Example 4.

gel

Using a single screw extruder (Toyo Seiki Seisakusho, Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: continuous) with 20 μm thickness of pellets of the embodiments and the comparative examples. The extrusion conditions are listed below: Extrusion temperature: 240 ° C Mold width: 30 cm Temperature of the removal roller: 80 ° C Schraubdrehgeschwindigkeit: 45 rpm Speed of the removal roller: 3.4 m / min

The produced single layer film of 20 μm in thickness was dried with a vacuum dryer at 60 ° C for 12 minutes, cut off and the mass was measured (W1).

One part by mass of the single layer film was soaked in 100 parts by mass of a mixed solvent of water (45% by mass) / propanol (55% by mass), and heated and dissolved at 75 ° C for 8 hours. Thereafter, the unresolved parts were collected with a metal mesh sieve (mesh number: 100) and a filtrate was obtained. The resulting filtrate was dried with a vacuum dryer at 60 ° C for 12 hours. Next, 1 part by weight of the filtrate was soaked in 100 parts by weight of 2,2,2-trifluoroethanol, and heated and dissolved at 50 ° C for 8 hours. Thereafter, the unresolved parts were collected with a metal mesh (mesh number: 100), the unresolved parts were dried with a vacuum dryer for 12 hours at 60 ° C. Thereafter, the mass was measured (W2). Gel content (G) (in%) was calculated by the following equation: $$\begin{array}{l}\text{gel}\left(\text{G}\right)\left(\text{in}\%\right)=100\times \text{dried non-soluble mass}\left(\text{W}2\right)\text{/Dimensions}\left(\text{W}1\right)\\ \text{the dried 20}\mathrm{\mu }{\text{m}}^{\text{-}}\text{single layer film}\end{array}$$

OTR (oxygen permeation rate)

The single-layer films of 20 μm thickness, which were obtained with the exemplary embodiments and the comparative examples, using an oxygen permeability meter (type OX-TRAN 2/20) from MOCON Inc. (detection limit value: 0.01 mL, 20 μm / m ² · Day · atm) at a temperature of 20 ° C and a humidity of 65% RH subjected to the measuring method described in JIS K 7126 (Isostatic method). The oxygen barrier properties were evaluated according to the following criteria. In cases A and B, it was judged that the gas barrier properties are good. Rating: criteria A: less than 0.25 B: at least 0.25 and less than 0.45 B: at least 0.45 (Unit: mL · 20 μm / m ² · day · atm)

Resistance to prolonged heating

The single-layered films of 20 μm in thickness obtained with the embodiments and the comparative examples, a biaxially stretched nylon 6 film ("Emblem ONBC" manufactured by Unitika, thickness 15 μm) and an unstretched polypropylene film ("Tohcello CP" manufactured by Mitsui Chemicals Tohcello, 50 μm thick) were each cut to A4 size, adhesive was applied to both sides of the single-layer film for dry lamination, and dry lamination was performed so that the nylon 6 film as the outer layer and the unstretched polypropylene film as the inner layer serves. This was dried at 80 ° C for 3 minutes to obtain a three-layered transparent laminated film. For the adhesive for lamination, "Takelac A-520" from Mitsui Chemicals, Inc. as a main component, "Takenate A-50" from Mitsui Chemicals, Inc. as a curing agent and ethyl acetate as a diluent were used. The adhesive application amount was set to 4.0 g / m ² , and after lamination, a three-time curing was carried out at 40 ° C.

Using the laminated film thus obtained, a square sealed bag measuring 12 cm × 12 cm was prepared. This was filled with water. This bag was placed in a prolonged heating apparatus (high temperature high pressure boiling sterilization tester "RCS-40RTGN" of Hitachi Limited), and then subjected to a prolonged heating at 120 ° C for 120 minutes. After this prolonged heating, after wiping water from the surface, the bag was allowed to stand at regular temperature and humidity of 20 ° C and 65% RH for one day, and then the external appearance was examined to evaluate the resistance to prolonged heating. In cases A to C, good resistance to prolonged heating was noted. Rating: criteria A: no fading B: strip-like fading recognizable C: slightly bleached D: bleached

Heat resistance 1 (long-term properties, viscosity stability)

Using a single-screw extruder (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: continuous), single-layer films of the plastic composition according to the embodiments and Figs Comparative examples produced for eight hours in one piece. The extrusion conditions are listed below: Extrusion temperature: 240 ° C Mold width: 30 cm Temperature of the removal roller: 80 ° C Schraubdrehgeschwindigkeit: 40 rpm Speed of the removal roller: 3.1 m / min

Eight hours after the start of the film production, a film sample of 10 cm × 10 cm was taken, and the number of all defects of at least 100 μm in size was visually counted. According to the number of defects, the heat resistance was evaluated as follows: Rating: criteria A: not more than 50/100 cm ² B: more than 50/100 cm ² and not more than 100/100 cm ² C: more than 100/100 cm ²

Heat resistance 2 (long-term properties, viscosity stability)

On 6.5 g of the resin composition obtained according to the working examples and the comparative examples, the torque change was measured by kneading at 100 rpm and 230 ° C with a Thermo Fischer Scientific "Thermo Haake MiniLab Rheomex CTW5". Five minutes after the start of kneading, the torque was measured and the time was measured until the torque value reached 1.5 times or 0.5 times. The longer this time, the lower the viscosity change and the better the heat resistance. The heat resistance was evaluated according to the following criteria. In cases A to D, it was judged that the heat resistance is good. Rating: criteria A: at least 40 minutes B: at least 30 minutes and less than 40 minutes C: at least 20 minutes and less than 30 minutes D: at least 10 minutes and less than 20 minutes e less than 10 minutes

Trim recoverability

According to the following procedure, material was repeatedly recovered and converted into pellets, and the amount of screw adhesion was measured to determine the trim recoverability.

- Preparation of the Reclaimed Material -

Using PP "Novatec EA7AD" from Japan Polypropylene Corp. as the outermost layer, the plastic composition as the innermost layer obtained with an embodiment or comparative example, and "Mod. AP P604V" from Mitsubishi Chemical Corp. as the adhesive resin layer, with a feed block die, 5-layer films of three materials having polyolefin layer / adhesive resin layer / plastic compound layer / adhesive resin layer / polyolefin layer = 200 μm / 20 μm / 20 μm / 20 μm / 200 μm coextruded and thus produced multilayer films. The addition of the respective resin materials to the feedblock occurred in the polyolefin layer with a 32 mmφ extruder, in the adhesive resin layer with a 20 mmφ extruder, and in the plastic composition layer with a 20 mmφ extruder at a temperature of the extruder the respective plastic or resin materials of 240 ° C, and a temperature of the moldings and Feedblockabschnitte of 230 ° C. Next, the resulting multilayer films were crushed with a size 8mmo mesh size grinder, thus preparing the recovered material. The mass ratio in the recovered material thus obtained was PP / EVOH / Adhesive Resin = 85.9 / 5.5 / 8.6.

- Repeated pelleting -

Using the in the WO 2011/136287 Masterbatch 1 (MB 1) described as a recovery additive, this mass-recovered material / recovery additive = 100/3 was dry mixed, and 10.3 kg of the resulting mixture was mixed with a co-axial twin-screw extruder ("Labo Plastomill" from Toyo Seiki Co., Ltd .) With 25 mm∅ at an extrusion temperature of 230 ° C and a discharge of 6 kg / h melt-kneaded and then pelletized. Next, the obtained pellets were dried with a hot air dryer at 80 ° C for 1 hour, and then again with the coaxial twin-screw extruder ("Labo Plastomill" of Toyo Seiki Co., Ltd.) with 25 mmφ at an extrusion temperature of 230 ° C and a discharge of 6 kg / h melt-kneaded and then pelletized. This process with the same drying and pelleting was repeated three more times.

- Measurement of the bolt adhesion quantity -

After being pelleted five times as described above, 0.5 kg of LDPE ("Novatec LD LA320" from Japan Polyethylene Corp.) was added and pelletized again. After the LDPE was discharged, the operation was stopped, the screw was taken out, the material adhering to the screw was recovered, and the weight of the material attached to the screw was determined. This material attached to the screw increases with the deterioration of the plastic composition, and has a negative effect on the appearance of molded products as a gel or defect. The trim recoverability was evaluated according to the following criteria. In cases A to C, it was judged that the trim recoverability is good. Rating: criteria A: not more than 200 g B: more than 200 g and not more than 400 g C: more than 400 g and not more than 600 g D: more than 600 g

hue

A multilayer film prepared by the method described in the item (6) "resistance to prolonged heating" was wound on a paper roll, and the color tone at the ends of the film was evaluated with the naked eye under the following conditions. Rating: criteria A: no discoloration B: slightly yellowed C: yellowed

Embodiment 1

There were 72 parts by mass of "L171B" (amount of ethylene units 27 mol%, MFR 4.0 g / 10 min, melting point 191 ° C) of Kuraray Co., Ltd.) as EVOH (A), 18 parts by mass "E105B" (Amount ethylene units 44 mol%, MFR 13 g / 10 min, melting point 165 ° C) by Kuraray Co., Ltd.) as EVOH (B), and 10 parts by mass of nylon 6 ("UBE NYLON SF1018A" by Ube Industries, Ltd., m.p. 220 ° C) as PA (C) as pellets dry and then a twin-screw extruder "TEX 30a" (screw diameter 30 mm) from Japan Steel Works, Ltd. fed. Further, in the twin-screw extruder as the fatty acid-based divalent metal salt (D), an aqueous magnesium acetate solution as an aqueous solution having a concentration of 1.5 g / L was added with a liquid pump. Downstream of this addition, using a forward kneading disk screw with L (screw length) / D (screw diameter) = 3 as a screw mechanism, a melt extrusion having a melt temperature of 220-230 ° C and an extrusion speed of 20 kg was carried out / h performed. Thereafter, the extruded strands were cooled in a cold bath and solidified, and then cut, whereby pellets of the plastic composition according to Embodiment 1 were obtained.

Using a single-screw extruder (Toyo Seiki Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: continuous), single-layer films of 20 μm were prepared from these pellets of the plastic composition , The extrusion conditions were as follows: Extrusion temperature: 240 ° C Mold width: 30 cm Temperature of the removal roller: 80 ° C Schraubdrehgeschwindigkeit: 45 rpm Speed of the removal roller: 3.4 m / min

Exemplary embodiments 2-27

The types of EVOH (A), EVOH (B) and PA (C) and their proportions, besides the kind of the fatty acid-based divalent metal salt (D), were as shown in Table 1 except that the concentration of the aqueous solution of the fatty acid-based divalent metal salt (D) was adjusted to give the content of the fatty acid-based divalent metal salt (D) shown in Table 1, same as in Working Example 1, whereby pellets of the plastic composition and single-layer films of Working Examples 2 to 27 were obtained.

Embodiment 28

There were 72 parts by mass of "L171B" (amount of ethylene units 27 mol%, MFR 4.0 g / 10 min, melting point 191 ° C) of Kuraray Co., Ltd.) as EVOH (A), 18 parts by mass "E105B" (Amount ethylene units 44 mol%, MFR 13 g / 10 min, melting point 165 ° C) by Kuraray Co., Ltd.) as EVOH (B), 10 parts by mass of nylon 6 ("UBE NYLON SF1018A" by Ube Industries, Ltd., melting point 220 ° C ° C) as PA (C), and magnesium acetate tetrahydrate as the fatty acid-based divalent metal salt (D), converted to metal atoms 2.08 μmol / g on the total amount of EVOH (A), EVOH (B) and PA (C) , mixed dry as pellets. Thereafter, 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 Dulmage), a single-layered film was used 20 microns thickness produced. The extrusion conditions were as follows: Extrusion temperature: 240 ° C Mold width: 30 cm Temperature of the removal roller: 80 ° C Schraubdrehgeschwindigkeit: 45 rpm Speed of the removal roller: 3.4 m / min

Exemplary embodiment 29

Pellets of a plastic composition were produced by the same method as in Embodiment 1 except that the screw in the preparation of the pellets of the plastic composition in Embodiment 1 was replaced with a screw having a forward kneading disk of L (screw length) / D (FIG. Screw diameter) = 1.5. Next, 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 Dulmage), a single-layered film was prepared manufactured with 20 microns thickness. The extrusion conditions were as follows: Extrusion temperature: 240 ° C Mold width: 30 cm Temperature of the removal roller: 80 ° C Schraubdrehgeschwindigkeit: 45 rpm Speed of the removal roller: 3.4 m / min

Comparative Example 1

Pellets and a single-layer film of the plastic composition were prepared as in Embodiment 1 except that the extrusion conditions in the production of the single-layer film in Embodiment 1 were changed as follows. Extrusion temperature: 240 ° C Mold width: 30 cm Temperature of the removal roller: 80 ° C Schraubdrehgeschwindigkeit: 90 rpm Speed of the removal roller: 6.8 m / min

Comparative Example 2

Pellets and a single layer film of the plastic composition were produced as in Embodiment 1, except that the screw in the production of pellets of the plastic composition in Embodiment 1 was replaced by a screw having a forward kneading disk with L (screw length) / D (Screw diameter) = 6.

Comparative Examples 3 - 5, 7

Pellets and a single layer film of the plastic composition of Embodiments 3 - 5 and 7 were prepared as in Embodiment 1 except for the kinds of EVOH (A), EVOH (B) and PA (C), and their proportions, besides the kind of the fatty acid-based divalent Metal salt (D) as shown in Table 1, and that the concentration of the aqueous solution of the fatty acid-based divalent metal salt (D) was adjusted to give the content of the fatty acid-based divalent metal salt (D) shown in Table 1.

Comparative Example 6

Single-layer films were produced by the same method as in Embodiment 28, except that a continuous screw was used as the screw for the single-screw extruder in the production of the single-layer film.

Comparative Example 8

60 kg of ε-caprolactam, 1.2 kg of water and octadecylamine, namely 6.78 meq to 1 mol of ε-caprolactam were placed in an autoclave, sealed in a nitrogen atmosphere heated to 250 ° C, and with stirring for two hours under pressure responding. Thereafter, the pressure was reduced to 180 Torr and reacted for two hours, then returned to normal pressure while adding nitrogen. Then, the stirring was stopped, and the contents were taken out as a strand and chipped, extracted with boiling water, the unreacted monomers and removed, and the whole dried, whereby PA (C) was obtained. The MFR (at 230 ° C and 2160 g load) of the obtained PA (C) was 2.5 g / 10 min, and the melting point was 220 ° C.

There were 49 parts by mass of "F171B" (amount of ethylene units 32 mol%, MFR 3.7 g / 10 min, melting point 183 ° C) of Kuraray Co., Ltd.) as EVOH (A), 21 parts by mass "E105B" (amount ethylene units 44 mol%, MFR 13 g / 10 min, melting point 165 ° C by Kuraray Co., Ltd.) as EVOH (B), 30 parts by mass of PA (C) prepared as above, and magnesium acetate tetrahydrate as fatty acid-based divalent Metal salt (D), converted metal atoms 2.0 μmol / g to the total amount of EVOH (A), EVOH (B) and PA (C), dry blended as pellets. This was a single screw extruder from Toyo Seiki Seisakusho, Co., Ltd. (Screw diameter (D) 40 mm, L / D = 26, screw: continuous, screw speed: 40 rpm) fed and melt-extruded at an extrusion temperature of 230 ° C, a mold temperature of 250 ° C and a plastic temperature of 245 ° C. Thereafter, the extruded strands were cooled in a cold bath and solidified, and then cut to obtain pellets of the plastic composition. These pellets of the plastic composition were fed to a T-type single screw extruder manufactured by Toyo Seiki Seisakusho, Co., Ltd. (Screw diameter (D) 40 mm, L / D = 26, screw: continuous, Screw speed 40 rpm), and melt-extruded at an extrusion temperature of 230 ° C, a mold temperature of 250 ° C and a plastic temperature of 245 ° C, thus producing a single-layer film.

Comparative Example 9

The same evaluation was conducted except that instead of the mixing ratio of Comparative Example 8, 68 parts by mass of "F171B" of "L171B" by Kuraray Co., Ltd. was used. as EVOH (A), 17 parts by mass "E105B" by Kuraray Co., Ltd.) as EVOH (B), and 15 parts by mass of the above-prepared PA (C) and magnesium acetate tetrahydrate as the fatty acid-based divalent metal salt (D) converted metal atoms 2.3 μmol / g was used on the total amount of EVOH (A), EVOH (B) and PA (C).

• · L171B: Menge an Ethyleneinheiten 27 mol%, MFR 4,0 g / 10 min, Schmelzpunkt 191°C
• · F171B: Menge an Ethyleneinheiten 32 mol%, MFR 3,7 g / 10 min, Schmelzpunkt 183°C
• · E105B: Menge an Ethyleneinheiten 44 mol%, MFR 13 g / 10 min, Schmelzpunkt 165°C
• · E171B: Menge an Ethyleneinheiten 44 mol%, MFR 3,3 g / 10 min, Schmelzpunkt 165°C
• · H171B:Menge an Ethyleneinheiten 38 mol%, MFR 3,4 g / 10 min, Schmelzpunkt 172°C
• · C109B: Menge an Ethyleneinheiten 35 mol%, MFR 21 g / 10 min, Schmelzpunkt 177°C

It should be noted that the "F171B" among EVOH (A) in Table 1 as well as the "E171B", "H171B" and "C109B" under EVOH (B) each include EVOHs from Kuraray Co., Ltd. are. The amount of ethylene units in the EVOHs, the MFR (at 210 ° C and 2160 g load) and the melting point were each as follows:

• · L171B: amount of ethylene units 27 mol%, MFR 4.0 g / 10 min, melting point 191 ° C
• F171B: Amount of ethylene units 32 mol%, MFR 3.7 g / 10 min, melting point 183 ° C
• · E105B: Amount of ethylene units 44 mol%, MFR 13 g / 10 min, melting point 165 ° C
• E171B: amount of ethylene units 44 mol%, MFR 3.3 g / 10 min, melting point 165 ° C
• · H171B: amount of ethylene units 38 mol%, MFR 3.4 g / 10 min, melting point 172 ° C
• C109B: amount of ethylene units 35 mol%, MFR 21 g / 10 min, melting point 177 ° C

Further, "UBE NYLON 1024B", "UBE NYLON 1030B" and "UBE NYLON 7024B" under PA (C) of Table 1 respectively designate PAs of Ube Industries, Ltd. "Ny6" in Table 1 designates nylon 6 and "Ny6, 12" designates nylon 6/12.

Pellets and monolayer films of the resulting plastic compositions were evaluated by the methods described above. The results of this evaluation are shown in Table 2. Further, Table 2 also shows the mixing ratios (A / B, (A + B) / C, B / C and D / C) of the individual components. When in the column for the TEM observation and the respective assessments in Table 2 is a "-", this means that the observation or assessment has not been carried out.

As shown in Table 2, each of Embodiments 1 to 29 achieves good gas barrier properties and resistance to prolonged heating. On the other hand, there are none of Comparative Examples 1 to 9 in which the gas barrier properties and the resistance to prolonged heating are good. In Comparative Example 1, in which the screw speed is high, and in Comparative Example 2, in which a screw having a large kneading strength was used, the kneading was too excessive, so that the above-described phase-separated structure was not formed, indicating the gas barrier properties and the resistance against prolonged heating deteriorates, and also a high gel content deteriorates the gas barrier properties and the resistance to prolonged heating. In Comparative Example 3, in which PA (C) was not contained, the resistance to prolonged heating deteriorated. In Comparative Example 4 which did not contain EVOH (B) and Comparative Example 5 in which EVOH (B) was used in which the melting point difference with EVOH (A) was low, the phase-separated structure described above was not formed. Due to the low melting point difference between EVOH (A) and EVOH (B), the gas barrier properties and the resistance to prolonged heating deteriorated, which deteriorates the gas barrier properties and the resistance to prolonged heating. In Comparative Example 6, in which a single-layered film was formed immediately after dry blending and the kneading strength of the screw was not adjusted (the kneading strength was not large), the kneading was insufficient so that the above-described phase-separated structure was not formed, resulting in the gas barrier properties and the Resistance to prolonged heating deteriorated, and also the gel content was low, which deteriorated the gas barrier properties and the resistance to prolonged heating. In Comparative Example 7, in which the content amount of PA (C) was comparatively large, the described phase-separated structure was not formed, which deteriorated the gas barrier properties, and also the gel content was small, which deteriorated the gas barrier properties. In Comparative Examples 8 and 9, the kneading degree was small, so that the above-described phase-separated structure was not formed, which deteriorated the resistance to prolonged heating, and also the gel content was low, which deteriorated the resistance to prolonged heating.

Among the embodiments, in the embodiment 21 in which the content amount of the fatty acid-based divalent metal salt (D) was small and in the embodiment 26 in which the content of the fatty acid-based divalent metal salt (D) was large, the evaluation of the heat stability 2 was a little worse , Further, in Embodiment 27, in which a higher fatty acid-based divalent metal salt was used instead of a lower fatty acid-based divalent metal salt, the trim recoverability was a little worse. Further, in Embodiments 25 and 26, in which the content amount of the fatty acid-based divalent metal salt was large, the evaluation of hue was relatively low. This shows that by including a certain amount of fatty acid-based divalent metal salt (D) and further, the fatty acid-based divalent metal salt (D) is a lower fatty acid-based divalent metal salt, the heat resistance, the trim recoverability and the hue are improved can.

INDUSTRIAL APPLICABILITY

The plastic composition of the present invention can be advantageously used as a packaging material and, in particular, as a packaging material for prolonged heating or as a packaging material for boiling.

LIST OF REFERENCE NUMBERS

11

sea phase

12

island phase

13

Third phase

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• JP 58129035A [0004]
• JP H04202549 A [0004]
• WO 2015/174396 [0004]
• JP 2014034647A [0037]
• WO 2011/136287 [0102]

Claims (18)

Plastic composition comprising: an ethylene-vinyl alcohol copolymer (A); an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and a polyamide (C); wherein the plastic composition has a phase separated structure having a sea phase, an island phase, and a third phase surrounded by the island phase; and wherein the sea phase comprises the ethylene-vinyl alcohol copolymer (A), the island phase comprises the ethylene-vinyl alcohol copolymer (B), and the third phase comprises the polyamide (C). Plastic composition according to Claim 1 wherein 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 at least 10 ° C. Plastic composition comprising: an ethylene-vinyl alcohol copolymer (A); an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and a polyamide (C); wherein 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 at least 10 ° C; and a gel content is at least 0.5% and at most 20%. Plastic composition according to one of Claims 1 to 3 wherein the mixing ratio (A / B) of the ethylene-vinyl alcohol copolymer (A) and the ethylene-vinyl alcohol copolymer (B) by mass is at least 1.0 and at most 20. Plastic composition according to one of Claims 1 to 4 wherein the mixing ratio ((A / B) / C) of the polyamide (C) to the entirety of ethylene-vinyl alcohol copolymer (A) and ethylene-vinyl alcohol copolymer (B) by mass is at least 0.67 and at most 99 is. Plastic composition according to one of Claims 1 to 5 wherein the mixing ratio (B / C) of the ethylene-vinyl alcohol copolymer (B) and the polyamide (C) by mass is at least 0.053 and at most 19. Plastic composition according to one of Claims 1 to 6 , wherein the melting point TmC of the polyamide (C) is at least 190 ° C. Plastic composition according to one of Claims 1 to 7 further comprising a fatty acid-based divalent metal salt (D); wherein the metal ion-converted content amount of the fatty acid-based divalent metal salt (D) relative to 100 parts by mass of the total of ethylene-vinyl alcohol copolymer (A), ethylene-vinyl alcohol copolymer (B) and polyamide (C) is at least 0.001 part by weight and at most 0.05 Mass parts is. Plastic composition according to Claim 8 wherein the metal ion-converted amount (D / C) of the fatty acid-based divalent metal salt (D) relative to the mass of the polyamide (C) is at least 3 μmol / g and at most 250 μmol / g. Plastic composition according to one of Claims 1 to 9 , wherein the plastic composition is in pellet form. Shaped body of a plastic composition according to one of Claims 1 to 10 , A molded article comprising: an ethylene-vinyl alcohol copolymer (A); an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and a polyamide (C); wherein the shaped body has a phase-separated structure having a sea phase, an island phase, and a third phase surrounded by the island phase; and wherein the sea phase comprises the ethylene-vinyl alcohol copolymer (A), the island phase comprises the ethylene-vinyl alcohol copolymer (B), and the third phase comprises the polyamide (C). Shaped body, comprising: an ethylene-vinyl alcohol copolymer (A); an ethylene-vinyl alcohol copolymer (B) having a melting point TmB below the melting point TmA of the ethylene-vinyl alcohol copolymer (A); and a polyamide (C); wherein 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 at least 10 ° C; and a gel content is at least 0.5% and at most 20%. Shaped body according to one of Claims 11 to 13 , wherein the shaped body is a film. Shaped body according to one of Claims 11 to 14 wherein the shaped body is a packaging material for prolonged heating or a packaging material for boiling. Secondary product of a shaped article according to one of the Claims 11 to 15 , Process for producing a plastic composition according to any one of Claims 1 to 10 composition comprising: a step of dry blending the ethylene-vinyl alcohol copolymer (A), the ethylene-vinyl alcohol copolymer (B) and the polyamide (C), and a step of melt-kneading the mixture obtained in the dry blending step. A method of producing a shaped article, comprising a step of melt-shaping the plastic composition according to any one of Claims 1 to 10 ,

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