JP2003327619A - Manufacturing method for modified ethylene-vinyl alcohol copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient manufacturing method for a modified ethylene- vinyl alcohol copolymer excellent in barrier property, transparency, extensibility, and resistance to bending. <P>SOLUTION: The modified ethylene-vinyl alcohol copolymer (C) is manufactured by melt kneading with an extruder an ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound (B) having a mol.wt. of 500 or less in the presence of a catalyst (D) containing a metal ion belonging to No.3-12 groups of the periodic table. In a preferable embodiment, after the above components are melt-kneaded, a catalyst deactivator (E) is added and a further melt kneading is conducted. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a modified ethylene-vinyl alcohol copolymer. The present invention also relates to a modified ethylene-vinyl alcohol copolymer having excellent barrier properties, transparency, stretchability and bending resistance, and a barrier material comprising the same.

[0002]

2. Description of the Related Art An ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is excellent in transparency and gas barrier property, but has a drawback that it lacks in stretchability and bending resistance. To remedy this drawback, EVOH
There is known a method of blending a flexible resin such as an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer. However, this method has a drawback that the transparency is greatly reduced.

Further, it has excellent stress cracking resistance, polar solvent resistance and water resistance, and also has good gas barrier properties against oxygen and the like and excellent moldability, especially stretchability, and has an ethylene content of 25 to 60 mol%. Silicon-containing E having a saponification degree of 95 mol% or more and a silicon content of 0.0005 to 0.2 mol%
A melt-molding material composed of VOH is known (Japanese Patent Laid-Open No. Sho 6).
0-144304).

JP-A-50-12186 discloses that the ethylene content is 20 to 90 mol% and the saponification degree is 9%.
0.01 with respect to 100 parts by weight of EVOH which is 5% or more
Disclosed is a method for producing an EVOH-modified product with improved moldability, which comprises reacting ˜0.8 parts by weight of a polyvalent epoxy compound.

[0005]

However, in the above-mentioned conventional techniques, the stretchability and flex resistance of EVOH are not always sufficient.
Furthermore, the stretchability and flex resistance of EVOH and transparency were not satisfied at the same time.

[0006] Japanese Patent Laid-Open No. 50-12186 discloses, as an improvement in molding processability, an improvement in neck-in (a phenomenon in which a product width is narrower than a die / slit width) when EVOH is formed into a film by a T-die. Is listed,
No mention is made of the improvement in stretchability and flex resistance that is the object of the present invention. In addition, EV described in the above publication, in which a specific amount of polyvalent epoxy compound is reacted
With OH, the effect of improving stretchability and bending resistance cannot be obtained. Furthermore, when a polyvalent epoxy compound is used, it is difficult to produce an EVOH specified by the present invention in which the amount of modification by the epoxy compound is within a specific range.

An object of the present invention is to provide a modified ethylene-vinyl alcohol copolymer having excellent barrier properties, transparency, stretchability and flex resistance, and a barrier material comprising the same. It also provides a method for producing such a modified ethylene-vinyl alcohol copolymer.

[0008]

[Means for Solving the Problems]
A vinyl alcohol copolymer (A) and a monovalent epoxy compound (B) having a molecular weight of 500 or less in an extruder in the presence of a catalyst (D) containing an ion of a metal belonging to Groups 3 to 12 of the periodic table. It is solved by providing a method for producing a modified ethylene-vinyl alcohol copolymer (C), which is characterized by melt-kneading.

In a preferred embodiment, the ethylene-vinyl alcohol copolymer (A) has an ethylene content of 5 to 55 mol% and a saponification degree of 90% or more (C). ) Is a manufacturing method. In a preferred embodiment, the monovalent epoxy compound (B) is a method for producing a modified ethylene-vinyl alcohol copolymer (C), which is an epoxy compound having 2 to 8 carbon atoms.

In a preferred embodiment, the catalyst (D) is a method for producing a modified ethylene-vinyl alcohol copolymer (C) containing zinc ions. Also, in a preferred embodiment,
Catalyst (D) is a modified ethylene-containing sulfonate ion
It is a method for producing a vinyl alcohol copolymer (C).

In a preferred embodiment, 1 to 50 parts by weight of the monovalent epoxy compound (B) is melt-kneaded with 100 parts by weight of the ethylene-vinyl alcohol copolymer (A) to prepare a modified ethylene-vinyl alcohol copolymer ( It is the manufacturing method of C). Further, in a preferred embodiment, a modified ethylene-vinyl alcohol copolymer in which 0.1 to 20 μmol / g of the catalyst (D) is present in terms of the number of moles of metal ion relative to the weight of the ethylene-vinyl alcohol copolymer (A). It is a manufacturing method of (C).

In a preferred embodiment, a modified ethylene-vinyl alcohol copolymer is prepared by adding a mixture of a monovalent epoxy compound (B) and a catalyst (D) to the ethylene-vinyl alcohol copolymer (A) in a molten state. It is a method for producing a united product (C).

In a preferred embodiment, the ethylene-vinyl alcohol copolymer (A) and the monovalent epoxy compound (B) are melt-kneaded in the presence of the catalyst (D), and then the catalyst deactivator (E) is added. It is a method for producing a modified ethylene-vinyl alcohol copolymer (C) which is added and further melt-kneaded. A more preferred embodiment is a method for producing a modified ethylene-vinyl alcohol copolymer (C) in which the catalyst deactivator (E) is a chelating agent.

In a preferred embodiment, the modified ethylene-in which the ratio (E / D) of the number of moles of the catalyst deactivator (E) to the number of moles of metal ions contained in the catalyst (D) is 0.2 to 10.
It is a method for producing a vinyl alcohol copolymer (C). Further, in a preferred embodiment, the ethylene-vinyl alcohol copolymer (A) and the monovalent epoxy compound (B) are melt-kneaded in the presence of the catalyst (D) to obtain an unreacted monovalent epoxy compound (B). ) Is removed and then the catalyst deactivator (E) is added to the modified ethylene-vinyl alcohol copolymer (C).

The problem to be solved by the present invention is as follows.
It contains 0.3 to 40 mol% of the following structural unit (I) and contains 0.1 to 20 ions of a metal belonging to Groups 3 to 12 of the periodic table.
It is also achieved by providing a modified ethylene-vinyl alcohol copolymer (C) containing μmol / g.

[0016]

[Chemical 2]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and 3 carbon atoms.
Represents an alicyclic hydrocarbon group having 10 to 10 or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ¹ , R ² , R ³ and R ⁴ may be the same group or different. R ³ and R ⁴ may be bonded. Further, R ¹ , R ² , R ³ and R ⁴ may have a hydroxyl group, a carboxyl group or a halogen atom. )

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) containing a sulfonate ion is used. In a more preferred embodiment, the content of alkali metal ion is 1 to 50 of the content of sulfonate ion.
It is a modified ethylene-vinyl alcohol copolymer (C) which is double (molar ratio).

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a barrier material. In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a molded article. In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a multilayer structure containing at least one layer composed of the modified ethylene-vinyl alcohol copolymer (C).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a catalyst (D) containing EVOH (A) and a monovalent epoxy compound (B) having a molecular weight of 500 or less and an ion of a metal belonging to Groups 3 to 12 of the periodic table.
Is a method for producing a modified EVOH (C), which comprises melt-kneading in an extruder in the presence of.

The EVOH (A) used in the present invention is preferably one obtained by saponifying an ethylene-vinyl ester copolymer. A typical vinyl ester used in the production of EVOH is vinyl acetate, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used. Further, as long as the object of the present invention is not impaired, other comonomers, for example, propylene, butylene, isobutene,
Α-Olefins such as 4-methyl-1-pentene, 1-hexene and 1-octene; unsaturated carboxylic acids such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate or esters thereof; Vinylsilane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidone such as N-vinylpyrrolidone can also be copolymerized.

When EVOH in which a vinylsilane compound is copolymerized as a copolymerization component is used as EVOH (A), the copolymerization amount is preferably 0.0002 to 0.2 mol%. By having a vinyl silane compound as a copolymerization component in such a range, the consistency of the melt viscosity between the base resin and the modified EVOH (C) at the time of performing coextrusion molding is improved, and a homogeneous coextrusion multilayer film molded product is obtained. May be possible to manufacture. In particular, when a base resin having a high melt viscosity is used, it becomes easy to obtain a homogeneous coextrusion multilayer film molded product. Here, examples of the vinylsilane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

The ethylene content of EVOH (A) used in the present invention is preferably 5 to 55 mol%. From the viewpoint that the modified EVOH (C) of the present invention obtains good stretchability and bending resistance, the lower limit of the ethylene content of EVOH (A) is more preferably 10 mol% or more, and further preferably 20 mol% or more, particularly preferably 25 mol%
It is above, and more preferably, it is 31 mol% or more. On the other hand, from the viewpoint of the gas barrier property of the modified EVOH (C) of the present invention, the upper limit of the ethylene content of EVOH (A) is more preferably 50 mol% or less, and further preferably 45 mol% or less. . If the ethylene content is less than 5 mol%, the melt moldability may deteriorate, and if it exceeds 55 mol%, the gas barrier property may be insufficient.

When the EVOH (A) is composed of a mixture of two or more kinds of EVOH having different ethylene contents, the ethylene content is the average value calculated from the blending weight ratio.

Further, EVOH used in the present invention
The saponification degree of the vinyl ester component (A) is preferably 9
It is 0% or more. The saponification degree of the vinyl ester component is more preferably 95% or more, further preferably 98.
% Or more, and optimally 99% or more. When the saponification degree is less than 90%, not only the gas barrier property, particularly the gas barrier property at high humidity may be deteriorated, but also the thermal stability may be insufficient, and gels or lumps may easily occur in the molded product. is there.

When EVOH (A) is composed of a mixture of two or more kinds of EVOH having different saponification degrees, the average value calculated from the blending weight ratio is the saponification degree.

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

Further, EVOH blended with a boron compound may be used as EVOH (A) within a range that does not impair the object of the present invention. Examples of the boron compound include boric acid, boric acid ester, borate, and borohydrides. Specifically, examples of boric acids include orthoboric acid, metaboric acid, tetraboric acid, etc., examples of boric acid esters include triethyl borate, trimethyl borate, etc. Alkali metal salts of acids, alkaline earth metal salts,
Examples include borax. Among these compounds, orthoboric acid (hereinafter sometimes simply referred to as boric acid)
Is preferred.

When EVOH blended with a boron compound is used as EVOH (A), the content of the boron compound is preferably 20 to 2000 pp in terms of boron element.
m, more preferably 50 to 1000 ppm. By blending the boron compound within this range, EVOH in which torque fluctuation during heating and melting is suppressed can be obtained. If it is less than 20 ppm, such effect is small, and
If it exceeds 00 ppm, gelation tends to occur, which may result in poor moldability.

Further, EVOH containing a phosphoric acid compound may be used as EVOH (A), but it is preferable that the amount of phosphate is as small as possible because it deactivates the catalyst.
This makes it possible to stabilize the quality (coloring, etc.) of the resin. The phosphoric acid compound used in the present invention is not particularly limited, and various acids such as phosphoric acid and phosphorous acid and salts thereof can be used. As phosphate, primary phosphate,
It may be contained in any form of a secondary phosphate and a tertiary phosphate, but a primary phosphate is preferred. Although the cation species is not particularly limited, it is preferably an alkali metal salt. Among these, sodium dihydrogen phosphate and potassium dihydrogen phosphate are preferable.

The content of the phosphoric acid compound in the EVOH (A) used in the present invention is preferably 200 in terms of phosphate radical.
ppm or less, more preferably 100 ppm or less, most preferably 50 ppm or less.

As will be described later, the modified EVO of the present invention
H (C) is preferably obtained by reacting EVOH (A) with a monovalent epoxy compound (B) having a molecular weight of 500 or less in an extruder, in which case EVOH
Is exposed to heating conditions. At this time, if the EVOH (A) excessively contains an alkali metal salt and / or an alkaline earth metal salt, the catalyst (D) of the present invention is deactivated, and therefore the addition amount thereof should be as small as possible. preferable. Further, if the content of the alkali metal salt and / or the alkaline earth metal salt is too large, the resulting modified EVOH (C) will be obtained.
There is also a possibility that coloring may occur, and a decrease in melt viscosity may deteriorate moldability.

To avoid the above problems, EVOH
The alkali metal salt contained in (A) is 5 in terms of metal element.
It is preferably 0 ppm or less. In a more preferred embodiment, the alkali metal salt contained in EVOH (A) is 30 ppm or less in terms of metal element conversion value, and more preferably 20 ppm or less. From the same viewpoint, E
The alkaline earth metal salt contained in VOH (A) is preferably 20 ppm or less in terms of metal element conversion, and 10 p
It is more preferably pm or less, further preferably 5 ppm or less, and most preferably the EVOH (A) does not substantially contain an alkaline earth metal salt.

EVOH (A) containing a heat stabilizer and an antioxidant may be used as long as it does not impair the object of the present invention.

The EVOH (A) used in the present invention preferably has an intrinsic viscosity of 0.06 L / g or more. EV
The intrinsic viscosity of OH (A) is more preferably 0.07-0.
Within the range of 2 L / g, more preferably 0.075
0.15 L / g, and particularly preferably 0.080
It is 0.12 L / g. When the intrinsic viscosity of EVOH (A) is less than 0.06 L / g, stretchability, flexibility and flex resistance may be reduced. In addition, if the intrinsic viscosity of EVOH (A) exceeds 0.2 L / g, gels or hard spots may be likely to occur in the molded product made of the modified EVOH (C).

A suitable melt flow rate (MFR) of EVOH (A) used in the present invention (190 ° C., 2160)
g under load) is 0.1 to 30 g / 10 minutes, more preferably 0.3 to 25 g / 10 minutes, and even more preferably 0.5 to 2
It is 0 g / 10 minutes. However, if the melting point is around 190 ° C. or exceeds 190 ° C., it is measured at a plurality of temperatures above the melting point under a load of 2160 g, and the reciprocal of absolute temperature is plotted on the horizontal axis and the logarithm of MFR is plotted on the vertical axis in a semi-log graph, The value is extrapolated to 190 ° C. Two or more types of EVOH with different MFR
It is also possible to mix and use.

It is essential that the monovalent epoxy compound (B) having a molecular weight of 500 or less used in the present invention is a monovalent epoxy compound. That is, it must be an epoxy compound having only one epoxy group in the molecule. The effect of the present invention cannot be obtained when a divalent or higher polyvalent epoxy compound is used. However, a very small amount of the polyvalent epoxy compound may be contained in the production process of the monovalent epoxy compound. A monovalent epoxy compound containing a very small amount of a polyvalent epoxy compound may be used as the monovalent epoxy compound (B) having a molecular weight of 500 or less in the present invention as long as the effect of the present invention is not impaired. is there.

The monovalent epoxy compound (B) having a molecular weight of 500 or less used in the present invention is not particularly limited. Specifically, compounds represented by the following formulas (III) to (IX) are preferably used.

[0039]

[Chemical 3]

[0040]

[Chemical 4]

[0041]

[Chemical 5]

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

[0045]

[Chemical 9]

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are
Hydrogen atom, aliphatic hydrocarbon group having 1 to 10 carbon atoms (alkyl group or alkenyl group, etc.), alicyclic hydrocarbon group having 3 to 10 carbon atoms (cycloalkyl group, cycloalkenyl group, etc.), 6 carbon atoms Represents 10 aromatic hydrocarbon groups (such as a phenyl group). Further, i, j, k, l and m are 1 to 8
Represents the integer. )

Examples of the monovalent epoxy compound (B) represented by the above formula (III) having a molecular weight of 500 or less include epoxyethane (ethylene oxide), epoxypropane, 1,2.
-Epoxybutane, 2,3-epoxybutane, 3-methyl-1,2-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 3-methyl-1,2-
Epoxy pentane, 4-methyl-1,2-epoxypentane, 4-methyl-2,3-epoxypentane, 3-ethyl-1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2-epoxyhexane, 4
-Methyl-1,2-epoxyhexane, 5-methyl-
1,2-epoxyhexane, 3-ethyl-1,2-epoxyhexane, 3-propyl-1,2-epoxyhexane, 4-ethyl-1,2-epoxyhexane, 5-methyl-1,2-epoxyhexane , 4-methyl-2,3-
Epoxyhexane, 4-ethyl-2,3-epoxyhexane, 2-methyl-3,4-epoxyhexane, 2,5
-Dimethyl-3,4-epoxyhexane, 3-methyl-
1,2-epoxyheptane, 4-methyl-1,2-epoxyheptane, 5-methyl-1,2-epoxyheptane, 6-methyl-1,2-epoxyheptane, 3-ethyl-1, 2-epoxyheptane, 3-propyl-1,2
-Epoxy heptane, 3-butyl-1,2-epoxy heptane, 4-ethyl-1,2-epoxy heptane, 4-
Propyl-1,2-epoxy heptane, 5-ethyl-
1,2-epoxyheptane, 4-methyl-2,3-epoxyheptane, 4-ethyl-2,3-epoxyheptane, 4-propyl-2,3-epoxyheptane, 2-methyl-3, 4-epoxyheptane, 5-methyl-3,4
-Epoxyheptane, 5-ethyl-3,4-epoxyheptane, 2,5-dimethyl-3,4-epoxyheptane, 2-methyl-5-ethyl-3,4-epoxyheptane, 1,2 -Epoxyheptane, 2,3-epoxyheptane, 3,4-epoxyheptane, 1,2-epoxyoctane, 2,3-epoxyoctane, 3,4-epoxyoctane, 4,5-epoxyoctane, 1,2- Epoxynonane, 2,3-epoxynonane, 3,4-epoxynonane, 4,5-epoxynonane, 1,2-epoxydecane, 2,3-epoxydecane, 3,4-epoxydecane, 4,5-epoxy Decane, 5,6-epoxydecane, 1,2-epoxyundecane, 2,3-epoxyundecane, 3,4-epoxyundecane, 4,5-epoxyundecane, 5, - epoxy undecane, 1, 2
-Epoxydodecane, 2,3-epoxydodecane, 3,
4-epoxydodecane, 4,5-epoxydodecane,
5,6-epoxydodecane, 6,7-epoxydodecane, epoxyethylbenzene, 1-phenyl-1,2-
Epoxy propane, 3-phenyl-1,2-epoxy propane, 1-phenyl-1,2-epoxy butane, 3-
Phenyl-1,2-epoxybutane, 4-phenyl-
1,2-epoxybutane, 1-phenyl-1,2-epoxypentane, 3-phenyl-1,2-epoxypentane, 4-phenyl-1,2-epoxypentane, 5-phenyl-1,2-epoxypentane , 1-phenyl-
1,2-epoxyhexane, 3-phenyl-1,2-epoxyhexane, 4-phenyl-1,2-epoxyhexane, 5-phenyl-1,2-epoxyhexane, 6-
Examples thereof include phenyl-1,2-epoxyhexane.

As the monovalent epoxy compound (B) represented by the above formula (IV) having a molecular weight of 500 or less, methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, Isobutyl glycidyl ether, tert-butyl glycidyl ether,
1,2-epoxy-3-pentyloxypropane, 1,
2-epoxy-3-hexyloxypropane, 1,2-
Epoxy-3-heptyloxypropane, 1,2-epoxy-3-octyloxypropane, 1,2-epoxy-3-phenoxypropane, 1,2-epoxy-3-benzyloxypropane, 1,2-epoxy-4 -Methoxybutane, 1,2-epoxy-4-ethoxybutane,
1,2-epoxy-4-propoxybutane, 1,2-epoxy-4-butoxybutane, 1,2-epoxy-4-
Pentyloxybutane, 1,2-epoxy-4-hexyloxybutane, 1,2-epoxy-4-heptyloxybutane, 1,2-epoxy-4-phenoxybutane,
1,2-epoxy-4-benzyloxybutane, 1,2
-Epoxy-5-methoxypentane, 1,2-epoxy-5-ethoxypentane, 1,2-epoxy-5-propoxypentane, 1,2-epoxy-5-butoxypentane, 1,2-epoxy-5-pentyl Oxypentane, 1,2-epoxy-5-hexyloxypentane,
1,2-epoxy-5-phenoxypentane, 1,2-
Epoxy-6-methoxyhexane, 1,2-epoxy-
6-ethoxyhexane, 1,2-epoxy-6-propoxyhexane, 1,2-epoxy-6-butoxyhexane, 1,2-epoxy-6-heptyloxyhexane,
1,2-epoxy-7-methoxyheptane, 1,2-epoxy-7-ethoxyheptane, 1,2-epoxy-7
-Propoxyheptane, 1,2-epoxy-7-butyloxyheptane, 1,2-epoxy-8-methoxyheptane, 1,2-epoxy-8-ethoxyheptane, 1,
2-epoxy-8-butoxyheptane, glycidol,
3,4-epoxy-1-butanol, 4,5-epoxy-1-pentanol, 5,6-epoxy-1-hexanol, 6,7-epoxy-1-heptanol, 7,8-
Epoxy-1-octanol, 8,9-epoxy-1-
Nonanol, 9,10-epoxy-1-decanol, 1
Examples thereof include 0,11-epoxy-1-undecanol.

Examples of the monovalent epoxy compound (B) represented by the above formula (V) having a molecular weight of 500 or less include ethylene glycol monoglycidyl ether, propanediol monoglycidyl ether, butanediol monoglycidyl ether and heptanediol monoglycidyl ether. , Hexanediol monoglycidyl ether, heptanediol monoglycidyl ether, octanediol monoglycidyl ether and the like.

The monovalent epoxy compound (B) represented by the above formula (VI) having a molecular weight of 500 or less is 3- (2,3-
Epoxy) propoxy-1-propene, 4- (2,3-
Epoxy) propoxy-1-butene, 5- (2,3-epoxy) propoxy-1-pentene, 6- (2,3-epoxy) propoxy-1-hexene, 7- (2,3-epoxy) propoxy-1. -Heptene, 8- (2,3-epoxy) propoxy-1-octene and the like.

As the monovalent epoxy compound (B) represented by the above formula (VII) having a molecular weight of 500 or less, 3,4-epoxy-2-butanol, 2,3-epoxy-1-butanol and 3,4- Epoxy-2-pentanol, 2,3-
Epoxy-1-pentanol, 1,2-epoxy-3-
Pentanol, 2,3-epoxy-4-methyl-1-pentanol, 2,3-epoxy-4,4-dimethyl-1
-Pentanol, 2,3-epoxy-1-hexanol, 3,4-epoxy-2-hexanol, 4,5-epoxy-3-hexanol, 1,2-epoxy-3-hexanol, 2,3-epoxy- 4-methyl-1-hexanol, 2,3-epoxy-4-ethyl-1-hexanol, 2,3-epoxy-4,4-dimethyl-1-hexanol, 2,3-epoxy-4,4-diethyl- 1
-Hexanol, 2,3-epoxy-4-methyl-4-
Ethyl-1-hexanol, 3,4-epoxy-5-methyl-2-hexanol, 3,4-epoxy-5,5-
Dimethyl-2-hexanol, 3,4-epoxy-2-
Heptanol, 2,3-epoxy-1-heptanol,
4,5-epoxy-3-heptanol, 2,3-epoxy-4-heptanol, 1,2-epoxy-3-heptanol, 2,3-epoxy-1-octanol, 3,4
-Epoxy-2-octanol, 4,5-epoxy-3
-Octanol, 5,6-epoxy-4-octanol, 2,3-epoxy-4-octanol, 1,2-epoxy-3-octanol, 2,3-epoxy-1-nonanol, 3,4-epoxy-2 -Nonanol, 4,5
-Epoxy-3-nonanol, 5,6-epoxy-4-
Nonanol, 3,4-epoxy-5-nonanol, 2,
3-epoxy-4-nonanol, 1,2-epoxy-3
-Nonanol, 2,3-epoxy-1-decanol,
3,4-epoxy-2-decanol, 4,5-epoxy-3-decanol, 5,6-epoxy-4-decanol, 6,7-epoxy-5-decanol, 3,4-epoxy-5-decanol, 2,3-epoxy-4-decanol, 1,2-epoxy-3-decanol and the like can be mentioned.

As the monovalent epoxy compound (B) represented by the above formula (VIII) having a molecular weight of 500 or less, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloheptane, 1 , 2-epoxycyclooctane, 1,2-epoxycyclononane,
1,2-epoxycyclodecane, 1,2-epoxycycloundecane, 1,2-epoxycyclododecane and the like can be mentioned.

The monovalent epoxy compound (B) represented by the above formula (IX) having a molecular weight of 500 or less includes 3,4-epoxycyclopentene, 3,4-epoxycyclohexene,
3,4-epoxycycloheptene, 3,4-epoxycyclooctene, 3,4-epoxycyclononene, 1,2
-Epoxycyclodecene, 1,2-epoxycycloundecene, 1,2-epoxycyclododecene and the like.

As the monovalent epoxy compound (B) having a molecular weight of 500 or less used in the present invention, an epoxy compound having 2 to 8 carbon atoms is particularly preferable. From the viewpoint of easy handling of the compound and reactivity with EVOH (A), the monovalent epoxy compound (B) preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. . Further, the monovalent epoxy compound (B) is preferably a compound represented by the above formula (III) or (IV). From the viewpoint of reactivity with EVOH (A) and gas barrier property of the obtained modified EVOH (C), 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane and glycidol are particularly preferable, Of these, epoxypropane and glycidol are preferable. In applications where hygiene is required, such as food packaging applications, beverage packaging applications, pharmaceutical packaging applications, etc., 1,2-epoxybutane, 2, as the epoxy compound (B), 2,
It is preferable to use 3-epoxybutane, epoxypropane and epoxyethane, and particularly preferable to use epoxypropane.

A suitable amount of the monovalent epoxy compound (B) mixed is 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and particularly preferably 100 parts by weight of EVOH (A). Is 5 to 35 parts by weight.

In the production method of the present invention, the above EVOH
Modified EVOH by melt-kneading (A) and the monovalent epoxy compound (B) in an extruder and reacting
(C) is produced. As a method other than melt-kneading in an extruder, a production method by a solution reaction can be considered.
Monovalent epoxy compound (B) in the presence of a catalyst in the solution of (A)
The modified EVOH (C) can also be obtained by reacting However, it is more preferable to melt-knead the EVOH (A) and the monovalent epoxy compound (B) in the extruder for the reasons described below.

When the production method of reacting in the extruder is compared with the production method of solution reaction, in the case of solution reaction, EV
A solvent that dissolves OH (A) is required, and the solvent needs to be collected and removed from the reaction system after the reaction is completed, which complicates the process. Further, in order to increase the reactivity between EVOH (A) and the monovalent epoxy compound (B), it is preferable to maintain the reaction system under heating and / or pressurizing conditions. Thus, in the reaction in the extruder, it is easy to maintain the heating and / or pressurizing conditions of such a reaction system, and from that viewpoint, the reaction in the extruder has a great merit.

Further, EVOH (A) is obtained by solution reaction.
When the reaction is carried out with the monovalent epoxy compound (B), it is not always easy to control the reaction, and there is a risk that the reaction will proceed excessively. That is, as a result of the reaction between the EVOH (A) and the monovalent epoxy compound (B), a modified EVOH (C) having the following structural unit (I) is obtained, but the hydroxyl group contained in the structural unit (I) is Furthermore, the reaction with the monovalent epoxy compound (B) may result in a product different from the structural unit specified in the present invention.

[0059]

[Chemical 10]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group or an alkenyl group), and an aliphatic group having 3 to 10 carbon atoms. It represents a cyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group, etc.) or an aromatic hydrocarbon group having 6 to 10 carbon atoms (phenyl group, etc.) R ¹ , R ² , R ³ and R ⁴ may be the same groups. R ³ and R ⁴ may be bonded (provided that R ³ and R ⁴ are both hydrogen atoms), and R ¹ and R ⁴ are the same or different. ² , R ³ and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group and a halogen atom.)

Specifically, when the monovalent epoxy compound (B) is ethylene oxide, an EV containing a structural unit (II) shown below is produced due to the progress of the above-mentioned excess reaction.
OH will be generated.

[0062]

[Chemical 11]

(In the formula, n represents a natural number of 1 or more.)

As a result of investigations by the present inventors, a modified EVOH obtained by increasing the proportion of the structural unit (II) different from the structural unit (I).
It was revealed that the gas barrier property of (C) was lowered. Furthermore, it has been found that when the reaction of EVOH (A) and the monovalent epoxy compound (B) is carried out in the extruder, the occurrence of such side reaction can be effectively suppressed. From this viewpoint, the modified EVOH is obtained by reacting the EVOH (A) with the monovalent epoxy compound (B) in the extruder.
The method of producing (C) is preferred.

Further, since the monovalent epoxy compound (B) having a molecular weight of 500 or less used in the present invention does not always have a high boiling point, in the production method by the solution reaction,
When the reaction system is heated, the monovalent epoxy compound (B) may volatilize outside the system. However, it is possible to suppress the volatilization of the monovalent epoxy compound (B) out of the system by reacting the EVOH (A) with the monovalent epoxy compound (B) in the extruder. In particular, when the monovalent epoxy compound (B) is added to the extruder, the reactivity between the EVOH (A) and the monovalent epoxy compound (B) is increased by press-fitting under pressure, and the monovalent epoxy compound is also added. The volatilization of (B) out of the system can be significantly suppressed.

In the production method of the present invention, EVOH (A) and monovalent epoxy compound (B) are extruded in the presence of a catalyst (D) containing an ion of a metal belonging to Groups 3 to 12 of the periodic table. Melt and knead in. The presence of the catalyst (D) containing the ions of the metal belonging to Groups 3 to 12 of the periodic table enables the EVOH to be efficiently produced even when melt kneading at a lower temperature.
(A) and the monovalent epoxy compound (B) can be reacted. That is, the modified EVOH (C) having a large modification amount can be easily obtained even by melt-kneading at a relatively low temperature. EVOH is not necessarily a resin having good melt stability at high temperatures, and thus melt kneading at low temperatures is preferable in that deterioration of the resin can be prevented. When the EVOH (A) is reacted with the monovalent epoxy compound (B) without using the catalyst (D), the MFR of the resulting modified EVOH (C) is M of the raw material EVOH (A).
Although it tends to be lower than FR, MFR hardly changes when catalyst (D) is used.

The catalyst (D) used in the present invention contains an ion of a metal belonging to Groups 3 to 12 of the periodic table. The most important metal ion used in the catalyst (D) is that it has a suitable Lewis acidity, and from this point, a metal ion belonging to Groups 3 to 12 of the Periodic Table is used. Among these, ions of metals belonging to Group 3 or Group 12 of the periodic table are suitable because they have appropriate Lewis acidity, and ions of zinc, yttrium, and gadolinium are more preferred. Among them, the catalyst (D) containing zinc ions has extremely high catalytic activity,
Moreover, the modified EVOH (C) obtained is excellent in thermal stability and is optimal.

It is preferable that the added amount of metal ions belonging to Groups 3 to 12 of the periodic table is 0.1 to 20 μmol / g in terms of the number of moles of metal ions with respect to the weight of EVOH (A). If the amount is too large, EVOH may gel during melt-kneading, and more preferably 10 μmol / g or less. On the other hand, if the amount is too small, the effect of adding the catalyst (D) may not be sufficiently exhibited, and more preferably 0.5
It is at least μmol / g. The suitable addition amount of the ions of the metals belonging to Groups 3 to 12 of the Periodic Table varies depending on the type of the metal used and the type of the anion described below. It should be done.

The anionic species of the catalyst (D) containing an ion of a metal belonging to Groups 3 to 12 of the periodic table is not particularly limited, but its conjugate acid is a monovalent one having a strong acid equal to or higher than sulfuric acid. It is preferable to include an anion. Since the anion in which the conjugate acid is a strong acid is usually low in nucleophilicity, it is difficult to react with the monovalent epoxy compound (B), and it is possible to prevent the anion species from being consumed by the nucleophilic reaction and loss of catalytic activity. is there. Also, by having such an anion as a counter ion, the Lewis acidity of the catalyst (D) is improved and the catalytic activity is improved.

As the monovalent anion whose conjugate acid is a strong acid equal to or more than sulfuric acid, sulfonic acid such as methanesulfonic acid ion, ethanesulfonic acid ion, trifluoromethanesulfonic acid ion, benzenesulfonic acid ion and toluenesulfonic acid ion can be used. Ion; chloride ion, bromide ion,
Halogen ions such as iodine ion; perchlorate ion; tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), hexafluoroarsinate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion, etc. Anions having 4 or more fluorine atoms; tetraphenylborate derivative ions such as tetrakis (pentafluorophenyl) borate ion; tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, bis (undecahydride-7, 8-
Dicarbaundecaborate) cobalt (III) ion,
Examples include carborane derivative ions such as bis (undecahydride-7,8-dicarboundecaborate) iron (III) ion.

When the catalyst (D) containing anionic species such as hexafluorophosphate and tetrafluoroborate among the anionic species exemplified above is used, the anionic species themselves are thermally stable and very nucleophilic. Low,
The anionic species may react with the hydroxyl group in EVOH to generate hydrogen fluoride, which may adversely affect the thermal stability of the resin. Also, the carborane derivative ion of cobalt is EV
Although it does not react with OH and the anion species themselves are thermally stable, they are very expensive.

The sulfonate ion is preferable as the anion species of the catalyst (D) because it does not react with EVOH, the anion species itself is thermally stable, and the price is appropriate. Examples of suitable sulfonate ion include methanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, and toluenesulfonate ion, and trifluoromethanesulfonate ion is most suitable.

The presumed mechanism of the reaction between EVOH (A) and monovalent epoxy compound (B) when zinc ion is used as the cation species of catalyst (D) and trifluoromethanesulfonate ion is used as the anion species is described below. It is shown in formula (X).

[0074]

[Chemical 12]

That is, the oxygen atom of the epoxy group of the monovalent epoxy compound (B) is coordinated with the zinc ion bonded to the hydroxyl group of EVOH in the form of a metal alkoxide, and the epoxy group is opened through the 6-membered ring transition state. I presume that. Here, since the conjugate acid of the trifluoromethanesulfonate ion, which is the counter ion of the zinc ion in the transition state, is a strong acid, the Lewis acidity of the zinc ion increases,
The catalytic activity is improved. On the other hand, the trifluoromethanesulfonate ion which is present as a counter ion itself does not react with the hydroxyl group of EVOH or the epoxy group of the monovalent epoxy compound (B), and is itself thermally stable, so that a side reaction occurs. The ring-opening reaction proceeds smoothly.

As described above, it is preferable that the catalyst (D) used in the present invention has a monovalent anion whose conjugate acid is a strong acid equal to or more than sulfuric acid. It is not necessary that all of the anionic species of are the same anionic species. Rather, it is preferable that the conjugated acid simultaneously contains an anion that is a weak acid. If the reaction mechanism is represented by the above formula (X), EV
When OH reacts with the catalyst (D) to form a metal alkoxide, one of the anions is released in the system as a conjugate acid.
If it is a strong acid, it may react with the monovalent epoxy compound (B) and may also adversely affect the melt stability of EVOH.

Examples of anions in which the conjugate acid is a weak acid include alkyl anions, aryl anions, alkoxides, aryloxy anions, carboxylates, and acetylacetonate and its derivatives. Among them, alkoxides, carboxylates, acetylacetonates and their derivatives are preferably used.

The number of moles of the anion in which the conjugate acid is a strong acid equal to or more than sulfuric acid is preferably 0.2 to 1.5 times the number of moles of the metal ion in the catalyst (D). If the molar ratio is less than 0.2 times, the catalytic activity may be insufficient, and it is more preferably 0.3 times or more, further preferably 0.4 times or more. On the other hand, if the above molar ratio exceeds 1.5 times, EVOH may gel, and it is more preferably 1.2 times or less. The molar ratio is optimally 1 time. When EVOH (A) as a raw material contains an alkali metal salt such as sodium acetate, the number of moles of anion, which is a strong acid whose conjugate acid is equal to or higher than that of sulfuric acid, is increased by the amount that is neutralized and consumed. Can be kept.

The method for preparing the catalyst (D) is not particularly limited, but as a suitable method, there are 3 to 12 of the periodic table.
A method of dissolving or dispersing a compound of a metal belonging to the group and adding a strong acid (sulfonic acid or the like) whose conjugate acid is equal to or higher than that of sulfuric acid to the solution or suspension obtained is mentioned. Examples of compounds of metals belonging to Groups 3 to 12 of the periodic table used as raw materials include alkyl metals, aryl metals, metal alkoxides, metal aryl oxides, metal carboxylates, and metal acetylacetonates. Here, when the strong acid is added to the solution or suspension of the compound of the metal belonging to Groups 3 to 12 of the periodic table, it is preferable to add it little by little. The solution containing the catalyst (D) thus obtained can be introduced directly into the extruder.

As a solvent for dissolving or dispersing a metal compound belonging to Groups 3 to 12 of the periodic table, an organic solvent, particularly an ether solvent is preferable. This is because it is difficult to react even at the temperature in the extruder and the solubility of the metal compound is good. Examples of ether solvents include dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like. As the solvent used,
It is preferable that the metal compound has excellent solubility, has a relatively low boiling point, and can be almost completely removed by the vent of the extruder. In that respect diethylene glycol dimethyl ether,
1,2-dimethoxyethane and tetrahydrofuran are especially preferred.

Further, in the above-mentioned method for preparing the catalyst (D), an ester of a strong acid (such as a sulfonic acid ester) may be used instead of the strong acid to be added. Since strong acid esters are usually less reactive than strong acids themselves, they may not react with metal compounds at room temperature, but when placed in a high-temperature extruder maintained at around 200 ° C, they have activity in the extruder. A catalyst (D) can be produced.

As a method for preparing the catalyst (D), another method described below can be adopted. First, a water-soluble metal compound belonging to Groups 3 to 12 of the periodic table and a strong acid (sulfonic acid or the like) whose conjugate acid is equal to or higher than sulfuric acid are mixed in an aqueous solution to prepare an aqueous catalyst solution. At this time, the aqueous solution may contain an appropriate amount of alcohol. The obtained catalyst aqueous solution is brought into contact with EVOH (A) and then dried to obtain EVOH (A) containing the catalyst (D). Specifically, a method of immersing EVOH (A) pellets, particularly porous hydrous pellets in the catalyst aqueous solution is preferable. In this case, the dry pellets thus obtained can be introduced into the extruder.

In the production method of the present invention, EVOH (A) and monovalent epoxy compound (B) are melt-kneaded in an extruder in the presence of catalyst (D). The extruder used is not particularly limited, but it is preferable to use a single-screw extruder, a twin-screw extruder, or a multi-screw extruder having two or more screws. When using a twin-screw extruder or a multi-screw extruder with two or more screws, it is easy to increase the pressure in the reaction part by changing the screw configuration,
The EVOH (A) and the monovalent epoxy compound (B) can be efficiently reacted. In the single-screw extruder, it is possible to increase the pressure in the reaction section by connecting two or more extruders and arranging a valve in the resin flow path between them.
Further, similarly, two or more twin-screw extruders or multi-screw extruders having two or more screws may be connected and manufactured.

EVOH during melt-kneading in the extruder
The mixing method of (A) and the monovalent epoxy compound (B) is not particularly limited. EVOH before feeding to extruder
A method of spraying a monovalent epoxy compound (B) on (A), or feeding EVOH (A) to an extruder,
A suitable method is, for example, a method of contacting the monovalent epoxy compound (B) in the extruder. Among these, from the viewpoint of suppressing the volatilization of the monovalent epoxy compound (B) to the outside of the system, a method in which EVOH (A) is fed to the extruder and then contacted with the monovalent epoxy compound (B) in the extruder is preferable. . In addition, the monovalent epoxy compound (B) into the extruder
Although the addition position of VO is arbitrary, from the viewpoint of reactivity between EVOH (A) and epoxy compound (B), molten EVO
It is preferable to add the monovalent epoxy compound (B) to H (A).

As described above, in the step of adding the monovalent epoxy compound (B), it is preferable to press the monovalent epoxy compound (B) under pressure. At this time,
If this pressure is insufficient, there is a problem that the reaction rate decreases and the discharge amount varies. The required pressure varies greatly depending on the boiling point of the monovalent epoxy compound (B) and the extrusion temperature, but is usually in the range of 0.5 to 30 MPa, preferably 1 to 2
The range of 0 MPa is more preferable.

The temperature inside the extruder is preferably 180 to 250 ° C. In the present invention, since the catalyst (D) is present when the EVOH (A) is reacted with the monovalent epoxy compound (B), even if the EVOH (A) and the monovalent epoxy compound (B) are melt-kneaded at relatively low temperature, The reaction of the epoxy compound (B) can proceed. If the temperature exceeds 250 ° C., EVOH may deteriorate, and more preferably 240 ° C.
It is below ℃. On the other hand, when the temperature is less than 180 ° C, E
The reaction between VOH (A) and the monovalent epoxy compound (B) may not proceed sufficiently, and it is more preferably 190 ° C or higher.

The method of allowing the catalyst (D) to exist when the EVOH (A) is reacted with the monovalent epoxy compound (B) is not particularly limited. A suitable method is to prepare a solution of the catalyst (D) and add the solution into the extruder. The method for preparing the solution of the catalyst (D) is as described above. According to this method, the productivity is higher than the other method described later, and the catalyst (D) can be stably supplied, so that the quality of the product can be stabilized. The position at which the solution of the catalyst (D) is introduced into the extruder is not particularly limited, but EVOH
It is preferable to add (A) at a place where it is completely melted, because it can be uniformly blended. In particular, it is preferable to add the monovalent epoxy compound (B) at the same place as the place where it is added or in the vicinity thereof. By blending the catalyst (D) and the monovalent epoxy compound (B) almost at the same time, the deterioration of the EVOH (A) due to the influence of the catalyst (D) which is a Lewis acid can be suppressed to a minimum and sufficient This is because the reaction time can be secured. Therefore, it is optimal to prepare a liquid in which the solution of the catalyst (D) and the monovalent epoxy compound (B) are mixed in advance and add it to the extruder from one place.

As another method of allowing the catalyst (D) to exist during the melt-kneading, a method of immersing the hydrous pellets of EVOH (A) in the solution of the catalyst (D) and then drying it can be mentioned. This method is as described above as another method of preparing the catalyst (D). In this case, the obtained dried pellets are introduced into the extruder from the hopper. However, a problem is that an expensive catalyst is treated as a waste liquid, which easily leads to an increase in cost. Still another method is to impregnate the dried pellets with a liquid catalyst or to mix a solid catalyst, and then dry the pellets if necessary. In this method, there is a problem that the number of steps is increased and the cost is easily increased, and it is not always easy to uniformly mix the catalyst. Further, in any of the above-mentioned alternative methods, EVOH (A) is deteriorated when melt-kneaded in the state where the monovalent epoxy compound (B) does not exist and only the catalyst (D) which is a Lewis acid exists. There is a risk.

In the production method of the present invention, EVOH (A) and the monovalent epoxy compound (B) are melt-kneaded in the extruder in the presence of the catalyst (D). )
It is preferable to add and melt-knead. Modified EV obtained when catalyst (D) is not deactivated
There is a possibility that the thermal stability of OH (C) may be deteriorated, which may cause a problem in use depending on the application.

The catalyst deactivator (E) used is not particularly limited as long as it reduces the action of the catalyst (D) as a Lewis acid. Alkali metal salts are preferably used. In order to deactivate the catalyst (D) containing a monovalent anion whose conjugate acid is a strong acid equal to or more than sulfuric acid, it is necessary to use an alkali metal salt of an anion of an acid weaker than the conjugate acid of the anion. Is. By doing so, the third to third periodic table constituting the catalyst (D)
This is because the counterion of the metal ion belonging to Group 12 is exchanged with the weak acid anion, and as a result, the Lewis acidity of the catalyst (D) is reduced. The cation species of the alkali metal salt used for the catalyst deactivator (E) is not particularly limited, and sodium salts, potassium salts and lithium salts are exemplified as preferable ones. The anion species is also not particularly limited, and carboxylates, phosphates and phosphonates are exemplified as suitable ones.

When a salt such as sodium acetate or dipotassium monohydrogen phosphate is used as the catalyst deactivator (E), the thermal stability is considerably improved, but it is still insufficient depending on the use. There is. The reason for this is that
It is considered that this is because the action of the Lewis acid remains to some extent in the ions of the metal belonging to Group 12 and thus acts as a catalyst for the decomposition and gelation of the modified EVOH (C). As a method for further improving this point, it is preferable to add a chelating agent that strongly coordinates with ions of a metal belonging to Groups 3 to 12 of the periodic table. Such a chelating agent can strongly coordinate to the ion of the metal, and as a result, the Lewis acidity thereof can be almost completely lost, and modified EVOH (C) excellent in thermal stability can be provided. Further, since the chelating agent is an alkali metal salt, it is possible to neutralize the strong acid that is the conjugate acid of the anion contained in the catalyst (D) as described above.

Suitable chelating agents used as the catalyst deactivator (E) include oxycarboxylic acid salts, aminocarboxylic acid salts, aminophosphonic acid salts and the like. Specifically, as the oxycarboxylic acid salt,
Examples include disodium citrate, disodium tartrate, disodium malate and the like. Examples of aminocarboxylic acid salts include trisodium nitrilotriacetate, disodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, tripotassium ethylenediaminetetraacetate, trisodium diethylenetriaminepentaacetate, trisodium 1,2-cyclohexanediaminetetraacetate, and ethylenediaminediacetate Examples include monosodium acetate and N- (hydroxyethyl) iminodiacetic acid monosodium. Examples of aminophosphonates include nitrilotrismethylenephosphonate hexasodium, ethylenediaminetetra (methylenephosphonate) octasodium, and the like. Among them, polyaminopolycarboxylic acid is preferable, and an alkali metal salt of ethylenediaminetetraacetic acid is most preferable in terms of performance and cost. The estimated reaction mechanism when trisodium ethylenediaminetetraacetate is used is shown in the following formula (XI).

[0093]

[Chemical 13]

The amount of the catalyst deactivator (E) added is not particularly limited and may be appropriately adjusted depending on the kind of metal ions contained in the catalyst (D), the number of coordination sites of the chelating agent, etc. It is preferable that the ratio (E / D) of the number of moles of the catalyst deactivator (E) to the number of moles of the metal ion contained in D) is 0.2 to 10. When the ratio (E / D) is less than 0.2, the catalyst (D) may not be sufficiently deactivated, and it is more preferably 0.5 or more, still more preferably 1 or more. On the other hand, when the ratio (E / D) exceeds 10, the obtained modified EVOH (C) may be colored and the manufacturing cost may be increased. More preferably, it is 5 or less, and It is preferably 3 or less.

The method of introducing the catalyst deactivator (E) into the extruder is not particularly limited, but in order to disperse it uniformly, the catalyst deactivator (E) is added to the modified EVOH (C) in the molten state. It is preferable to introduce it as a solution. Considering the solubility of the catalyst deactivator (E) and the influence on the surrounding environment, it is preferable to add it as an aqueous solution.

The catalyst deactivator (E) was added to the extruder at the position where EVOH (A) and monovalent epoxy compound (B) were added.
It may be after melt-kneading in the presence of the catalyst (D). However, the ethylene-vinyl alcohol copolymer (A) and the monovalent epoxy compound (B) are melt-kneaded in the presence of the catalyst (D) to remove the unreacted monovalent epoxy compound (B) and then the catalyst. It is preferable to add a quenching agent (E). As described above, when the catalyst deactivator (E) is added as an aqueous solution, the catalyst deactivator (E) may be added before removing the unreacted monovalent epoxy compound (B). This is because water will be mixed in the monovalent epoxy compound (B) that is removed and collected for use, etc., and the separation operation will be troublesome. In addition, it is also preferable to remove water by venting after adding the aqueous solution of the catalyst deactivator (E).

In the production method of the present invention, when a catalyst deactivator (E) is used, suitable production processes include (1) EVOH (A) melting step; (2) monovalent epoxy compound (B) And (C) a mixture of catalyst (D); (3) a step of removing unreacted monovalent epoxy compound (B); (4) a step of adding a catalyst deactivator (E) aqueous solution; Steps: those comprising each step are exemplified.

From the viewpoint of smoothly carrying out the reaction, it is preferable to remove water and oxygen from the system. Therefore, water and oxygen may be removed using a vent or the like before adding the monovalent epoxy compound (B) into the extruder.

The object of the present invention is to provide the following modified ethylene-
It is also achieved by providing a vinyl alcohol copolymer (C). The modified ethylene-vinyl alcohol copolymer (C) is preferably produced by the production method described above.

That is, the present invention provides the following structural unit (I)
Is a modified ethylene-vinyl alcohol copolymer (C) containing 0.1 to 20 μmol / g of ions of a metal belonging to Groups 3 to 12 of the periodic table.

[0101]

[Chemical 14]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group or an alkenyl group), an aliphatic group having 3 to 10 carbon atoms). It represents a cyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group, etc.) or an aromatic hydrocarbon group having 6 to 10 carbon atoms (phenyl group, etc.) R ¹ , R ² , R ³ and R ⁴ may be the same groups. R ³ and R ⁴ may be bonded (provided that R ³ and R ⁴ are both hydrogen atoms), and R ¹ and R ⁴ are the same or different. ² , R ³ and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group and a halogen atom.)

In a more preferred embodiment, R ¹ and R
Both ² are hydrogen atoms. In a further preferred embodiment, both R ¹ and R ² are hydrogen atoms,
^{One of 3} and R ⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the other is a hydrogen atom. Preferably, the aliphatic hydrocarbon group is an alkyl group or an alkenyl group. From the viewpoint of particularly emphasizing the gas barrier property when the modified EVOH (C) is used as a barrier material, the R
It is more preferable that one of ³ and R ⁴ is a methyl group or an ethyl group and the other is a hydrogen atom.

From the viewpoint of gas barrier properties when the modified EVOH (C) is used as a barrier material, one of R ³ and R ⁴ is a substituent represented by (CH ₂ ) _i OH (provided that , I = 1 to 8) and the other is preferably a hydrogen atom. When the gas barrier property as a barrier material is particularly emphasized, in the substituent represented by (CH ₂ ) _i OH, i is preferably an integer of 1 to 4 and more preferably 1 or 2. It is preferably 1 and more preferably 1.

The amount of the above-mentioned structural unit (I) contained in the modified EVOH (C) of the present invention needs to be within the range of 0.3 to 40 mol%. The lower limit of the amount of the structural unit (I) is preferably 0.5 mol% or more, and 1 mol%
More preferably, it is more preferably 2 mol% or more. On the other hand, the upper limit of the amount of the structural unit (I) is preferably 35 mol% or less, and 30 mol%
It is more preferably at most 25 mol%, still more preferably at most 25 mol%. When the amount of the structural unit (I) contained is within the above range, a modified EVOH (C) having gas barrier properties, transparency, stretchability and bending resistance can be obtained.

The modified EVOH (C) of the present invention preferably has an ethylene content of 5 to 55 mol%. From the viewpoint that the modified EVOH (C) of the present invention obtains good stretchability and bending resistance, the lower limit of the ethylene content of the modified EVOH (C) is more preferably 10 mol% or more, and further preferably Is 20 mol% or more, particularly preferably 25 mol% or more, and further preferably 31 mol% or more. On the other hand, from the viewpoint of the gas barrier property of the modified EVOH (C) of the present invention, the upper limit of the ethylene content of the modified EVOH (C) is more preferably 50 mol% or less, and further preferably 4
It is 5 mol% or less. If the ethylene content is less than 5 mol%, the melt moldability may deteriorate, and if it exceeds 55 mol%, the gas barrier property may be insufficient.

Constituting the modified EVOH (C) of the present invention,
The constituents other than the structural unit (I) and the ethylene unit are mainly vinyl alcohol units. This vinyl alcohol unit is a vinyl alcohol unit that has not reacted with the monovalent epoxy compound (B) among the vinyl alcohol units contained in the EVOH (A) as a raw material. Also, E
The unsaponified vinyl acetate unit that may be contained in VOH (A) is usually contained in the modified EVOH (C) as it is. It was found from the measurement results of NMR and the melting point that the modified EVOH (C) was a random copolymer containing these constituent components. Further, other components may be contained within the range not impairing the object of the present invention.

The preferred melt flow rate (MFR) of the modified EVOH (C) of the present invention (190 ° C., under a load of 2160 g) is 0.1 to 30 g / 10 minutes, and more preferably 0.3 to 25 g / 10 minutes, more preferably 0.5 to 20 g
/ 10 minutes. However, the melting point is around 190 ° C or 1
Those that exceed 90 ° C are measured at multiple temperatures above the melting point under a load of 2160 g, and the reciprocal of absolute temperature is plotted on the abscissa and the logarithm of MFR is plotted on the ordinate in a semilogarithmic graph. Represent

The modified EVOH (C) of the present invention contains ions of a metal belonging to Groups 3 to 12 of the Periodic Table of 0.1 to 20 μm.
Contains ol / g. Such a metal ion can be contained as a catalyst residue when the catalyst (D) is used in the above-mentioned production method, and the suitable kind of the metal ion is described in the explanation of the above-mentioned catalyst (D). As I mentioned. It is more preferably 0.5 μmol / g or more. Further, it is more preferably 10 μmol / g or less.

The modified EVOH (C) of the present invention preferably contains a sulfonate ion. The sulfonate ion is used as the catalyst (D) in the above-mentioned production method.
Can be contained as a catalyst residue when used, and suitable types of sulfonate ions are as described in the description of the catalyst (D).
Sulfonate ion content is 0.1 to 20 μmol / g
Is preferred. More preferably 0.5 μmol
/ G or more. Further, more preferably 10 μmol / g
It is the following.

Further, the content of the alkali metal ion in the modified EVOH (C) is 1 to the content of the sulfonate ion.
It is preferably 50 times (molar ratio). The alkali metal ion is used as a catalyst deactivator (E) in the above-mentioned production method.
It can be contained as a residue when used, and can be contained due to EVOH (A) as a raw material.
When the content of the alkali metal ion is less than 1 time the content of the sulfonate ion, in the production process,
Catalyst (D) has not been sufficiently deactivated, and modified EVO
There may be a problem in the thermal stability of H (C), and it is more preferably double or more. On the other hand, if the content of alkali metal ions exceeds 50 times the content of sulfonate ions, the modified EVOH (C) may be colored, and is preferably 30 times or less.

The modified EVOH (C) of the present invention contains at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids and phosphoric acid compounds, EV
It can also be added after the modified EVOH (C) is obtained by the reaction of OH (A) with the monovalent epoxy compound (B). Generally, EVO such as improving adhesion and suppressing coloring
In order to improve various physical properties of H, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids and phosphoric acid compounds is often added to EVOH as needed. However, as described above, the addition of the various compounds described above can be achieved by the EV of the extruder.
When the OH (A) reacts with the monovalent epoxy compound (B), it may cause coloration or decrease in viscosity. Therefore, after the reaction between the EVOH (A) and the monovalent epoxy compound (B), the remaining monovalent epoxy compound (B) is removed by a vent, and then the alkali metal salt, alkaline earth metal salt, carboxylic acid and phosphorus At least one selected from the group consisting of acid compounds is preferably added to the obtained modified EVOH (C). By adopting this addition method,
The modified EVOH (C) of the present invention can be obtained without causing problems such as coloring and viscosity reduction.

If desired, various additives may be added to the modified EVOH (C) of the present invention. Examples of such additives may include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers, or other polymeric compounds. It can be blended within the range in which the effects of the present invention are not impaired. Specific examples of the additives include the following.

Antioxidants: 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2 '-Methylene-bis- (4-methyl-6-
t-butylphenol), octadecyl-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6-t-butylphenol) and the like.

UV absorber: ethylene-2-cyano-
3,3'-diphenyl acrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5) '-Methylphenyl) 5-
Chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the like.

Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphoric acid ester and the like. Antistatic agent: pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins,
Polyethylene oxide, carbowax, etc. Lubricants: ethylene bis stearamide, butyl stearate, etc. Coloring agent: carbon black, phthalocyanine, quinacridone, indoline, azo pigment, red iron oxide, etc. Filler: glass fiber, asbestos, ballastonite, calcium silicate, etc.

Also, many other polymer compounds can be blended to the extent that the effects of the present invention are not impaired.

In addition, the modified EVOH (C) of the present invention contains
In order to improve the melt stability and the like, hydrotalcite compounds, hindered phenol-based, hindered amine-based heat stabilizers, metal salts of higher aliphatic carboxylic acids (for example, calcium stearate, to the extent that the effects of the present invention are not impaired) , Magnesium stearate, etc.) may be added to the modified EVOH (C) to the extent that the effects of the present invention are not impaired (0.01 to 1% by weight).

The modified EVOH (C) of the present invention has a temperature of 20 ° C.
Oxygen permeation rate at 65% RH is 100cc ・ 20μ
It is preferably m / m ² · day · atm or less.
The upper limit of oxygen permeation rate is 50 cc · 20 μm / m ² · d
more preferably not more than ay · atm, 20 cc
・ 20 μm / m ² · day · atm or less is more preferable, and 10 cc · 20 μm / m ² · day · a
Particularly preferably, it is tm or less. Since the resin having such a low oxygen transmission rate, the modified EVOH (C) of the present invention is preferably used as a barrier material, and particularly preferably used as a container for food packaging.

The modified EVOH (C) of the present invention is 2
Carbon dioxide permeation rate at 0 ° C and 65% RH is 500c
It is preferably c · 20 μm / m ² · day · atm or less. The upper limit of carbon dioxide permeation rate is 200 cc.2
0 μm / m ² · day · atm or less is more preferable, and 100 cc · 20 μm / m ² · day · atm
The following is more preferable, and 50 cc · 20 μm
/ M ² · day · atm or less is particularly preferable. Because of the resin having such a low carbon dioxide gas permeation rate, the modified EVOH (C) of the present invention is preferably used as a barrier material, and particularly preferably used as a container for carbonated beverages.

The modified EVOH (C) of the present invention is preferably molded by melt molding into various molded products such as films, sheets, containers, pipes, hoses and fibers. These molded products can be crushed and molded again for the purpose of reuse. It is also possible to uniaxially or biaxially stretch a film, sheet, fiber or the like. As the melt molding method, extrusion molding, melt spinning, injection molding, injection blow molding and the like are possible. The melting temperature varies depending on the melting point of the modified EVOH (C) and the like, but is preferably about 120 to 270 ° C.

The modified EVOH (C) of the present invention is preferably used as an extrusion molded product. The method for producing the extrusion molded article is not particularly limited, but film extrusion cast molding, sheet extrusion cast molding, pipe extrusion molding, hose extrusion molding, profile extrusion molding, extrusion blow molding, inflation extrusion molding, etc. are exemplified as suitable ones. . It is also possible to subject the extrusion molded product obtained by these molding methods to secondary processing such as uniaxial or biaxial stretching, or thermoforming.

As described above, the conventional EVOH is excellent in transparency and gas barrier property, but has a drawback that it lacks in stretchability and bending resistance. Therefore, when EVOH is used for applications such as bottles that require impact resistance, or for applications such as films or flexible packaging containers that require bending resistance, it is necessary to stack EVOH and another resin. There were many things. However, the modified EVOH of the present invention
Since (C) has excellent properties in terms of barrier properties, transparency, stretchability and bending resistance, it can be used as a single layer even in applications requiring impact resistance and / or bending resistance. It can be used as a molded product. The present invention is also significant in terms of the expansion of the embodiment.

From the viewpoint of effectively utilizing the modified EVOH (C) of the present invention, which is excellent in barrier properties, impact resistance and bending resistance, a single layer molded product made of the modified EVOH (C) is a film or an extruded product. Blow-molded products (preferably bottles etc.), flexible packaging containers (preferably flexible tubes or pouches etc.), pipes, hoses and shaped articles are preferred.

Further, as the above-mentioned film, a stretched film is particularly preferable from the viewpoint of utilizing the characteristic of the modified EVOH (C) of the present invention that it is excellent in stretchability. Above all, a stretched film obtained by stretching at least two times in at least one uniaxial direction is preferable. Furthermore, it is also preferable to use the stretched film as a heat-shrinkable film.

Although the modified EVOH (C) of the present invention can be put to practical use as a single-layer molded product as described above, the modified EOH
It is also preferable to use it as a multilayer structure in which VOH (C) and a resin other than the modified EVOH (C) are laminated. As the layer structure of the multilayer structure, the modified EVOH (C) of the present invention which is often used as a barrier material is Ba.
where r is the adhesive resin, Ad is the adhesive resin, R is the resin other than the barrier material, and the scrap recovery layer is Reg.
rier / R, R / Barrier / R, Barrie
r / Ad / R, Reg / Barrier / R, R / Ad
/ Barrier / Ad / R, R / Reg / Ad / Ba
Examples include, but are not limited to, rlier / Ad / Reg / R. When a resin other than the modified EVOH (C) is provided on both surfaces of the layer composed of the modified EVOH (C), different types or the same may be used. Furthermore, the recovered resin may be blended with a resin other than the modified EVOH (C). Each layer may be a single layer or may be a multilayer in some cases.

The method for producing the above-mentioned multilayer structure is not particularly limited. For example, a method of melt-extruding another resin into a molded article (film, sheet, etc.) made of modified EVOH (C), conversely, a method of melt-extruding modified EVOH (C) onto a substrate such as a resin, modified EVOH (C ) And another resin, and a molded product obtained from the modified EVOH (C) of the present invention and a film or sheet of another base material, an organic titanium compound, an isocyanate compound, a polyester compound. A method of laminating using a known adhesive such as Among these, the method of coextrusion molding the modified EVOH (C) and another resin is preferably used.

The resin laminated with the modified EVOH (C) of the present invention is at least selected from the group consisting of polyolefin, polyamide, polyester, polystyrene, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile, thermoplastic polyurethane and polycarbonate. One resin is preferred. Among these, polyolefin, polyamide, polystyrene, polyester and thermoplastic polyurethane are preferably used.

The polyolefin used in the present invention is not particularly limited. For example, linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene, propylene-α-olefin copolymer (carbon number 4 ~ 20 α-
Olefin), polybutene, polypentene, and other olefin homopolymers or copolymers thereof. Copolymer components other than these α-olefins include diolefins and N
-Vinylcarbazole, vinyl chloride, vinylidene chloride,
Vinyl compounds such as styrene, acrylonitrile and vinyl ether, unsaturated carboxylic acids such as maleic acid, acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid and itaconic acid, their esters and their acid anhydrides, or hydroxyl groups or epoxy groups It is possible to add those that have been added. For example, various copolymers such as a copolymer of a graftable monomer and a polyolefin or an ionomer resin which is a reaction product of an α-olefin / α, β-unsaturated carboxylic acid copolymer and an ionic metal compound can be used. It can also be used. Also, as the polyolefin, chlorinated polyethylene, chlorinated polypropylene, etc. can be used. These polyolefin-based resins may be used alone or in combination of two or more. Among the above examples, polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer are particularly preferably used.

As described above, the modified EVOH (C) of the present invention
A multilayer structure comprising a layer of is preferably modified EVOH
It is produced by coextrusion of (C) and another resin.
At this time, the modified EVOH (C) and another resin may be laminated via an adhesive resin depending on the type of the resin laminated with the modified EVOH (C). In this case, the adhesive resin is preferably an adhesive resin made of carboxylic acid-modified polyolefin. Here, the carboxylic acid-modified polyolefin is a modified olefin system containing a carboxyl group obtained by chemically bonding an ethylenically unsaturated carboxylic acid or an anhydride thereof to an olefin polymer (for example, by an addition reaction or a graft reaction). It refers to a polymer. Further, here, the olefin-based polymer is a polyolefin such as polyethylene (low pressure, medium pressure, high pressure), linear low-density polyethylene, polypropylene, and boribten, and a comonomer (vinyl ester, copolymer) capable of copolymerizing the olefin with the olefin. (Saturated carboxylic acid ester, etc.), for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ethyl ester copolymer and the like.
Among them, linear low-density polyethylene, ethylene-vinyl acetate copolymer (vinyl acetate content 5 to 55% by weight),
Ethylene-acrylic acid ethyl ester copolymer (content of acrylic acid ethyl ester is 8 to 35% by weight) is preferable, and linear low-density polyethylene and ethylene-vinyl acetate copolymer are particularly preferable. Ethylenically unsaturated carboxylic acid or its anhydride and ethylenically unsaturated monocarboxylic acid, its ester, ethylenically unsaturated dicarboxylic acid,
Examples thereof include mono- or diesters and anhydrides thereof, and among them, ethylenically unsaturated dicarboxylic acid anhydride is preferable. Specific examples include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, among others, maleic anhydride. Acids are preferred.

The addition amount or graft amount (modification degree) of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer is 0.0001 to 15 relative to the olefin polymer.
%, Preferably 0.001 to 10% by weight. The addition reaction and grafting reaction of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer can be obtained, for example, by a radical polymerization method in the presence of a solvent (such as xylene) and a catalyst (such as peroxide). The carboxylic acid-modified polyolefin thus obtained has a temperature of 190 ° C., 216
The melt flow rate (MFR) measured under 0 g load is preferably 0.2 to 30 g / 10 minutes, more preferably 0.5 to 10 g / 10 minutes. These adhesive resins may be used alone or in combination of two or more.

When the modified EVOH (C) of the present invention and another resin are coextrusion-molded, there are the following merits as compared with ordinary EVOH. One of the merits is that the modified EVOH (C) of the present invention has excellent barrier properties, transparency,
Modified EVOH (C) due to its stretchability and flex resistance
It is also possible to impart such excellent physical properties to a multilayer molded product including a layer composed of

Another advantage is the modified EV of the present invention.
OH (C) is a merit due to its low melting point as compared with ordinary EVOH. Modified EVOH (C)
The melting point of is different depending on the content of the structural unit (I), but the melting point of the modified EVOH (C) containing the structural unit (I) is lower than that of a normal unmodified EVOH.

EVOH is often used as a laminate with a polyolefin, but the laminate is often produced by coextrusion. However, in general, EVOH having an ethylene content of 5 to 55 mol% is a resin having a higher melting point than polyolefin and the like.
When H and polyolefin were melt-molded by coextrusion, it was necessary to mold them at a temperature higher than the melting point of EVOH. That is, the coextrusion molding was carried out at a molding temperature which was not necessarily optimum as the molding temperature of the polyolefin.

However, by using the modified EVOH (C) of the present invention, it becomes possible to carry out coextrusion molding at a molding temperature closer to the optimum molding temperature of polyolefin. In this way, the range of molding temperatures during the coextrusion molding is expanded, so that the polyolefin and the modified EVOH are
It became easier to adjust the viscosity matching with (C), and a coextruded product could be obtained under more preferable operating conditions. From this viewpoint, the significance of the present invention is great.

The method of coextrusion molding the modified EVOH (C) of the present invention and another resin is not particularly limited. For example,
The multi-manifold method, the feed block method, the multi-slot die method, etc. are exemplified as preferable ones. By such a molding method, a multilayer film, a multilayer sheet, a multilayer pipe, a multilayer hose, a multilayer irregularly shaped product and the like are molded. Further, a multilayer film or a multilayer bottle can be obtained by a coextrusion inflation molding method, a coextrusion blow molding method, or the like.

By subjecting the coextruded multilayer structure thus obtained to secondary processing, various molded products (films, sheets, tubes, bottles, etc.) can be obtained. Examples include the following. To be (1) Multilayer co-stretched sheet or film obtained by uniaxially or biaxially stretching or biaxially stretching and heat-treating a multilayer structure (sheet or film) (2) Multilayer structure (sheet or film) Multi-layer rolled sheet or film by rolling (3) Multi-layer structure (sheet or film, etc.) Vacuum forming, pressure forming, vacuum pressure forming, multi-layer tray cup-shaped container by thermoforming (4) Multi-layer structure Bottles and cup-shaped containers formed by stretch blow molding (pipe etc.) are not particularly limited to such secondary processing methods, and known secondary processing methods (blow molding etc.) other than the above can also be adopted.

Since the modified EVOH (C) of the present invention is excellent in all of the barrier property, transparency, stretchability and flex resistance, a multi-layer structure containing a layer composed of the modified EVOH (C) of the present invention. Can be used for various purposes. For example, it is used for flexible films, flexible packaging materials, thermoformed containers, blow molded products (multi-layer coextrusion blow molded containers, multi-layer co-injection blow molded containers, etc.), heat-shrinkable films (skin pack films, etc.), hoses, balloons, etc. It is preferable. Among the above, as an application that can sufficiently exert the effect of bending resistance,
Suitable examples include flexible packaging materials (flexible pouches, tubes, etc.) and flexible films.

The modified EVOH (C) of the present invention and the multilayer structure containing a layer composed of the modified EVOH (C) are also preferably used as a wallpaper or a decorative plate. EVOH
Has an excellent antifouling property and a barrier property against a plasticizer, and therefore the multilayer structure containing the EVOH layer is suitably used as a wallpaper. However, wallpaper is often stored in a rolled state during transportation or storage in a warehouse. When the transportation is repeated many times, the EVOH layer may be wrinkled due to an increase in the frequency of bending, or if the severity is severe, whitening may occur.
Sometimes the appearance was poor. However, the modified EVOH (C) of the present invention has excellent flexibility and flex resistance while maintaining excellent barrier properties against plasticizers, and is therefore very suitable for such applications.

Further, since the flexible film comprising the modified EVOH (C) of the present invention is excellent in antifouling property, flexibility and flex resistance as described above, it can be laminated with, for example, artificial leather or the like to form a book. It is also preferable to use it for a cover or the like. It is also preferably used as a cover of a book, a cover of a notebook, and the like.

By using the modified EVOH (C) of the present invention as a multi-layer pipe including a layer made of the modified EVOH (C), a multi-layer pipe excellent in crack resistance can be obtained. In a preferred embodiment, the multi-layer pipe is a multi-layer pipe made of a laminate having an intermediate layer made of modified EVOH (C) and inner and outer layers made of polyolefin. As the multilayer pipe, it is particularly preferable to use it as a fuel pipe or a pipe for circulating hot water. The fuel pipe can be used not only as a fuel pipe for automobiles but also as a so-called fuel line for transporting fuel from an oil field or the like. These multilayer pipes are usually used by joining the pipes with each other using a joining tool. When joining such multi-layered pipes using a joining tool, the pipes are often enlarged slowly with a special enlargement jig by dividing the diameter of the pipe ends into several times.

In such a process, in the conventional multi-layer pipe using ordinary EVOH as the intermediate layer, cracks may occur in the EVOH in the portion where the diameter of the multi-layer pipe is enlarged. Especially when working in an environment where the outside air temperature is extremely low, such as in areas where floor heating pipes are laid,
There are cases where large cracks occur in the layer made of VOH. Due to the crack, the oxygen barrier property at the joint portion of the multi-layer pipe sometimes deteriorated. However, since the modified EVOH (C) of the present invention is excellent in flexibility, it is possible to effectively suppress the generation of cracks in the layer composed of the modified EVOH (C) even in such a joining step of pipes. is there.

On the other hand, the multilayer pipe is also suitably used as a fuel pipe. In this case, the fuel pipe is particularly preferably used as a fuel pipe for an automobile, and is used as a fuel pipe for supplying fuel from a fuel tank to an engine. In such an embodiment, the vibration due to the engine, the vibration during the traveling of the automobile, and the like continue to apply a load to the fuel pipe, so that cracks and the like are likely to occur in the barrier layer. However, since the modified EVOH (C) of the present invention has excellent flexibility, it is possible to effectively suppress the generation of cracks in the layer composed of the modified EVOH (C) even when used as a fuel pipe.

From the above viewpoints, the modified EV of the present invention
It is very useful to use a multilayer structure including a layer made of OH (C) as a multilayer pipe, and it is particularly preferable to use it as a fuel pipe or a pipe for circulating hot water.
It is also preferable to use the multilayer structure including the layer of the modified EVOH (C) of the present invention as a multilayer hose.
Since the hose is more flexible than the pipe, the advantage of using the modified EVOH (C) of the present invention having excellent flexibility is great. Particularly preferably, it is used as a fuel hose.

By using the multilayer structure containing the layer of the modified EVOH (C) of the present invention as a multilayer blow molded product, a multilayer blow molded product excellent in impact resistance can be obtained. As the multilayer blow molded product, a multilayer coextrusion blow molded container is preferable. As the multilayer blow-molded container, it is preferable to use modified EVOH (C) as the intermediate layer and polyolefin as the inner and outer layers. In particular, it is preferable to use polyethylene or polypropylene as the polyolefin.

The multi-layer blow molded container is preferably used as a fuel container for automobiles or a fuel container for motorcycles. When the multi-layer coextrusion blow-molded container is used as the fuel container, it is preferable to use high-density polyethylene as the polyolefin. High-density polyethylene can be used by appropriately selecting it from commercially available products, but from the viewpoint of rigidity, impact resistance, moldability, drawdown resistance, gasoline resistance, etc., the density of high-density polyethylene is It is preferably 0.95 to 0.98 g / cm ³ , and more preferably 0.96 to 0.98 g / cm ^3.
Is. Also, the melt flow rate (MFR) of high-density polyethylene used as the inner and outer layers of a multi-layer fuel container
Is 0.01 to 0.5 g / 10 minutes (190 ° C.-2160
g under load), and more preferably 0.01 to 0.1 g / 10 min (under 190 ° C.-2160 g load).

[0147]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. EVOH (A) and modified EVOH
The analysis regarding (C) was performed according to the following method.

(1) Ethylene content and degree of saponification of EVOH (A) ¹ H-NM using deuterated dimethyl sulfoxide as a solvent
R (nuclear magnetic resonance) measurement ("JNM-GX-" manufactured by JEOL Ltd.)
It was calculated from the spectrum obtained by using "Model 500").

(2) Intrinsic viscosity of EVOH (A) 0.20 g of dry pellets consisting of dry EVOH (A) as a sample was precisely weighed and 40 ml of water-containing phenol (water / phenol = 15/85: weight ratio) 3 at 60 ℃
The mixture was heated and melted for 4 hours, measured at an Ostwald viscometer at a temperature of 30 ° C. (t0 = 90 seconds), and the intrinsic viscosity [η] was determined by the following formula. [Η] = (2 × (ηsp-lnηrel)) ^1/2 / C (L /
g) ηsp = t / t0-1 (specific viscosity) ηrel = t / t0 (relative viscosity) C; EVOH concentration (g / L) t0: time for blank (hydrous phenol) to pass through viscometer t: sample dissolution Time for the hydrous phenolic solution to pass through the viscometer

(3) Quantitative determination of acetic acid content in EVOH (A) 20 g of dry pellets of EVOH (A) as a sample were put into 100 ml of ion-exchanged water, and heated and extracted at 95 ° C. for 6 hours. Extract the extract with phenolphthalein as an indicator,
The content of acetic acid was quantified by neutralization titration with 1/50 N NaOH.

(4) EVOH (A) and modified EVOH
Na ion, K ion, Mg ion and Ca in (C)
10 g of dry pellets of EVOH (A) or modified EVOH (C) to be used as a quantitative sample of ions, 50 ml of 0.01 N hydrochloric acid aqueous solution
And stirred at 95 ° C. for 6 hours. The aqueous solution after stirring is quantitatively analyzed using ion chromatography, and Na,
The amounts of K, Mg and Ca ions were quantified. The columns are
ICS-C25 manufactured by Yokogawa Electric Corporation was used, and the eluent was an aqueous solution containing 5.0 mM tartaric acid and 1.0 mM 2,6-pyridinedicarboxylic acid. In addition, when quantifying, sodium chloride aqueous solution, potassium chloride aqueous solution,
A calibration curve prepared using an aqueous solution of magnesium chloride and an aqueous solution of calcium chloride was used.

(5) EVOH (A) and modified EVOH
10 g of dry pellets of EVOH (A) or modified EVOH (C), which is a quantitative sample of phosphate ion and trifluoromethanesulfonate ion in (C), and 50 ml of 0.01 N hydrochloric acid aqueous solution
And stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to quantify the amounts of phosphate ion and trifluoromethanesulfonate ion. The column is ICS-A2 manufactured by Yokogawa Electric Corporation.
3 was used, and the eluent was an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium hydrogen carbonate.
For the quantification, a calibration curve prepared from an aqueous solution of sodium dihydrogen phosphate and an aqueous solution of sodium trifluoromethanesulfonate was used.

(6) Determination of zinc ion and yttrium ion in modified EVOH (C) 10 g of modified EVOH (C) dry pellets as a sample were put into 50 ml of 0.01N hydrochloric acid aqueous solution and stirred at 95 ° C. for 6 hours. did. The aqueous solution after stirring was analyzed by ICP emission spectrometry. The device is Optima of Perkin Elmer
4300 DV was used. The measurement wavelength used was 206.20 nm for zinc ion measurement and 360.07 nm for yttrium ion measurement. In the quantification, a calibration curve prepared using a commercially available zinc standard solution and a yttrium standard solution was used.

(7) EVOH (A) and modified EVOH
The melting points of (C) EVOH (A) and modified EVOH (C) are the differential scanning calorimeter (DSC) RDC manufactured by Seiko Instruments Inc.
220 / SSC5200H type, JISK7121
It was measured based on. However, indium and lead were used for temperature calibration.

Example 1 28 parts by weight of zinc acetylacetonate monohydrate was added to
It was mixed with 957 parts by weight of 2-dimethoxyethane to obtain a mixed solution. 15 parts by weight of trifluoromethanesulfonic acid was added to the obtained mixed solution with stirring to obtain a catalyst (D).
A solution containing was obtained. That is, a solution was prepared in which 1 mol of trifluoromethanesulfonic acid was mixed with 1 mol of zinc acetylacetonate monohydrate.

Ethylene content 32 mol%, saponification degree 9
100 parts by weight of water-containing pellets (water content: 130% (dry base)) consisting of an ethylene-vinyl alcohol copolymer having a viscosity of 9.6% and an inherent viscosity of 0.0882 L / g were mixed with 0.1 g / L of acetic acid and diphosphoric acid. Potassium hydrogen 0.044g / L
It was immersed and stirred at 25 ° C. for 6 hours in 370 parts by weight of an aqueous solution containing. The obtained pellets were dried at 105 ° C. for 20 hours to obtain dry EVOH pellets. The dry EVOH
The potassium content of the pellets is 8 ppm (metal element conversion), the acetic acid content is 53 ppm, the phosphoric acid compound content is 20 ppm (phosphoric acid group conversion value), and the alkaline earth metal salt (Mg salt or Ca salt) content is It was 0 ppm.
The MFR of the dried pellet is 8 g / 10 minutes (19
It was 0 ° C. and under a load of 2160 g). The EVOH thus obtained was used as EVOH (A). Epoxypropane was used as the monovalent epoxy compound (B) having a molecular weight of 500 or less.

TEM-35BS extruder manufactured by Toshiba Machine Co., Ltd. (3
7 mmφ, L / D = 52.5) was used, and the screw configuration, vent and pressure inlet were installed as shown in FIG.
The barrel C1 was water-cooled, the barrels C2 to C15 were set to 200 ° C., and the screw rotation speed was 250 rpm. C
1 kg of EVOH (A) from the resin feed port of 1
/ Hr, the pressure of the vent 1 is reduced to 60 mmHg, and 1.5 of epoxy propane is introduced from the pressure inlet 1 of C8.
Both were mixed and fed so that the catalyst (D) solution prepared by the above method was added at a rate of kg / hr and at a rate of 0.22 kg / hr (pressure during feeding: 3 MPa). . Next, after removing unreacted epoxypropane from the vent 2 under normal pressure, the catalyst deactivator (E)
As an ethylenediaminetetraacetic acid trisodium trihydrate 8.2 wt% aqueous solution from the C13 pressure inlet 2 of 0.11
It was added at a rate of kg / hr.

In the melt-kneading operation, the mixing ratio of the monovalent epoxy compound (B) was 13.6 parts by weight with respect to 100 parts by weight of EVOH (A). The catalyst (D) was added in an amount of 2 μmol / g of metal ion based on the weight of EVOH (A). The ratio of the number of moles of the catalyst deactivator (E) to the number of moles of metal ions contained in the catalyst (D) (E
/ D) was 1.

Vent 3 was depressurized to an internal pressure of 20 mmHg to remove water, and modified EVOH (C) was obtained. The MFR of the obtained modified EVOH (C) was 7 g / 10 minutes (190 ° C,
It was under a load of 2160 g) and the melting point was 132 ° C.
The zinc ion content is 120 ppm (1.9 μmo
1 / g), and the alkali metal salt content is 138 ppm (5.9 μmol / g) [sodium:
130 ppm (5.7 μmol / g), potassium: 8 p
pm (0.2 μmol / g)], and the content of trifluoromethanesulfonate ion is 280 ppm (1.9
μmol / g). The content of alkali metal ions was 3.1 times (molar ratio) the content of trifluoromethanesulfonate ions.

The chemical structure of the modified EVOH (C) modified with epoxypropane thus obtained was determined by performing NMR measurement after trifluoroacetylation of the modified EVOH (C) according to the following procedure.

The modified EVOH (C) produced above was pulverized to a particle size of 0.2 mm or less, and 1 g of this powder was then treated to 100 m.
The mixture was placed in a 1-necked flask, 20 g of methylene chloride and 10 g of trifluoroacetic anhydride were added, and the mixture was stirred at room temperature. One hour after the start of stirring, the modified EVOH (C) was completely dissolved. After the modified EVOH (C) was completely dissolved, the mixture was stirred for 1 hour, and then the solvent was removed by a rotary evaporator. The obtained trifluoroacetylated modified EVOH (C) was dissolved in a mixed solvent of deuterated chloroform and trifluoroacetic anhydride (deuterated chloroform / trifluoroacetic anhydride = 2/1 (weight ratio)) at a concentration of 2 g / L. And tetramethylsilane as an internal standard at 500 MH
z ¹ H-NMR was measured. Figure 2 shows the NMR measurement chart.
Shown in.

Modified EVOH Modified with Epoxy Propane
Regarding the chemical structure in (C), the contents of the following structural units were determined. w: ethylene content (mol%) x: content of unmodified vinyl alcohol unit (mol%) y: structural unit (mol%) represented by the following formula (XII) z: represented by the following formula (XIII) Structural units (mol%)

[0163]

[Chemical 15]

[0164]

[Chemical 16]

Between the above w to z, the following formulas (1) to (4)
The relationship shown by is established. 4w + 2x + 5y + 5z = A (1) 3y + 2z = B (2) 2z = C (3) x + y = D (4)

However, in the above formulas (1) to (4), A to D
Of modified EVOH (C) ¹For H-NMR measurement
It is the integrated value of the signal in the following range. A: integrated value of signal at δ1.1 to 2.5 ppm B: integrated value of signals at δ 3.1 to 4 ppm C: integrated value of signals at δ 4.1 to 4.6 ppm D: integrated value of signal at δ 4.8 to 5.6 ppm

From the above formulas (1) to (4), modified EVOH
The ethylene content of (C) is determined as follows. Ethylene content (mol%) of modified EVOH (C) = {w / (w + x + y + z)} × 100 = {(2A-2B-3C-4D) / (2A-2B + C + 4D)} × 100

Similarly, the content of the structural unit (I) of the modified EVOH (C) is determined as follows. Content (mol%) of structural unit (I) of modified EVOH (C) = {(y + z) / (w + x + y + z)} × 100 = {(8B + 4C) / (6A-6B + 3C + 12D)} × 100

Modified EVOH prepared in Example 1 above
The ethylene content of (C) was 32 mol%, and the content of structural unit (I) was 5.5 mol%.

Using the modified EVOH (C) thus obtained, a 40φ extruder (PLA manufactured by Plastic Engineering Laboratory)
BOR GT-40-A) and a T-die were used to form a film under the following extrusion conditions to obtain a single-layer film having a thickness of 25 μm. Model: Single-screw extruder (non-vent type) L / D: 24 Caliber: 40 mmφ Screw: Single-row full flight type, surface nitrided steel Screw rotation speed: 40 rpm Die: 550 mm width coat hanger die Lip gap: 0.3 mm Cylinder, die Temperature setting: C1 / C2 / C3 / adapter / die = 180/200/210/210/210 (° C)

Using the single-layer film prepared as described above, the oxygen permeation rate and haze were measured according to the following methods, and a flex resistance test was conducted.

Measurement of oxygen permeation rate The monolayer film prepared above was subjected to 5 ° C. at 20 ° C. and 65% RH.
Humidified for days. 2 samples of humidity-controlled single layer film
MOCON O made by Modern Control Co., Ltd.
Using an X-TRAN 2/20 type, the oxygen permeation rate was measured according to the method described in JIS K7126 (isobaric method) under the conditions of 20 ° C. and 65% RH, and the average value was obtained. Oxygen transmission rate is 1.5cc ・ 20μm / m ²・ day ・ at
m, indicating a good barrier property.

Measurement of Haze Using the monolayer film prepared above, an integral formula H.M. manufactured by Nippon Seimitsu Optical Co., Ltd. was used. T. Using R meter, JIS
The haze was measured according to D8741. The haze was 0.1%, indicating extremely good transparency.

Evaluation of Flexing Resistance 50 sheets of the above-prepared single-layer films cut into 21 cm × 30 cm were prepared, and each film was heated at 20 ° C.
After conditioning at -65% RH for 5 days, ASTMF 392
According to -74, using a Gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., the bending times are 50 times, 75 times, 100 times,
125 times, 150 times, 175 times, 200 times, 225 times,
After being bent 250 times and 300 times, the number of pinholes was measured. The measurement was performed 5 times at each bending number, and the average value was used as the number of pinholes. The number of bends (P) is plotted on the horizontal axis and the number of pinholes (N) is plotted on the vertical axis. The above measurement results are plotted, and the number of bends (Np1) when the number of pinholes is 1 is determined by extrapolation and is effective. I used two numbers. As a result, Np1 was 160 times, showing extremely excellent bending resistance.

Evaluation of Stretchability Next, using the obtained modified EVOH (C), the following 3 types 5
Multi-layer sheet (ionomer resin layer / adhesive resin layer / modified EVOH) using the layer coextrusion equipment under the following coextrusion molding conditions.
(C) layer / adhesive resin layer / ionomer resin layer) was prepared. The sheet is composed of the ionomer resin for both outermost layers (“Mimi DuPont Polychemical's“ HIMIRAN 165 ”).
2 ") layer is 250 μm each, an adhesive resin (“ Admer NF500 ”manufactured by Mitsui Chemicals, Inc.) layer is 30 μm each, and a modified EVOH (C) layer is 90 μm.

The coextrusion conditions are as follows. Layer composition: ionomer resin / adhesive resin / modified EVOH (C) /
Adhesive resin / ionomer resin (thickness 250/30/90/30/250: unit is μ
m) Extrusion temperature of each resin: C1 / C2 / C3 / die = 170/170/220/2
Extruder specifications of each resin at 20 ° C .: Ionomer resin; 32φ extruder GT-32-A type (manufactured by Plastic Engineering Laboratory Co., Ltd.) Adhesive resin; 25φ extruder P25-18AC (manufactured by Osaka Seiki Co., Ltd.) Modified EVOH (C); 20φ extruder Lab machine ME type CO-EXT (manufactured by Toyo Seiki Co., Ltd.) T-die specification: 300 mm width 3 types for 5 layers (manufactured by Plastic Engineering Laboratory Co., Ltd.) Cooling roll temperature: 50 ° C. Take-off speed : 4m / min

The obtained multilayer sheet was put in a pantograph type biaxial stretching device manufactured by Toyo Seiki, and simultaneously biaxially stretched at 60 ° C. and a stretching ratio of 4 × 4. The appearance of the stretched film was evaluated according to the following evaluation criteria. Judgment: Criteria A: No unevenness or local uneven thickness. B: There is no local uneven thickness, although there is slight unevenness. C: There is a slight unevenness and a slight local uneven thickness, but it can be put to practical use. D: Large unevenness and large local uneven thickness. E: The film was torn. The stretched film of this example had neither unevenness nor local uneven thickness, and the evaluation was A.

Physical properties and the like of the modified EVOH (C) are summarized in Table 1, and evaluation results of the film are summarized in Table 2.

Example 2 Ethylene content 44 mol%, saponification degree 99.8%, intrinsic viscosity 0.096 L / g, MFR = 5 g / 10 min (190
EVOH (under acetic acid content of 2160 g) (acetic acid content 53 p
pm, sodium content 1 ppm (metal element conversion), potassium content 8 ppm (metal element conversion), phosphoric acid compound content 20 ppm (phosphate radical conversion value)} pellet 5k
g was placed in a polyethylene bag. Then, 27.44 g (0.125 mol) of zinc acetate dihydrate and 15 g (0.1 mol) of trifluoromethanesulfonic acid were added to 500 parts of water.
An aqueous solution was prepared by dissolving in g and the aqueous solution was added to EVOH in the bag. The EVOH to which the catalyst solution had been added as described above was occasionally heated for 5 hours at 90 ° C. with the bag mouth closed while shaking to impregnate the EVOH with the catalyst solution. The obtained EVOH was vacuum dried at 90 ° C. to obtain an EVOH containing the zinc ion-containing catalyst (D).

As EVOH (A), ethylene content is 44
Mol%, saponification degree 99.8%, intrinsic viscosity 0.096 L /
g, MFR = 5 g / 10 min (190 ° C., under a load of 2160 g) EVOH {acetic acid content 53 ppm, sodium content 1 ppm (metal element conversion), potassium content 8 pp
m (metal element conversion), phosphoric acid compound content 20ppm
(Phosphate radical conversion value)} 90 parts by weight of EVOH was dry-blended with 10 parts by weight of EVOH containing the catalyst (D) containing zinc ions. Also, the molecular weight is 5
1,2-epoxybutane was used as the monovalent epoxy compound (B) of 00 or less.

TEM-35BS extruder manufactured by Toshiba Machine Co., Ltd. (3
7 mmφ, L / D = 52.5) was used, and the screw configuration, vent and pressure inlet were installed as shown in FIG.
Barrel C1 is water-cooled, and barrels C2 to C3 are set to 200 ° C and C
4 to C15 set to 220 ℃, screw rotation speed 20
It was operated at 0 rpm. The EVOH (A) composed of the dry blended mixture and containing the catalyst (D) was fed from the C1 resin feed port at a rate of 11 kg / hr, the vent 1 was depressurized to an internal pressure of 60 mmHg, and the C8 pressure inlet 1 From the above, epoxy butane was fed at a rate of 2.5 kg / hr (pressure at feeding: 3.5 MPa). The vent 2 was depressurized to an internal pressure of 200 mmHg to remove unreacted epoxy butane, and 0.14 kg /
A 8.2% by weight aqueous solution of trisodium ethylenediamine tetraacetate trihydrate was added at a rate of hr.

In the melt-kneading operation, the mixing ratio of the monovalent epoxy compound (B) was 22.7 parts by weight with respect to 100 parts by weight of EVOH (A). 2.5 μmol / g in terms of mole number of metal ion relative to the weight of EVOH (A)
Catalyst (D) was added. The ratio (E / D) of the number of moles of the catalyst deactivator (E) to the number of moles of metal ions contained in the catalyst (D) was 1.

Vent 3 was depressurized to an internal pressure of 20 mmHg to remove water, and modified EVOH (C) was obtained. The modified E
MOH of VOH (C) is 5g / 10min (190 ℃, 21
(Under a load of 60 g) and the melting point was 109 ° C. The zinc ion content is 150 ppm (2.3 μmol
/ G), and the alkali metal salt content is 168 ppm (7.1 μmol / g) [sodium: 1 in terms of metal element].
60 ppm (6.9 μmol / g), potassium: 8 pp
m (0.2 μmol / g)], and the content of trifluoromethanesulfonate ion is 270 ppm (1.8 μm).
mol / g). The content of alkali metal ions was 3.9 times (molar ratio) the content of trifluoromethanesulfonate ions.

The chemical structure of the modified EVOH (C) modified with epoxybutane thus obtained was determined by NMR measurement after trifluoroacetylation of the modified EVOH (C) according to the following procedure.

The modified EVOH (C) produced above was pulverized to a particle size of 0.2 mm or less, and 1 g of this powder was treated for 100 m.
The mixture was placed in a 1-necked flask, 20 g of methylene chloride and 10 g of trifluoroacetic anhydride were added, and the mixture was stirred at room temperature. One hour after the start of stirring, the modified EVOH (C) was completely dissolved. After the modified EVOH (C) was completely dissolved, the mixture was stirred for 1 hour, and then the solvent was removed by a rotary evaporator. The obtained trifluoroacetylated modified EVOH (C) was dissolved in a mixed solvent of deuterated chloroform and trifluoroacetic anhydride (deuterated chloroform / trifluoroacetic anhydride = 2/1 (weight ratio)) at a concentration of 2 g / L. And tetramethylsilane as an internal standard at 500 MH
z ¹ H-NMR was measured.

Modified EVOH modified with epoxy butane
Regarding the chemical structure in (C), the contents of the following structural units were determined. w: ethylene content (mol%) x: content of unmodified vinyl alcohol unit (mol%) y: structural unit (mol%) represented by the following formula (XIV) z: represented by the following formula (XV) Structural units (mol%)

[0187]

[Chemical 17]

[0188]

[Chemical 18]

Between the above w to z, the following equations (5) to (8)
The relationship shown by is established. 4w + 2x + 4y + 4z = A (5) 3y + 2z = B (6) 2z = C (7) x + y = D (8)

However, in the above formulas (5) to (8), A to D
Of modified EVOH (C) ¹For H-NMR measurement
It is the integrated value of the signal in the following range. A: integrated value of signals at δ1.1 to 2.4 ppm B: integrated value of signals at δ 3.1 to 3.8 ppm C: integrated value of signals at δ 4.1 to 4.5 ppm D: integrated value of the signal at δ 4.8 to 5.5 ppm

From the above formulas (5) to (8), modified EVOH
The ethylene content of (C) is determined as follows. Ethylene content (mol%) of modified EVOH (C) = {w / (w + x + y + z)} × 100 = {(3A-2B-4C-6D) / (3A-2B + 2C + 6D)} × 100

Similarly, the content of the structural unit (I) of the modified EVOH (C) is obtained as follows. Content (mol%) of structural unit (I) of modified EVOH (C) = {(y + z) / (w + x + y + z)} × 100 = {(4B + 2C) / (3A-2B + 2C + 6D)} × 100

The modified EVOH (C) produced in Example 2 had an ethylene content of 44 mol% and a structural unit (I) content of 7 mol%.

Using the modified EVOH (C) thus obtained, a monolayer film and a multilayer film were produced in the same manner as in Example 1, the oxygen permeation rate and haze were measured, and the flex resistance and stretchability were evaluated. did. The physical properties and the like of the modified EVOH (C) are summarized in Table 1, and the evaluation results and the like of the film are summarized in Table 2.

Example 3 In Example 2, 27.44 g of zinc acetate dihydrate
Yttrium acetate 4 instead of (0.125 mol)
Using 42.26 g (0.125 mol) of the hydrate, the same operation was performed except for the above to obtain EVOH containing a catalyst containing yttrium ions.

Modified EVOH (C) was obtained in the same manner as in Example 2 except that EVOH containing the catalyst containing yttrium ions prepared in the above-mentioned method was used. At this time, the mixing ratio of the monovalent epoxy compound (B) was 22.7 parts by weight with respect to 100 parts by weight of EVOH (A). 2.5 μmol / g of catalyst (D) was added in moles of metal ion relative to the weight of EVOH (A). The ratio (E / D) of the number of moles of the catalyst deactivator (E) to the number of moles of metal ions contained in the catalyst (D) was 1.

The modified EVOH (C) has an MFR of 6 g /
It was for 10 minutes (190 ° C., under a load of 2160 g), and the melting point was 147 ° C. The yttrium ion content is 210 ppm (2.4 μmol / g), and the alkali metal salt content is 178 ppm (7.5 μm) in terms of metal element.
mol / g) [Sodium: 170 ppm (7.3 μm)
ol / g), potassium: 8 ppm (0.2 μmol /
g)], and the content of trifluoromethanesulfonate ion was 290 ppm (1.9 μmol / g). The content of alkali metal ions was 3.9 times (molar ratio) the content of trifluoromethanesulfonate ions. The modified EVOH (C) has an ethylene content of 44 mol% and a structural unit (I) content of 2.3.
It was mol%.

Using the modified EVOH (C) thus obtained, a monolayer film and a multilayer film were produced in the same manner as in Example 1, the oxygen permeation rate and haze were measured, and the flex resistance and stretchability were evaluated. did. The physical properties and the like of the modified EVOH (C) are summarized in Table 1, and the evaluation results and the like of the film are summarized in Table 2.

Comparative Example 1 Modified EVOH (C) was obtained in the same manner as in Example 1 except that the feed of the catalyst (D) solution and the catalyst deactivator (E) aqueous solution was stopped. It was The modified E
The MFR of VOH (C) is 3.7 g / 10 minutes (190 ° C,
2160g under load), zinc ion content is 0pp
m, and the alkali metal salt content is 8 p in terms of metal elements.
It was pm (all potassium), and the content of trifluoromethanesulfonate ion was 0 ppm. The modified EVOH (C) obtained had an ethylene content of 32 mol% and a structural unit (I) content of 1.8 mol%.

Using the modified EVOH (C) thus obtained, a monolayer film and a multilayer film were produced in the same manner as in Example 1, the oxygen permeation rate and haze were measured, and the flex resistance and stretchability were evaluated. did. The physical properties and the like of the modified EVOH (C) are summarized in Table 1, and the evaluation results and the like of the film are summarized in Table 2.

Comparative Example 2 A modified EVOH (C) was obtained in the same manner as in Example 2, except that the catalyst (D) and the catalyst deactivator (E) were not used. MF of the modified EVOH (C)
R is 1.8 g / 10 minutes (under 190 ° C. and 2160 g load)
The zinc ion content was 0 ppm, the alkali metal salt content (metal element conversion value) was 15 ppm (sodium: 5 ppm, potassium: 10 ppm), and the trifluoromethanesulfonate ion content was 0 ppm. . The resulting modified EVOH (C) had an ethylene content of 44 mol% and a structural unit (I) content of 1.5.
It was mol%.

Using the modified EVOH (C) thus obtained, a monolayer film and a multilayer film were produced in the same manner as in Example 1, the oxygen permeation rate and haze were measured, and the flex resistance and stretchability were evaluated. did. The physical properties and the like of the modified EVOH (C) are summarized in Table 1, and the evaluation results and the like of the film are summarized in Table 2.

Comparative Example 3 100 parts by weight of water-containing pellets (water content: 130% (dry base)) made of EVOH having an ethylene content of 32 mol%, a saponification degree of 99.6% and an intrinsic viscosity of 0.0959 L / g, Acetic acid 0.1 g / L, potassium dihydrogen phosphate 0.04
6 parts at 25 ° C. in 370 parts by weight of an aqueous solution containing 4 g / L.
It was immersed and stirred for a time. The pellets obtained are heated at 105 ° C for 2
After drying for 0 hour, dry EVOH pellets were obtained. The potassium content of the dry EVOH pellets was 8 ppm (metal element conversion), the acetic acid content was 53 ppm, the phosphoric acid compound content was 20 ppm (phosphate radical conversion value), and the alkaline earth metal salt content was 0 ppm. . The MFR of the dried pellet was 4.5 g / 10 minutes (190 ° C, 216
It was 0 g load).

Except that the unmodified EVOH (A) was used in place of the modified EVOH (C) used in Example 1,
A monolayer film and a multilayer film were produced in the same manner as in Example 1, the oxygen permeation rate and the haze were measured, and the stretchability was evaluated.

The bending resistance was evaluated as follows. Using the unmodified EVOH (A) pellets, a film forming machine consisting of a 40φ extruder and a T-die was used to form a film at an extrusion temperature of 180 to 210 ° C. and a T-die temperature of 210 ° C. to obtain a film having a thickness of 25 μm. It was Next, 21 cm
40 single-layer films made of the above-prepared EVOH cut into 30 cm were prepared, and the humidity of each film was adjusted at 20 ° C.-65% RH for 5 days.
According to F 392-74, using a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., the number of flexing was 25 times, 30 times,
After bending 35 times, 40 times, 50 times, 60 times, 80 times and 100 times, the number of pinholes was measured. The measurement was performed 5 times at each bending number, and the average value was used as the number of pinholes. The number of bends (P) is taken on the horizontal axis and the number of pinholes (N) is taken on the vertical axis, and the above measurement results are plotted.
The number of bends (Np1) when the number of pinholes was 1 was determined by extrapolation. The Np1 of the film of this comparative example was 34 times.

Table 1 shows the physical properties of EVOH (A).
Table 2 shows the evaluation results of the films.

Comparative Example 4 100 parts by weight of water-containing pellets (water content: 130% (dry base)) made of EVOH having an ethylene content of 44 mol%, a saponification degree of 99.6% and an intrinsic viscosity of 0.0948 L / g, Acetic acid 0.12 g / L, potassium dihydrogen phosphate 0.0
It was immersed and stirred at 25 ° C. for 6 hours in 370 parts by weight of an aqueous solution containing 44 g / L. The obtained pellets were dried at 105 ° C. for 20 hours to obtain dry EVOH pellets. The potassium content of the dry EVOH pellets was 8 ppm (metal element conversion), the acetic acid content was 62 ppm, the phosphoric acid compound content was 20 ppm (phosphate radical conversion value), and the alkaline earth metal salt content was 0 ppm. . The MFR of the dried pellet was 5.5 g / 10 minutes (190 ° C, 21 ° C).
The load was 60 g).

Except that the unmodified EVOH (A) was used in place of the modified EVOH (C) used in Example 1,
A monolayer film and a multilayer film were produced in the same manner as in Example 1, the oxygen permeation rate and the haze were measured, and the stretchability was evaluated. In addition, bending resistance was evaluated in the same manner as in Comparative Example 3. Table 1 shows the physical properties of EVOH (A), and Table 2 shows the evaluation results of the film.

[0209]

[Table 1]

[0210]

[Table 2]

In Examples 1 to 3 using the catalyst (D),
Even when melt kneading at a relatively low temperature of 200 to 220 ° C., the EVOH (A) can be efficiently reacted with the monovalent epoxy compound (B), and the modified EVOH (C having a large content of the structural unit (I) (C) can be obtained. ) Was able to be obtained. At this time, the MFR of the modified EVOH (C) is the MFR of the raw material EVOH (A).
Almost no change compared to FR. EVOH (A)
The effect of accelerating the reaction between the monovalent epoxy compound (B) and the monovalent epoxy compound (B) is that the catalyst (D) containing zinc ions (Example 1) more than the catalyst (D) containing yttrium ions (Example 3).
And 2) is larger.

On the other hand, in Comparative Examples 1 and 2 in which the catalyst (D) was not used, only the modified EVOH (C) having a smaller content of the structural unit (I) was obtained as compared with the above Examples 1 to 3. There wasn't. In addition, M of the obtained modified EVOH (C)
FR was lower than the MFR of the raw material EVOH (A).

Modified EVOH Containing Structural Unit (I)
(C) (Examples 1 to 3) are unmodified EVOH (A)
Compared with (Comparative Examples 3 and 4), the oxygen permeation rate increased to some extent, but the transparency, bending resistance, and stretchability were greatly improved. Further, since the melting point is lowered, it is possible to perform melt molding at a lower temperature. As the content of the structural unit (I) increases, the bending resistance and stretchability are improved, and the melting point is also lowered. It is necessary to set the content. According to the method for producing a modified EVOH (C) of the present invention, it is possible to melt-knead at a relatively low temperature and set the content of the structural unit (I) in a wide range.

[0214]

INDUSTRIAL APPLICABILITY The modified EVOH (C) of the present invention has excellent barrier properties, transparency, stretchability and bending resistance, and is suitably used as a barrier material. Further, it can be suitably used for various molded products and multilayer structures. In producing such a modified EVOH (C), according to the production method of the present invention, an EV can be used efficiently at a relatively low temperature using an extruder.
The modified EVOH (C) can be obtained by reacting OH (A) with the monovalent epoxy compound (B).

[Brief description of drawings]

FIG. 1 is a schematic diagram of a configuration of an extruder used for producing a modified EVOH (C) in Example 1.

FIG. 2 ¹ H of modified EVOH (C) obtained in Example 1
It is a figure which shows a-NMR chart.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA15X AA29X AA76 AA78                       AB11A AB23A AC04A AC19                       AE22A AF08 AH04 BA01                       BB06 BC01                 4J100 AA02P AD02Q BA02H BA03H                       BA04H BC02H BC21H BC43H                       CA04 CA31 DA32 HA61 HA62                       HB24 HB50 HB57 HB63 HC01                       HC04 HC08 HC12 HC27 HC28                       HC33 HC43 HC71 HC75 HD16                       HE17 HE41 JA58

Claims (18)

[Claims] 1. An ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound (B) having a molecular weight of 500 or less.
Of the modified ethylene-vinyl alcohol copolymer (C), characterized by melt-kneading and in the presence of a catalyst (D) containing ions of a metal belonging to Groups 3 to 12 of the periodic table. Production method. 2. The modified ethylene-vinyl alcohol copolymer (A) according to claim 1, wherein the ethylene-vinyl alcohol copolymer (A) has an ethylene content of 5 to 55 mol% and a saponification degree of 90% or more. Method C). 3. The monovalent epoxy compound (B) has 2 to 10 carbon atoms.
The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to claim 1 or 2, which is the epoxy compound of 8. 4. The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to claim 1, wherein the catalyst (D) contains zinc ions. 5. The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to claim 1, wherein the catalyst (D) contains a sulfonate ion. 6. A monovalent epoxy compound (B) based on 100 parts by weight of the ethylene-vinyl alcohol copolymer (A).
The modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 5, wherein 1 to 50 parts by weight is melt-kneaded.
Manufacturing method. 7. The number of moles of metal ion relative to the weight of the ethylene-vinyl alcohol copolymer (A) is 0.1-2.
7. The catalyst (D) is present in an amount of 0 μmol / g.
5. The method for producing the modified ethylene-vinyl alcohol copolymer (C) according to any one of 1. 8. The modification according to claim 1, wherein a mixture of the monovalent epoxy compound (B) and the catalyst (D) is added to the molten ethylene-vinyl alcohol copolymer (A). Ethylene-vinyl alcohol copolymer (C)
Manufacturing method. 9. An ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound (B) are melt-kneaded in the presence of a catalyst (D) and then a catalyst deactivator (E) is added. The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8, which comprises melt-kneading. 10. The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to claim 9, wherein the catalyst deactivator (E) is a chelating agent. 11. A ratio (E / D) of the number of moles of the catalyst deactivator (E) to the number of moles of metal ions contained in the catalyst (D).
Is 0.2-10, The manufacturing method of the modified ethylene-vinyl alcohol copolymer (C) of Claim 9 or 10. 12. The ethylene-vinyl alcohol copolymer (A) and the monovalent epoxy compound (B) are melt-kneaded in the presence of the catalyst (D) to remove the unreacted monovalent epoxy compound (B). The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 9 to 11, wherein the catalyst deactivator (E) is added after that. 13. A modified ethylene-containing 0.3 to 40 mol% of the following structural unit (I) and 0.1 to 20 μmol / g of an ion of a metal belonging to Groups 3 to 12 of the periodic table.
Vinyl alcohol copolymer (C). [Chemical 1] (In the formula, R ¹ , R ² , R ^3, and R ⁴ are each a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or 6 to 10 carbon atoms. Represents an aromatic hydrocarbon group of R ¹ , R ² , R ³ and R ⁴ may be the same group,
It can be different. R ³ and R ⁴ may be bonded. Further, R ¹ , R ² , R ³ and R ⁴ may have a hydroxyl group, a carboxyl group or a halogen atom. ) 14. The composition according to claim 1, which contains a sulfonate ion.
The modified ethylene-vinyl alcohol copolymer (C) according to item 3. 15. The modified ethylene-vinyl alcohol copolymer (C) according to claim 14, wherein the content of the alkali metal ion is 1 to 50 times (molar ratio) the content of the sulfonate ion. 16. A barrier material comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 13 to 15. 17. A molded article comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 13 to 15. 18. A multilayer structure comprising at least one layer comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 13 to 15.