JP2003231715A - Modified ethylene - vinyl alcohol copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified ethylene - vinyl alcohol copolymer excellent in barrier property, transparency, drawability, flexibility and flex proofness. <P>SOLUTION: This modified ethylene - vinyl alcohol copolymer contains an ethylene content of 5 to 55 mol % and 0.3 to 40 mol % of a structural unit expressed by formula (I) (wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>each represents a hydrogen atom, a 1-10C aliphatic hydrocarbon group, a 3-10C alicyclic hydrocarbon group, a 6-10C aromatic hydrocarbon group, where R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>may be same or different and R<SP>3</SP>and R<SP>4</SP>may be linked to each other, and the R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>may each contain a hydroxy group, a carboxy group and/or a halogen atom.). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to barrier properties, transparency,
Modified ethylene with excellent stretchability, flexibility and flex resistance
TECHNICAL FIELD The present invention relates to a vinyl alcohol copolymer and a method for producing 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, flexibility and bending resistance. In order to improve this drawback, a method of blending EVOH with a flexible resin such as an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer is known. However, this method has a drawback that the transparency is greatly reduced.

Further, the ethylene content is 25 to 60 mol%, which is excellent in stress cracking resistance, polar solvent resistance, water resistance, and has good gas barrier properties such as oxygen and excellent moldability, especially stretchability. 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
To 0.8 parts by weight of a polyvalent epoxy compound are reacted, and a method for producing an EVOH-modified product with improved moldability is disclosed.

[0005]

However, in the above-mentioned conventional technique, the stretchability, flexibility, and flex resistance of EVOH are not always sufficient. Furthermore, the stretchability, flexibility and flex resistance of EVOH and transparency were not satisfied at the same time. An object of the present invention is to provide a modified ethylene-vinyl alcohol copolymer (C) which is excellent in all of barrier properties, transparency, stretchability, flexibility and bending resistance.

[0006]

[Means for Solving the Problems] The above-mentioned problems are solved ethylene-vinyl alcohol copolymer (C) containing 0.3 to 40 mol% of the following structural unit (I) and having an ethylene content of 5 to 55 mol%. Will be solved by providing.

[0007]

[Chemical 3]

(Wherein R ¹ , R ² , R ³ and R ⁴ are
It represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, 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. In addition, R ³ and R ⁴ may be bonded. Further, the above 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-
The vinyl alcohol copolymer (C) has the same structure as R ¹ and R
² is a modified ethylene-vinyl alcohol copolymer (C) in which both are hydrogen atoms. In a more preferred embodiment,
One of R ³ and R ⁴ is a modified ethylene-vinyl alcohol copolymer (C) in which one is an aliphatic hydrocarbon group having 1 to 10 carbon atoms and the other is a hydrogen atom. In another more preferred embodiment, one of R ³ and R ⁴ is a substituent represented by (CH ₂ ) _i OH (where i is an integer of 1 to 8), and the other is a hydrogen atom. Is a modified ethylene-vinyl alcohol copolymer (C).

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) has an oxygen permeation rate of 100 cc · 20 μm / m ² · da at 20 ° C. and 65% RH.
It is y · atm or less. Furthermore, in a preferred embodiment,
Carbon dioxide permeation rate at 20 ° C and 65% RH is 500
cc · 20 μm / m ² · day · atm or less.

In a preferred embodiment, modified ethylene-vinyl chloride
Of alcoholic copolymer (C) at 23 ° C and 50% RH
Young's modulus in tensile strength / elongation measurement is 140 kgf /
mm ^TwoIt is the following. Also in a preferred embodiment, 23
Tensile yield in tensile strength and elongation measurement at 50 ° C and 50% RH
The yield strength is 0.5 to 7 kgf / mm^TwoAnd tension
The breaking elongation is 150% or more.

The problem to be solved by the present invention is as follows.
Ethylene-vinyl alcohol copolymer (A) and molecular weight 5
It is also solved by providing a method for producing a modified ethylene-vinyl alcohol copolymer (C), which comprises reacting with a monovalent epoxy compound (B) of 00 or less.

In a preferred embodiment, a modified ethylene-vinyl alcohol copolymer is prepared by reacting 100 parts by weight of the ethylene-vinyl alcohol copolymer (A) with 1 to 50 parts by weight of a monovalent epoxy compound (B) having a molecular weight of 500 or less. Coalescence (C)
Is a manufacturing method.

In a preferred embodiment, the ethylene-vinyl alcohol copolymer (A) is a modified ethylene-vinyl copolymer which is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 55 mol% and a saponification degree of 90% or more. It is a method for producing an alcohol copolymer (C).

In a preferred embodiment, the ethylene-vinyl alcohol copolymer (A) is an ethylene-vinyl alcohol copolymer having an alkali metal salt content of 50 ppm or less in terms of a metal element. Modified ethylene-vinyl It is a method for producing an alcohol copolymer (C). Further, in a preferred embodiment, the ethylene-vinyl alcohol copolymer (A) is a modified ethylene- which is an ethylene-vinyl alcohol copolymer having an alkaline earth metal salt content of 20 ppm or less in terms of metal element. It is a method for producing a vinyl alcohol copolymer (C).

In a preferred embodiment, the monovalent epoxy compound (B) having a molecular weight of 500 or less 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 modified ethylene-vinyl alcohol is characterized in that the reaction of the ethylene-vinyl alcohol copolymer (A) with the monovalent epoxy compound (B) having a molecular weight of 500 or less is carried out in an extruder. It is a method for producing the copolymer (C). In a more preferred embodiment, a modified ethylene-vinyl alcohol copolymer (A) in which a monovalent epoxy compound (B) having a molecular weight of 500 or less is added to the ethylene-vinyl alcohol copolymer (A) in a molten state in the extruder ( It is the manufacturing method of C).

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) contains the structural unit (I) below in an amount of 0.3 to 40 mol% and an ethylene content of 5 to 55.
It is a method for producing a modified ethylene-vinyl alcohol copolymer (C), which is a modified ethylene-vinyl alcohol copolymer in mol%.

[0019]

[Chemical 4]

(Wherein R ¹ , R ² , R ³ and R ⁴ are
It represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, 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. In addition, R ³ and R ⁴ may be bonded. Further, the above 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) is used as a barrier material. In a more preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a gas barrier material.

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a composition consisting of it.

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as an extruded product. Also, in a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a film or sheet. Furthermore, in a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a stretched film. In another preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a heat shrink film.

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a wallpaper or a decorative plate. In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as a pipe or hose. In another preferred embodiment, it is used as a shaped article. Also, in a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is used as an extrusion blow-molded article. Furthermore, in a preferred embodiment,
The modified ethylene-vinyl alcohol copolymer (C) is used as a flexible packaging material.

In a preferred embodiment, the modified ethylene-vinyl alcohol copolymer (C) is a resin other than the modified ethylene-vinyl alcohol copolymer (C) and the modified ethylene-vinyl alcohol copolymer (C). It is used as a multilayer structure formed by laminating and. In a more preferred embodiment, the resin other than the modified ethylene-vinyl alcohol copolymer (C) is selected from the group consisting of polyolefin, polyamide, polyester, polystyrene, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile and polycarbonate. It is a multi-layer structure which is at least one kind. In another more preferred embodiment, the resin other than the modified ethylene-vinyl alcohol copolymer (C) is a multilayer structure in which it is an elastomer.

In a preferred embodiment, the multilayer structure is used as a coextruded film or sheet.

In another preferred embodiment, the multilayer structure is used as a multilayer pipe or a multilayer hose. In a more preferred embodiment, the multilayer pipe is used as a fuel pipe or a pipe for circulating hot water. Also,
In another more preferred embodiment, said multi-layer hose is used as a fuel hose.

In a preferred embodiment, the multilayer structure is
Used as a co-extrusion blow molded container.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The modified ethylene-vinyl alcohol copolymer (C) of the present invention comprises the following structural unit (I):
It is a modified ethylene-vinyl alcohol copolymer (C) containing 3 to 40 mol% and having an ethylene content of 5 to 55 mol%.

[0030]

[Chemical 5]

(Wherein R ¹ , R ² , R ³ and R ⁴ are
It represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, 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. In addition, R ³ and R ⁴ may be bonded. In addition, the above R ¹ , R ² , R ³ and R ⁴ are other groups, for example, a hydroxyl group, a carboxyl group,
It may have a halogen atom or the like. )

In a more preferred embodiment, the R¹and
R^TwoAre both hydrogen atoms. Further preferred embodiment
Then, R¹And R^TwoAre both hydrogen atoms, and
Note R ^ThreeAnd R^FourOf these, one is a C1-C10 fat
It is a group hydrocarbon group, and the other is a hydrogen atom. Good
Suitably, the aliphatic hydrocarbon group is an alkyl group or an alkyl group.
It is a kenyl group. Gas barrier property of modified EVOH (C)
From the viewpoint of particular importance, R^ThreeAnd R^FourOut of
One is a methyl or ethyl group and the other is a hydrogen atom
Is more preferable.

From the viewpoint of the gas barrier property of the modified EVOH (C), one of R ³ and R ⁴ is (C
H ₂ ) _i OH is a substituent (provided that i is an integer of 1 to 8) and the other is preferably a hydrogen atom.
When particular importance is attached to the gas barrier property of the modified EVOH (C), in the substituent represented by (CH ₂ ) _i OH, i is an integer of 1 to 4, preferably 1 or 2. Is more preferred, and 1 is even more preferred.

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 in the modified EVOH (C) is within the above range, a modified EVOH (C) having gas barrier properties, transparency, stretchability, flexibility and bending resistance is obtained. be able to.

The ethylene content of the modified EVOH (C) of the present invention is preferably 5 to 55 mol%. From the viewpoint that the modified EVOH (C) of the present invention obtains good stretchability, flexibility and flex resistance, the lower limit of the ethylene content of the modified EVOH (C) is more preferably 10 mol% or more,
It is more preferably at least 20 mol%, and particularly preferably 2
It is 5 mol% or more, and more 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, further preferably 45 mol% or less. is there. 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 constituent components other than the structural unit (I) and the ethylene unit are mainly vinyl alcohol units. The vinyl alcohol unit is usually a vinyl alcohol unit which has not reacted with the monovalent epoxy compound (B) among the vinyl alcohol units contained in the raw material EVOH (A).
The unsaponified vinyl acetate unit that may be contained in EVOH (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 constituents may be contained within a range not impairing the object of the present invention.

A 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, 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 method for producing the modified EVOH (C) is not particularly limited. The method recommended by the present inventors is to modify ethylene-vinyl alcohol copolymer (A) having an ethylene content of 5 to 55 mol% with a monovalent epoxy compound (B) having a molecular weight of 500 or less to obtain a modified EVOH.
This is a method of obtaining (C).

The problem to be solved by the present invention is as follows.
Ethylene-vinyl alcohol copolymer (A) and molecular weight 5
It is also achieved by providing a method for producing a modified ethylene-vinyl alcohol copolymer (C), which comprises reacting with a monovalent epoxy compound (B) of not more than 00.

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; It is also possible to copolymerize vinylsilane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidone such as N-vinylpyrrolidone.

When EVOH obtained by copolymerizing a vinylsilane compound 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, flexibility and flex resistance, the lower limit of the ethylene content of EVOH (A) is more preferably 10 mol% or more, and It is preferably 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 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 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. If 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 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 can be determined by the nuclear magnetic resonance (NMR) method.

Further, as the EVOH (A), EVOH blended with a boron compound may be used within a range not impeding 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 (A) containing a phosphoric acid compound may be used as EVOH (A). 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. The phosphate may be contained in any form of a first phosphate, a second phosphate and a third phosphate, but the first 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 EVOH (A) used in the present invention is preferably 200 in terms of phosphate radical.
ppm or less, more preferably 5 to 100 ppm, most preferably 5 to 50 ppm.

Further, as 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
(A) is exposed to heating conditions. At this time, EVOH
The modified EVOH obtained when (A) contains an excessive amount of an alkali metal salt and / or an alkaline earth metal salt.
(C) may be colored. In addition, modified EVOH
A problem such as a decrease in the viscosity of (C) may occur and the moldability may decrease.

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 also be used as long as it does not impair the object of the present invention.

The intrinsic viscosity of EVOH (A) used in the present invention is preferably 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, the stretchability, flexibility and flex resistance may decrease. When the intrinsic viscosity of EVOH (A) exceeds 0.2 L / g, modified EVOH (C)
There is a concern that gels and lumps may be easily generated in the molded product made of.

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. These EVOH resins may be used alone or in combination of two or more.

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,
In the production process of the monovalent epoxy compound, a very small amount of the polyvalent epoxy compound may be contained. However, a monovalent epoxy compound containing a very small amount of polyvalent epoxy compound may be used as the monovalent epoxy compound (B) of the present invention having a molecular weight of 500 or less as long as the effect of the present invention is not impaired. It is possible.

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.

[0058]

[Chemical 6]

[0059]

[Chemical 7]

[0060]

[Chemical 8]

[0061]

[Chemical 9]

[0062]

[Chemical 10]

[0063]

[Chemical 11]

[0064]

[Chemical 12]

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R
⁹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group or an alkenyl group), and 3 to 1 carbon atoms
It represents an alicyclic hydrocarbon group having 0 (cycloalkyl group, cycloalkenyl group, etc.) and an aromatic hydrocarbon group having 6 to 10 carbon atoms (phenyl group, etc.). Moreover, i, j, k, l, and m represent the integers of 1-8. )

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) and 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.

Examples of the monovalent epoxy compound (B) represented by the above formula (VII) having a molecular weight of 500 or less include 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. 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 requiring hygiene such as food packaging, beverage packaging, and pharmaceutical packaging, 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane and epoxyethane are used as the epoxy compound (B). It is preferable to use epoxy propane.

By reacting the above EVOH (A) with the above monovalent epoxy compound (B), a modified EVOH is obtained.
(C) is obtained. At this time, the preferable mixing ratio of EVOH (A) and monovalent epoxy compound (B) is (A) 1
(B) 1 to 50 parts by weight with respect to 00 parts by weight, and more preferably (B) 2 to 40 parts with respect to 100 parts by weight of (A).
Parts by weight, and particularly preferably 5 to 35 parts by weight (B) per 100 parts by weight of (A).

The method for producing the modified EVOH (C) by reacting EVOH (A) with a monovalent epoxy compound (B) having a molecular weight of 500 or less is not particularly limited,
Suitable methods include a production method in which EVOH (A) and a monovalent epoxy compound (B) are reacted in a solution, and a production method in which EVOH (A) and a monovalent epoxy compound (B) are reacted in an extruder. To be

In the production method by the solution reaction, EVOH is used.
The modified EVOH (C) is obtained by reacting the solution of (A) with the monovalent epoxy compound (B) in the presence of an acid catalyst or an alkali catalyst. The modified EVOH (C) can also be produced by dissolving EVOH (A) and the monovalent epoxy compound (B) in a reaction solvent and performing heat treatment. The reaction solvent is preferably a polar aprotic solvent which is a good solvent for EVOH (A) such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

Examples of the reaction catalyst include acid catalysts such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid and boron trifluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium methoxide. Alkali catalyst of. Of these, it is preferable to use an acid catalyst. As the amount of catalyst,
0.0001 to 1 with respect to 100 parts by weight of EVOH (A)
About 0 parts by weight is suitable. A suitable reaction temperature is from room temperature to 150 ° C.

In the production method in which the EVOH (A) and the monovalent epoxy compound (B) are reacted in the extruder, the extruder to be used is not particularly limited, but a single-screw extruder, a twin-screw extruder or a twin-screw extruder or more. Using a multi-screw extruder of 200 ℃ ~
It is preferable to react the EVOH (A) with the monovalent epoxy compound (B) at a temperature of about 300 ° C. When a twin-screw extruder or a multi-screw extruder having two or more screws is used, it is easy to increase the pressure in the reaction section by changing the screw configuration, and the EVOH (A) and the monovalent epoxy compound (B) are combined. The reaction can be carried out efficiently. 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.

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 is required, and it is necessary to collect and remove the solvent from the reaction system after the reaction is completed, which complicates the process. Further, in order to increase the reactivity between the EVOH (A) and the monovalent epoxy compound (B), it is preferable to maintain the reaction system under heating and / or pressurizing conditions, but as compared with the case of solution reaction. Thus, in the reaction in the extruder, it is easy to maintain the heating and / or pressurizing conditions of the reaction system, and from that viewpoint, the reaction in the extruder has a great merit.

Further, EVOH (A) was 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 EVOH (A) and the monovalent epoxy compound (B), a modified EVOH (C) having the above-mentioned structural unit (I) is obtained, but the hydroxyl group contained in the structural unit (I) is Further, the reaction with the monovalent epoxy compound (B) may result in a product different from the structural unit specified in the present invention.

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

[0082]

[Chemical 13]

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

As a result of the investigations by the present inventors, a modification obtained by increasing the proportion of the structural unit (II) shown above, which is different from the structural unit (I) specified in the present invention, is obtained. It was revealed that the gas barrier property of EVOH (C) is lowered. In addition, EVOH (A) in the extruder
When the reaction of the monovalent epoxy compound (B) with
It has been found that the occurrence of such side reaction can be effectively suppressed. From this point of view, EVOH in the extruder is also
A method of producing a modified EVOH (C) by reacting (A) with a monovalent epoxy compound (B) is preferable.

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.

EVOH (A) during the reaction in the extruder
The method for mixing the monovalent epoxy compound (B) and the monovalent epoxy compound (B) is not particularly limited, and the EVOH (A) before being fed to the extruder is sprayed with the monovalent epoxy compound (B) or the EVOH (A ) Is fed and brought into contact with the monovalent epoxy compound (B) in the extruder, and the like. Among these, monovalent epoxy compounds (B)
From the viewpoint of suppressing the volatilization of the EVO to the outside of the system, EVO
A method in which H (A) is fed and then contacted with the monovalent epoxy compound (B) in the extruder is preferable. Further, the position of addition of the monovalent epoxy compound (B) into the extruder is also arbitrary, but from the viewpoint of the reactivity between the EVOH (A) and the epoxy compound (B), it may be added to the molten EVOH (A). It is preferable to add the monovalent epoxy compound (B).

The production method by the reaction of EVOH (A) and monovalent epoxy compound (B) in the extruder recommended by the present inventor is (1) EVOH (A) melting step, (2) And a step of removing the unreacted monovalent epoxy compound (B) by a vent or the like. 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.

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 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,
It can also be added after the modified EVOH (C) is obtained by the reaction of VOH (A) with the epoxy compound (B). Generally, EVOH is used for improving adhesion and suppressing coloring.
In order to improve various physical properties of (1), EVOH is often added with at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids and phosphoric acid compounds, if necessary. However, as described above, the addition of the various compounds described above can be achieved by the EV of the extruder.
At the time of the reaction between OH (A) and the epoxy compound (B), there is a risk of causing coloration or a decrease in viscosity. Therefore, EV
After the reaction between OH (A) and the epoxy compound (B), the remaining epoxy compound (B) is removed by a vent, and then selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids and phosphoric acid compounds. At least one
It is preferable to add to the obtained modified EVOH (C). By adopting this addition method, the modified EVOH of the present invention can be produced without causing problems such as coloring and viscosity reduction.
(C) is obtained.

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.

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 has such a low oxygen permeation rate, the modified EVOH (C) of the present invention is preferably used as a barrier material, more preferably as a gas barrier material. One particularly preferred embodiment is a food packaging container.

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. Since the resin has such a low oxygen permeation rate, the modified EVOH (C) of the present invention is preferably used as a barrier material, more preferably as a gas barrier material. More preferably, a food packaging container is used, and it is particularly preferably used as a container for carbonated beverages.

The modified EVOH (C) of the present invention has a temperature of 23 ° C.
The Young's modulus in the tensile strength / elongation measurement at 50% RH is preferably 140 kgf / mm ² or less. The modified EVOH (C) of the present invention, more preferably the upper limit of the Young's modulus is 120 kgf / mm ² or less, and more preferably 100 kgf / mm ² or less. The modified EVOH (C) of the present invention has a temperature of 23 ° C.
The Young's modulus in the tensile strength / elongation measurement at 50% RH is preferably 1 kgf / mm ² or more. By using such modified EVOH (C), the obtained molded article such as a sheet or film becomes flexible and can be favorably subjected to secondary processing when it is stretched or thermoformed.
Modified EVO with Young's modulus of 140 kgf / mm ² or less
H (C) is a structural unit (I) contained in the modified EVOH (C).
It is obtained by setting the amount of 0.3 to 40 mol%.
More preferably, the structural unit (I) of modified EVOH (C)
Content of 1 to 35 mol%, more preferably 2
˜30 mol%, and particularly preferably 4 to 30 mol%.

The modified EVOH (C) of the present invention has a temperature of 23 ° C., 5
A molded product such as a sheet or film having a tensile yield strength of 0.5 to 7.0 kgf / mm ² in a tensile strength and elongation measurement at 0% RH and a tensile breaking elongation of 150% or more. Is preferable because it exhibits good moldability when stretched or thermoformed. As the modified EVOH (C) of the present invention, it is more preferable that the tensile yield strength is 1.0 to 6.5 kgf / mm ² and the tensile elongation at break is 200% or more, and the tensile yield strength is 1.5-6.0 kgf /
a mm ^2, and a tensile breaking elongation of 250% or more is more preferable. In addition, the modified EVOH of the present invention
It is preferable that (C) has a tensile yield strength of 0.5 to 7.0 kgf / mm ² in a tensile strength / elongation measurement at 23 ° C. and 50% RH, and a tensile elongation at break of 1000% or less. . Tensile yield strength at 23 ° C, 50% RH is 0.
The modified EVOH (C) having a tensile elongation at break of 150% or more is 5 to 7.0 kgf / mm ^2.
It is obtained by adjusting the amount of the structural unit (I) contained in H (C) to 0.3 to 40 mol%. More preferably, modified E
The content of the structural unit (I) of VOH (C) is 1 to 35 mol%, more preferably 2 to 30 mol%, and particularly preferably 4 to 30 mol%.

The modified EVOH (C) of the present invention is preferably molded into various molded products such as films, sheets, containers, pipes, hoses and fibers by melt molding. 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 and the like are exemplified as suitable ones. It 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 is lacking in stretchability, flexibility 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 flexibility and flex resistance, etc., EVOH and other resins are laminated. I had to do a lot. However, the modified EVOH (C) of the present invention is transparent, stretchable,
Since it has excellent performance in both flexibility and flex resistance, it can be used as a single-layer molded product even in applications where impact resistance, flexibility and / or flex resistance are required. is there. 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 impact resistance, flexibility and bending resistance, a single layer molded article made of the modified EVOH (C) is a film or an extruded product. Blow-molded articles (preferably bottles etc.), flexible packaging containers (preferably flexible tubes or pouches etc.), pipes, hoses and shaped articles are preferable.

The film is particularly preferably a stretched film from the viewpoint of utilizing the characteristic of the modified EVOH (C) of the present invention that it has excellent 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.

The modified EVOH (C) of the present invention is used to improve the barrier property and shape retention under high temperature and high humidity, or to improve the shrinkage when used for heat shrink film and the like. In addition, a crosslinked structure can be applied to such an extent that the effects of the present invention are not impaired. The method for forming the crosslinked structure is not particularly limited, but a preferable method is a method of irradiating with energy rays. Examples of energy rays include ionizing radiation such as ultraviolet rays, electron rays, X-rays, α rays, and γ rays, and electron rays are preferable.

Regarding the electron beam irradiation method, after the primary processing by extrusion molding, the molded body is introduced into an electron beam irradiation apparatus,
The method of irradiating with an electron beam is mentioned. The electron beam dose is not particularly limited, but preferably 1 to 40 Mra
It is within the range of d. If the electron dose to be irradiated is lower than 1 Mrad, crosslinking will be difficult to proceed. On the other hand, when the electron dose to be irradiated exceeds 40 Mrad, the deterioration of the molded body is likely to proceed. More preferably, the electron dose range is 2 to 30 Mrad.
Is.

After the primary molding, (uniaxial and / or 2
For a molded product that requires secondary molding such as axial drawing and thermoforming, it is preferable to perform electron beam irradiation between the primary molding and the secondary molding.

Electron beams that can be used in the above crosslinking treatment are generally Kotsucroft-Watson type, Van De Graaf type, resonance transformer type, insulating core transformer type, linear accelerator, dynamitron type, high frequency wave. 150 to 10 emitted from various electron beam accelerators such as cyclotron
The one with energy of 000 KeV is used,
Not so.

In addition, the above-mentioned cross-linking treatment is performed with modified EVOH.
Modified EVO with a cross-linking aid when applied to (C)
It is preferable to use H (C). As a crosslinking aid,
Preferred examples of the polyfunctional allyl compound and the polyfunctional (meth) acrylic compound include allyl compounds having at least two functional groups and (meth) acrylic compounds. Specifically, triallyl cyanurate (TAC), triallyl isocyanurate (TAI)
C), pentaerythritol tetramethacrylate (P
ETMA), glutaraldehyde (GA), ethylene glycol dimethacrylate (EGDMA), diallyl maleate (DAM), dipropazyl maleate (DP)
M), dipropadyl monoallyl cyanurate (DPMA
C), trimethylolpropane triacrylate (TM)
PTAT), tetraethylene glycol diacrylate (TEGDA), 1,6 hexaglycol diacrylate, tetramethylolmethane tetraacrylate, dipropadyl succinate, diallyl fumarate, diallyl phthalate, and the like are exemplified. Among these, triallyl cyanate and Triallyl isocyanate is particularly preferred.

Although the modified EVOH (C) of the present invention can be put to practical use as a single-layer molded article as described above, the modified E
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.
rlier, Adhesive resin Ad, the modified EVOH
When the resins other than (C) are represented by R and the scrap recovery layer is represented by Reg, Barrier / R, R / Barrier /
R, Barrier / Ad / R, Reg / Barrie
r / R, R / Ad / Barrier / Ad / R, R / R
Examples thereof include, but are not limited to, eg / Ad / Barrier / Ad / Reg / R. In addition, modified EVOH
When a resin other than the modified EVOH (C) is provided on both surfaces of the layer composed of (C), different types may be used,
It may be the same. Furthermore, the recovered resin is modified with EVOH.
It may be blended with a resin other than (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 are 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-
Olefins), homopolymers of olefins such as polybutene and polypentene, and copolymers thereof. These α-
As a copolymerization component other than olefin, diolefin,
Vinyl compounds such as N-vinylcarbazole, vinyl chloride, vinylidene chloride, styrene, acrylonitrile, vinyl ether, etc., unsaturated carboxylic acids such as maleic acid, acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, itaconic acid, their esters and the like. Examples thereof include acid anhydrides and those obtained by adding a hydroxyl group or an epoxy group thereto. For example, a copolymer of a graftable monomer and a polyolefin or α-olefin / α,
Various copolymers such as an ionomer resin which is a reaction product of a β-unsaturated carboxylic acid copolymer and an ionic metal compound 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 the polyamide used in the present invention,
Polycapramide (nylon-6), poly-ω-aminoheptanoic acid (nylon-7), poly-ω-aminononanoic acid (nylon-9), polyundecaneamide (nylon-)
11), polylauryl lactam (nylon-12), polyethylene adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6) ), Polyhexamethylene sebacamide (nylon-6,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon) -10,6), polydodecamethylene sebacamide (nylon-12,10), or caprolactam / lauryllactam copolymer (nylon-6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon-6) / 9), caprolactam / hexamethylene adipamide copolymer (nylon-6
/ 6,6), lauryl lactam / hexamethylene adipamide copolymer (nylon-12 / 6,6), hexamethylene adipamide / hexamethylene sebacamide copolymer (nylon-6,6 / 6,6) 10), ethylene adipamide / hexamethylene adipamide copolymer (nylon-2,
6/6, 6), caprolactam / hexamethylene adipamide / hexamethylene sebacamide copolymer (nylon-
6/6, 6/6, 10), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexamethylene isophthalamide / terephthalamide copolymer and the like. These polyamides may be used alone or in combination of two or more.

Among these polyamides, polyamides containing a caproamide component (for example, nylon-6, nylon-6,12, nylon-6 / 12, nylon-6 /
6, 6, etc.) are preferred.

The polyester used in the present invention is not particularly limited. For example, poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene terephthalate / isophthalate), poly (ethylene glycol / cyclohexanedimethanol /
Preferred examples include terephthalate).
Among these, poly (ethylene terephthalate) is particularly preferable. As the polyester, ethylene glycol, butylene glycol, cyclohexanedimethanol, neopentyl glycol as a copolymerization component,
Diols such as pentanediol, or isophthalic acid, benzophenone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenylmethane dicarboxylic acid, propylene bis (phenyl carboxylic acid), diphenyl oxide dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipine It is also possible to use a polyester containing a dicarboxylic acid such as acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and diethylsuccinic acid.

It is also preferable to use an elastomer as the resin to be laminated with the modified EVOH (C) of the present invention. The elastomer used in the present invention is not particularly limited. For example, polyurethane-based elastomers, polystyrene-based elastomers, polyamide-based elastomers, polyester elastomers, polyolefin-based elastomers, elastomers composed of a copolymer of a vinyl aromatic compound and a conjugated diene compound, etc. are preferred examples.

The polyurethane elastomer used in the present invention includes, but is not particularly limited to, those comprising two or three components such as a high molecular diol and an organic diisocyanate, and / or a low molecular diol. Specific examples of each component will be described below.

The polymeric diol is a diol of a polymeric compound obtained by polycondensation, addition polymerization (for example, ring-opening polymerization) or polyaddition. Typical examples are polyester diol, polyether diol and polycarbonate diol. Alternatively, a co-condensate thereof (for example, polyester, ether diol) may be mentioned. These may be used alone or in combination of two or more.

Examples of the polyester diol include aliphatic diols such as ethylene glycol, propylene glycol and 1,5-pentanediol, or a mixture thereof, and aliphatic or aromatic dicarboxylic acids such as glutaric acid, adipic acid and terephthalic acid, or Polyester diols obtained from these mixtures can be used. Alternatively, a polylactone diol such as polycaprolactone glycol, polypropiolactone glycol or polyvalerolactone glycol is preferably used.

As the polyether diol, polyalkylene ether diols such as polyethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol are preferably used.

Further, as the polycarbonate diol, 1,4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, 1,8-octanediol, 1,10-
A polycarbonate diol obtained by polycondensation of an aliphatic diol having 2 to 12 carbon atoms such as decanediol or a mixture thereof with diphenyl carbonate or phosgene is preferably used.

The average molecular weight of these polymer diols is 50.
It is preferably in the range of 0 to 3000, preferably 500 to 2500. If the average molecular weight is too small, the compatibility with the organic diisocyanate is too good, and the elasticity of the resulting polyurethane becomes poor, while if the average molecular weight is too large, the compatibility with the organic diisocyanate becomes poor and mixing in the polymerization process does not go well, A gel-like lump may be formed or a stable polyurethane cannot be obtained.

The low molecular weight diol as the second raw material is a low molecular weight diol having a molecular weight of less than 500, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methylpentane. Glycols, 1,6-hexanediol, 1,4-bishydroxyethylbenzene and the like include aliphatic, alicyclic or aromatic diols. These may be used alone or in combination of two or more.

As the organic diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) is used.
Examples thereof include aromatic, alicyclic or aliphatic diisocyanates such as benzene, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate. These organic diisocyanates may be used alone or in combination of two or more.

The nitrogen content of the polyurethane elastomer used in the present invention is determined by appropriately selecting the use ratios of the polymeric diol, the low molecular weight and the organic diisocyanate, but in the practical range of 1 to 7%. Is preferably used in. When using thermoplastic polyurethane, a suitable catalyst that accelerates the reaction between the organic diisocyanate and the diol may be used if necessary. In addition, various additives such as colorants, fillers, antioxidants, and ultraviolet absorbers or lubricants can be added depending on the purpose.

The polyolefin elastomer used in the present invention is not particularly limited, but an ethylene-propylene copolymer elastomer (EPR) is exemplified as a suitable one. The ethylene-propylene copolymer is not particularly limited, and examples thereof include a random copolymer of ethylene and propylene, and a block copolymer. Further, the content of each composition is preferably at least 10% by weight or more, more preferably 20% by weight or more, from the viewpoint of having sufficient flexibility.

Further, the elastomer comprising the copolymer of the vinyl aromatic compound and the conjugated diene compound used in the present invention is not particularly limited. Examples of such vinyl aromatic compounds include styrene, α-methylstyrene, and 2
-Methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-
Benzylstyrene, 4- (phenylbutyl) styrene,
Styrenes such as 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and t-butoxystyrene; vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene. Vinyl group-containing aromatic compounds; vinylene group-containing aromatic compounds such as indene and acenaphthylene can be exemplified. The vinyl aromatic monomer unit may be only one kind or two or more kinds. However, it is preferably a unit derived from styrene.

The conjugated diene compound used in the copolymer composed of the vinyl aromatic compound and the conjugated diene compound is also not particularly limited. Examples of the conjugated diene compound include butadiene, isoprene, 2,3-dimethylbutadiene, pentadiene and hexadiene. At this time, the conjugated diene compound may be partially or completely hydrogenated. Examples of the copolymer consisting of a partially hydrogenated vinyl aromatic compound and a conjugated diene compound include styrene-ethylene / butylene-styrene triblock copolymer (SEBS) and styrene-
Examples thereof include ethylene / propylene-styrene triblock copolymer (SEPS) and hydrogenated products of styrene-conjugated diene copolymer.

Among the various elastomers exemplified above, it is preferable to use a polyurethane elastomer from the viewpoint of excellent interlayer adhesion between the layer made of modified EVOH (C) and the elastomer layer.

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. Examples of the ethylenically unsaturated carboxylic acid or its anhydride include ethylenically unsaturated monocarboxylic acid, its ester, ethylenically unsaturated dicarboxylic acid, its mono- or diester, and its anhydride. Among these, ethylenically unsaturated dicarboxylic acid Anhydrous is preferred. 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 the olefin polymer.
It is 15% by weight, 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 by, for example, a radical polymerization method in the presence of a solvent (such as xylene) and a catalyst (such as peroxide). 190 of the carboxylic acid-modified polyolefin thus obtained
The melt flow rate (MFR) measured under a temperature of 2160 g at a temperature of 0.2 to 30 g / 10 min is preferable, and 0.5 to 10 g / 10 min is more preferable.
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 transparency, stretchability, flexibility and bending resistance, and therefore the modified EVOH (C)
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.

Another advantage is as follows. When producing a multilayer structure by coextrusion molding, it is usually desirable that the melt viscosities of the resins to be laminated do not differ greatly. However, a preferred application of EVOH is a coextrusion blow-molded fuel container. In such a fuel container, EVOH is usually used as an intermediate layer and high-density polyethylene is used as inner and outer layers. The high-density polyethylene has an MFR of 0.0 in terms of rigidity, impact resistance, moldability, drawdown resistance, gasoline resistance, and the like.
1-0.5g / 10 minutes (under 190 ° C-2160g load)
It is preferable to use high density polyethylene of 0.0
More preferably, high density polyethylene of 1 to 0.1 g / 10 min is used. Therefore, the EVOH to be laminated with the high-density polyethylene is preferably one that does not significantly differ in melt viscosity from the high-density polyethylene at the molding temperature when performing coextrusion molding.

As a method for obtaining EVOH having such a low melt viscosity, a method for producing EVOH having a high degree of polymerization can be considered. However, production of EVOH having a high degree of polymerization is not always easy, and sufficient productivity may not be obtained in some cases. However, as is clear from the examples described below, the modified EVOH (C) containing 0.3 to 40 mol% of the above structural unit (I) has a smaller MFR than the EVOH before modification. In addition, since the modified EVOH (C) containing the structural unit (I) has a lower melting point than that of a normal unmodified EVOH, it is possible to reduce the temperature of the EVOH during coextrusion, and the MFR during molding can be reduced. Can be made smaller. By using such modified EVOH (C), as used in the inner and outer layers of the fuel container,
When performing coextrusion molding with polyethylene having a low melt viscosity, multilayer coextrusion molding can be performed under more preferable production 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,
Multi-layer pipes, multi-layer hoses, multi-layer irregularly shaped products, etc. 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.

The modified EVOH (C) of the present invention has transparency,
Since it has excellent stretchability, flexibility and bending resistance, the multilayer structure containing the layer of the modified EVOH (C) of the present invention can be used for various purposes. For example, it is preferably used for flexible films, flexible packaging materials, thermoformed containers, blow-molded products (multilayer coextrusion blow-molded containers, etc.), heat-shrinkable films (skin pack films, etc.), hoses or balloons. Among the above, flexible packaging materials (flexible pouches, tubes, etc.), flexible films, and the like are exemplified as suitable applications that can sufficiently exhibit the effect of bending resistance.

Further, a multi-layer structure including the modified EVOH (C) of the present invention and a layer composed of the modified EVOH (C) is
It is also preferable to use it as a wallpaper or a makeup plate. EVO
Since H has excellent antifouling properties and barrier properties against plasticizers, the multilayer structure including 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 folding, and if the EVOH layer is severe, whitening may occur, resulting in a poor appearance. . 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. 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.

Further, by using the modified EVOH (C) of the present invention as a multi-layer pipe including a layer composed 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 multi-layer 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 multi-layer 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 hot water circulation pipe.

It is also preferable to use the multilayer structure containing 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).

[0151]

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. The analysis in Examples and the like was performed as follows.

<Measurement of Characteristic Value of EVOH (A)> (1) Ethylene Content and Saponification Degree of EVOH (A): ¹ H-with Deuterated Dimethyl Sulfoxide as a Solvent
NMR (nuclear magnetic resonance) measurement ("JNM-G" manufactured by JEOL Ltd.)
X-500 type "was used).

(2) Intrinsic viscosity: dry EVOH used as a sample
0.20 g of dry pellets composed of (A) was precisely weighed, dissolved in 40 ml of water-containing phenol (water / phenol = 15/85: weight ratio) at 60 ° C. for 3 to 4 hours, and heated at 30 ° C. , Measured with Ostwald viscometer (t0
= 90 seconds), the intrinsic viscosity [η] was calculated 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: Dissolve sample Time for the hydrous phenolic solution to pass through the viscometer

(3) Determination of content of alkali metal salt and alkaline earth metal salt (ion chromatography):
The alkali metal ion and alkaline earth metal ion contents were measured by the following method. 0.01 g of 10 g of dried pellets composed of dried EVOH (A) as a sample
50 ml of a specified aqueous hydrochloric acid solution was added, and the mixture was stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to obtain the content of alkali metal ions or alkaline earth metal ions. The column uses ICS-C25 manufactured by Yokogawa Electric Corporation, and the eluent is 5.0 m.
This was a mixed solution of the M tartaric acid aqueous solution and the 1.0 mM 2,6-pyridinedicarboxylic acid aqueous solution. For the quantification, a calibration curve prepared from an aqueous solution of hydrochloride of various metals (for example, aqueous solution of sodium chloride, aqueous solution of potassium chloride, aqueous solution of magnesium chloride and aqueous solution of calcium chloride) was used.
From the amounts of the alkali metal ion and the alkaline earth metal ion thus obtained, the amount of the alkali metal salt and the alkaline earth metal salt in the dry pellet was obtained as a metal element conversion value.

(4) Determination of acetic acid content: E as sample
20 g of dried pellets composed of VOH (A) was put into 100 ml of ion-exchanged water, and heated and extracted at 95 ° C. for 6 hours.
1/5 of the extract using phenolphthalein as an indicator
The content of acetic acid was quantified by neutralization titration with 0N NaOH.

(5) Quantification of phosphoric acid compound: E as a sample
10 g of dried pellets composed of VOH (A) was put into 50 ml of 0.01 N hydrochloric acid aqueous solution, and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to quantify the amount of phosphate ions. As the column, ICS-A23 manufactured by Yokogawa Electric Corporation was used, and the eluent was an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium hydrogen carbonate. A calibration curve prepared with an aqueous solution of sodium dihydrogen phosphate was used for the quantification. From the amount of phosphate ion thus obtained, the content of the phosphate compound was obtained in terms of phosphate radical.

Synthetic Example 1 Water-containing pellets (water content: 130% (dry basis) consisting of an ethylene-vinyl alcohol copolymer having an ethylene content of 32 mol%, a saponification degree of 99.6%, and an intrinsic viscosity of 0.0882 L / g. ) 100 parts by weight was immersed and stirred in 370 parts by weight of an aqueous solution containing 0.1 g / L of acetic acid and 0.044 g / L of potassium dihydrogen phosphate at 25 ° C for 6 hours. The pellets obtained are dried at 105 ° C. for 20 hours and dried EVO
H pellets were obtained. The dry EVOH pellets had a potassium content of 8 ppm (metal element conversion) and an acetic acid content of 5
3 ppm, phosphoric acid compound content is 20 ppm (phosphoric acid radical conversion value), alkaline earth metal salt content is 0 ppm
Met. The dry pellet MFR is 8 g / 1.
It was 0 minutes (190 ° C., under a load of 2160 g). The EVOH thus obtained was used as EVOH (A). In addition, 1,2-epoxybutane 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. Barrel C1 is water cooled and barrels C2 to C3 are cooled to 200
The barrel C4 to C15 was set to 240 ° C., and the screw was rotated at 400 rpm. The EVOH (A) was fed at a rate of 11 kg / hr from the resin feed port of C1 and melted, water and oxygen were removed from the vent 1, and 1,2-epoxybutane was added from the liquid pressure inlet of C9 to 2. It was fed at a rate of 5 kg / hr (pressure during feeding: 6 MPa). After that, unreacted 1, from vent 2
2-Epoxybutane was removed to obtain modified EVOH (C). The MFR of the obtained modified EVOH (C) is 2.5 g.
/ 10 minutes (190 ° C., under a load of 2160 g).

Regarding the chemical structure of the modified EVOH (C) modified with 1,2-epoxybutane thus obtained, NMR measurement is carried out after trifluoroacetylation of the modified EVOH (C) according to the following procedure. Sought by. At this time, the peaks in the NMR measurement chart of the modified EVOH (C) were assigned by synthesizing the following model compounds and comparing them with the NMR measurement charts of the model compounds.

Trifluoroacetylation and NMR measurement of modified EVOH (C): modified EVOH prepared above
After pulverizing (C) to a particle size of 0.2 mm or less, 1 g of this powder
In a 100 ml eggplant flask, and add 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 polymer was completely dissolved. After the polymer was completely dissolved and stirred for another hour, the solvent was removed by a rotary evaporator. The obtained trifluoroacetylated modified ethylene-vinyl alcohol copolymer (C) was mixed with deuterated chloroform and trifluoroacetic anhydride at a concentration of 2 g / L (deuterated chloroform / trifluoroacetic anhydride = 2/1 ( (Weight ratio)), and 500 MHz ¹ H-NMR was measured using tetramethylsilane as an internal standard. Obtained NM
The R chart is shown in FIG.

<Synthesis of Model Compound (1)> 1-isopropoxy-2-butanol and 1- (1-
Synthesis of isopropoxy-2-butoxy) -2-butanol: 180 g isopropanol and 2 epoxybutane in a 1 L separable flask equipped with stirrer and condenser.
After charging 16 g and purging with nitrogen, 1.6 g of sodium was added and refluxed for 16 hours. After adding 5 g of phosphoric acid thereto, 1-isopropoxy-2-butanol (boiling point: 100 ° C./120 mmHg) and 1-isopropoxy-2-butanol were obtained by vacuum distillation.
(1-Isopropoxy-2-butoxy) -2-butanol (boiling point: 105 ° C / 50 mmHg) was obtained by fractional distillation.
The 1-isopropoxy-2-butanol thus obtained is a model compound when one molecule of 1,2-epoxybutane reacts with the hydroxyl group of EVOH, and is 1- (1-isopropoxy-2-butoxy) -2. -Butanol is EV
It is a model compound when two molecules of 1,2-epoxybutane react with the hydroxyl group of OH.

<Synthesis (2) of Model Compound> Synthesis of 1-isopropoxy-2-trifluoroacetoxy-butane and NMR measurement: 530 mg of 1-isopropoxy-2-butanol and 5 g of methylene chloride prepared above were placed in a 20 ml eggplant flask. After that, 1.7 g of trifluoroacetic anhydride was added. After stirring at room temperature for 1 hour, the solvent was removed by a rotary evaporator.
About the obtained 1-isopropoxy-2-trifluoroacetoxy-butane, a mixed solvent of deuterated chloroform and trifluoroacetic anhydride (deuterated chloroform / trifluoroacetic anhydride = 2/1 (weight ratio)) was used as a solvent, and 500 MHz ¹
1 H-NMR was measured. The obtained NMR chart is shown in FIG.
Shown in.

<Synthesis of Model Compound (3)> Synthesis and NMR measurement of 1- (1-isopropoxy-2-butoxy) -2-trifluoroacetoxy-butane:
820 mg of 1- (1-isopropoxy-2-butoxy) -2-butanol prepared above and 5 methylene chloride
After charging g to a 20 mL round-bottomed flask, 1.7 g of trifluoroacetic anhydride was added. After stirring at room temperature for 1 hour, the solvent was removed by a rotary evaporator. For the obtained 1-isopropoxy-2-trifluoroacetoxy-butane, a mixed solvent of deuterated chloroform and trifluoroacetic anhydride (deuterated chloroform / trifluoroacetic anhydride = 2/1 (weight ratio)) was used as a solvent, and 500 MHz ¹ H-
NMR was measured. The obtained NMR chart is shown in FIG.

<Analysis of NMR Measurement Chart> As is apparent from FIG. 3, in ¹ H-NMR of ¹ -isopropoxy-2-trifluoroacetoxy-butane, δ 0.8-
Signal derived from methyl proton is 1 at 1.1 ppm
There was one. Then, as is clear from FIG.
In ¹ H-NMR of-(1-isopropoxy-2-butoxy) -2-trifluoroacetoxy-butane, δ0.
There were two signals derived from methyl protons at 8 to 1.1 ppm. On the other hand, as shown in FIG. 2, the modified EVOH (C) produced in Synthesis Example 1 had a δ of 0.8-1.
There is one signal derived from the methyl proton at 1 ppm, and the modified EVOH obtained in Synthesis Example 1 above
It was clear that (C) had the following structural unit (X).

[0165]

[Chemical 14]

<Determination of ethylene content of modified EVOH (C) and content of structural unit (I) (1)> Ethylene content of modified EVOH (C): w (mol%) Unmodified EVOH (C) Content of modified vinyl alcohol: x (mol%) Structural unit represented by the above formula (X) contained in the modified EVOH (C): y (mol%) The following formula (XI) contained in the modified EVOH (C) ) The structural unit represented by the formula: z (mol%).

[0167]

[Chemical 15]

Between the above w to z, the following formulas (1) to (4)
The relationship shown by is established. 4w + 2x + 4y + 4z = A (1) 3y + 2z = B (2) 2z = C (3) x + y = D (4) However, A: δ in ¹ H-NMR measurement of modified EVOH (C)
Integrated value B of signal from 1.1 to 2.4 ppm: δ in ¹ H-NMR measurement of modified EVOH (C)
Integrated value C of signal at 3.1 to 3.8 ppm: δ in ¹ H-NMR measurement of modified EVOH (C)
Integral value D of signals at 4.1 to 4.5 ppm: δ in ¹ H-NMR measurement of modified EVOH (C)
The integrated value of the signal at 4.8 to 5.5 ppm is shown.

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 = {(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 Synthesis Example 1 had an ethylene content of 32 mol% and a structural unit (I) content of 4.8 mol%.

Melting point of modified EVOH (C): modified EVOH
The melting point of (C) was measured based on JIS K7121 using a differential scanning calorimeter (DSC) RDC220 / SSC5200H type manufactured by Seiko Denshi Kogyo. However, indium and lead were used for temperature calibration. The melting point of the modified EVOH (C) produced in Synthesis Example 1 was 141 ° C.

Synthesis Example 2 In Synthesis Example 1, EVO from the resin feed port of C1
Same as Synthesis Example 1 except that the feed amount of H (A) was 16 kg / hr and the feed amount of 1,2-epoxybutane from the hydraulic inlet of C9 was 1.2 kg / hr. Extrusion is performed under the conditions, MFR = 3 g / 10 minutes (190 ° C., 21
Under a load of 60 g), a modified EVOH (C) having a structural unit (I) content of 3 mol% was obtained.

Synthesis Example 3 EVO from the resin feed port of C1 in Synthesis Example 1
The feed amount of H (A) was set to 16 kg / hr, and a molecular weight of 5 was used instead of 1,2-epoxybutane from the hydraulic inlet of C9.
Extruded under the same conditions as in Synthesis Example 1 except that epoxypropane was fed as a monovalent epoxy compound (B) of not more than 00 at a rate of 2.4 kg / hr, and MFR = 2.8 g
/ 10 minutes (190 ° C., under a load of 2160 g), a modified EVOH (C) having a structural unit (I) content of 5 mol% was obtained.

Synthesis Example 4 EVO from the resin feed port of C1 in Synthesis Example 1
The feed amount of H (A) was set to 15 kg / hr, and a molecular weight of 5 was used instead of 1,2-epoxybutane from the hydraulic pressure inlet of C9.
Glycid as a monovalent epoxy compound (B) of 00 or less
Extrusion was carried out under the same conditions as in Synthesis Example 1 except that the resin was fed at a rate of 2.5 kg / hr, and MFR = 1.8 g / 1
Modified EVOH for 0 minutes (190 ℃, under 2160g load)
(C) was obtained.

The chemical structure of the modified EVOH (C) modified with glycidol thus obtained was determined by performing NMR measurement after trifluoroacetylation of the modified EVOH (C) according to the following procedure. At this time, the following model compound was synthesized and the peak in the NMR measurement chart in the modified EVOH (C) was assigned by comparing with the NMR measurement chart of the model compound.

Trifluoroacetylation of modified EVOH (C) and NMR measurement The modified EVOH (C) prepared above was pulverized to a particle size of 0.2 mm or less, and 1 g of this powder was placed in a 100 ml round-bottomed flask, 20 g of methylene chloride and anhydrous. 10 g of trifluoroacetic acid was added, and the mixture was stirred at room temperature. One hour after the start of stirring, the polymer was completely dissolved. After the polymer was completely dissolved and stirred for another hour, the solvent was removed by a rotary evaporator. The obtained trifluoroacetylated modified ethylene-vinyl alcohol copolymer (C) was mixed with deuterated chloroform and trifluoroacetic anhydride at a concentration of 2 g / L (deuterated chloroform / trifluoroacetic anhydride = 2/1 ( (Weight ratio)), and 500 MHz ¹ H-NMR was measured using tetramethylsilane as an internal standard. The obtained NMR chart is shown in FIG.

<Synthesis (4) of Model Compound> Synthesis of 3-isopropoxy-1,2-propanediol: 1200 g of isopropanol was charged into 3 L separable with a stirrer and a condenser, 4.6 g of sodium was added, and the mixture was heated to 80 ° C. It was heated and dissolved. After completely dissolving sodium, 300 g of glycidol was added dropwise at 80 ° C. over 1 hour. After the dropping was completed, the mixture was stirred for 3 hours, then stopped, and cooled to room temperature. At this time, an upper layer and a lower layer were separated. The upper layer was separated and concentrated by an evaporator. Furthermore, 3-isopropoxy-1,2-propanediol was obtained by distillation under reduced pressure (boiling point 60 ° C./2 m
mHg). 3-isopropoxy-1,2 thus obtained
-Propanediol is a model compound when one molecule of glycidol reacts with the hydroxyl group of EVOH.

<Synthesis (5) of Model Compound> Synthesis of 1-isopropoxy-2,3-ditrifluoroacetoxy-propane and NMR measurement: 3 prepared above
-Isopropoxy-1,2-propanediol 270 m
g and methylene chloride 5 g were charged in a 20 ml eggplant flask, and then trifluoroacetic anhydride 1.7 g was added.
After stirring at room temperature for 1 hour, the solvent was removed by a rotary evaporator. The obtained 1-isopropoxy-2,3
For ditrifluoroacetoxy-propane, 500 MHz ¹ H-NMR was measured using a mixed solvent of deuterated chloroform and trifluoroacetic anhydride (deuterated chloroform / trifluoroacetic anhydride = 2/1 (weight ratio)) as a solvent. The obtained NMR chart is shown in FIG.

<Analysis of NMR Measurement Chart> As is clear from comparison between FIGS. 5 and 6, 1-isopropoxy-2,3-ditrifluoroacetoxy-propane, which is a model compound, was prepared in Synthesis Example 4. Modified EVOH
The ¹ H-NMR of (C) shows δ 3.5 to 3.9 p in all cases.
pm, 4.5-4.8 ppm and 5.3-5.5 pp
It had a characteristic signal common to m. Also, δ
The integrated value of the signal of 3.5 to 3.9 ppm and δ4.5
The ratio with respect to the integrated value of the signal at ˜4.8 ppm is 1-isopropoxy-2,3-ditrifluoroacetoxy-propane as a model compound and the modified E prepared in Synthesis Example 4.
When compared with VOH (C), both were about 3: 2, showing extremely good agreement. From the above, it was clear that the modified EVOH (C) obtained in Synthesis Example 1 had the following structural unit (XII).

[0181]

[Chemical 16]

<Determination of Ethylene Content of Modified EVOH (C) and Content of Structural Unit (I) (2)> Ethylene Content of Modified EVOH (C): w (mol%) Unmodified EVOH (C) Modified vinyl alcohol content: x (mol%) Structural unit represented by the above formula (XII) contained in the modified EVOH (C): y (mol%) The following formula (XIII) contained in the modified EVOH (C) ) The structural unit represented by the formula: z (mol%).

[0183]

[Chemical 17]

Between the above w to z, the following equations (5) to (8)
The relationship shown by is established. 4w + 2x + 2y + 2z = A (5) 4z = B (6) 2y = C (7) x + y = D (8) However, A: δ in ¹ H-NMR measurement of the modified EVOH (C)
Integrated value B of signal from 1.1 to 2.4 ppm: δ in ¹ H-NMR measurement of modified EVOH (C)
Integral value C of signal at 4.2 to 4.5 ppm: δ in ¹ H-NMR measurement of modified EVOH (C)
Integrated value D of signal at 4.5 to 4.8 ppm: δ in ¹ H-NMR measurement of modified EVOH (C)
The integrated value of the signal at 4.8 to 5.6 ppm is shown.

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 = {(2A-B-4D) / (2A + B + 4D)} × 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 = {(2B + 4C) / (2A + B + 4D)} × 100

The modified EVOH (C) produced in Synthesis Example 4 had an ethylene content of 32 mol% and a structural unit (I) content of 5 mol%.

Synthesis Example 5 Water-containing pellets (water content: 130% (dry base) of ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol%, a saponification degree of 99.6% and an intrinsic viscosity of 0.0855 L / g) 100) parts by weight of acetic acid 0.12 g / L,
It was dipped and stirred in 370 parts by weight of an aqueous solution containing 0.044 g / L of potassium dihydrogen phosphate at 25 ° C. for 6 hours. The obtained pellets are dried at 105 ° C for 20 hours and dried EV
OH pellets were obtained. The dry EVOH pellets had a potassium content of 8 ppm (metal element conversion), an acetic acid content of 62 ppm, a phosphoric acid compound content of 20 ppm (phosphoric acid radical conversion value), and an alkaline earth metal salt content of 0 pp.
It was m. Also, the dry pellet has an MFR of 12 g.
/ 10 minutes (190 ° C., under a load of 2160 g). The EVOH thus obtained was used as EVOH (A).

On the other hand, glycidyl was used as the epoxy compound (B). A TEM-35BS extruder (37 mmφ, L / D = 52.5) manufactured by Toshiba Machine Co., Ltd. was used, and a screw configuration, a vent and a pressure inlet 1 were installed as shown in FIG. Barrel C1 is water cooled and barrels C2-C3 are 2
The temperature was set to 00 ° C and barrels C4 to C15 were set to 240 ° C, and the screw was rotated at 400 rpm. The EVOH (A) was fed from the resin feed port of C1 at a rate of 15 kg / hr and melted, water and oxygen were removed from the vent 1, and glycidyl was removed from the liquid pressure inlet of C9 to 2 g. .5k
Feeding was performed at a rate of g / hr (pressure at feeding: 7
MPa). Then, unreacted glycidyl was removed from the vent 2, and MFR = 1.6 g / 10 min (190 ° C., 21 ° C.).
Under a load of 60 g), a modified EVOH (C) having a structural unit (I) content of 6 mol% was obtained.

Example 1 Using the modified EVOH (C) obtained in Synthesis Example 1, 40
φ Extruder (PLABOR G made by Plastic Engineering Laboratory
T-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 40mmφ Screw-single full flight type, surface nitrided steel Screw-rotation speed 40rpm Die 550mm width coat hanger-Die lip gap 0.3mm Cylinder-die temperature setting C1 / C2 / C3 / Adapter- / Die = 180/200/210/210/2 10 (℃)

Using the monolayer film prepared above, the oxygen permeation rate, carbon dioxide permeation rate, Young's modulus, tensile yield strength, tensile elongation at break and haze were measured according to the following methods, and the flex resistance test was conducted. I went.

Measurement of oxygen permeation rate: The monolayer film produced above was conditioned at 20 ° C. and 65% RH for 5 days. Using two samples of the above-mentioned humidity-controlled monolayer film,
MOCON OX-TRAN2 made by Modern Control
/ 20 type, JIS under 20 ° C-65% RH condition
The oxygen permeation rate was measured according to the method described in K7126 (isobaric method), and the average value was obtained. The oxygen transmission rate is ^2.5 cc · 20 μm / m ² · day · atm,
It showed a good gas barrier property.

Measurement of carbon dioxide permeation rate: The monolayer film prepared above was conditioned at 20 ° C. and 65% RH for 5 days.
MOCONPERMA-TRAN C manufactured by Modern Control Co., Ltd. is used by using the two samples that have been conditioned.
-Type IV, JISK under 20 ° C-65% RH condition
The carbon dioxide permeation rate was measured according to the method described in 7126 (isobaric method), and the average value thereof was obtained. The carbon dioxide gas permeation rate was 11 cc · 20 μm / m ² · day · atm, showing a good gas barrier property.

Measurement of Young's modulus: The monolayer film prepared above was conditioned under an atmosphere of 23 ° C. and 50% RH for 7 days, and then a strip of 15 mm width was prepared. Shimadzu autograph AGS-H using the film sample
With the mold, chuck spacing 50mm, pulling speed 5mm / mi
Young's modulus was measured under the condition of n. The measurement was performed for each of 10 samples, and the average value was obtained. Young's modulus is 4
It was 6 kgf / mm ² .

Measurement of tensile yield strength and tensile elongation at break: The monolayer film prepared above was conditioned for 7 days in an atmosphere of 23 ° C. and 50% RH, and then a strip of 15 mm width was prepared. Using the film sample, using an autograph AGS-H type manufactured by Shimadzu Corporation, a chuck interval of 50
The tensile yield strength and the tensile elongation at break were measured under conditions of mm and a tensile speed of 500 mm / min. Each measurement is 10
It performed about the sample and calculated | required the average value. Tensile yield strength and tensile elongation at break were 5.3 kgf /
mm ² and 278%.

Measurement of haze: Using the above-prepared monolayer film, integral formula H. T. R-me
The haze was measured according to JIS D8741 using a taper. The haze was 0.1%, indicating extremely good transparency.

Evaluation of flex resistance: 50 single-layer films prepared above, which were cut into 21 cm × 30 cm, were prepared, and the humidity of each film was adjusted at 20 ° C.-65% RH for 5 days, and then ASTMF 392- According to No. 74, using a Gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., the number of bending times is 50 times, 75 times, 100 times, 125 times, 150 times,
After bending 175 times, 200 times, 225 times, 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. , 2 significant figures were used. As a result, Np1 is 16
It was 0 times and showed extremely excellent flex resistance.

Next, using the obtained modified EVOH (C), using the following three-kind five-layer coextrusion apparatus, under the following coextrusion molding conditions, a multilayer sheet (ionomer resin layer / adhesive resin layer) was prepared. / Modified EVOH (C) / adhesive resin layer / ionomer-resin layer) was prepared. The composition of the sheet is such that the outermost ionomer resin (Mitsui DuPont Polychemical “HIMIRAN 1652”) layer is 250 μm each, and the adhesive resin (Mitsui Chemicals “Adma-NF500”) layer is 30 μm each. The modified EVOH (C) layer is 90 μm. (Coextrusion molding conditions) Layer structure: ionomer resin / adhesive resin / modified EVOH
(C) / adhesive resin / ionomer resin (thickness 250 /
30/90/30/250: Unit is μm) Extrusion temperature of each resin: C1 / C2 / C3 / die = 170 /
170/220/220 ° C. Extruder of each resin, T-die specifications: Ionomer resin; 32φ extruder GT-32-A type (manufactured by Plastic Engineering Laboratory Co., Ltd.) Adhesive resin; 25φ extruder P25-18AC (Osaka Seiki) Kosaku Co., Ltd.) Modified EVOH (C); 20φ extruder Lab machine ME type CO
-EXT (manufactured by Toyo Seiki Co., Ltd.) T die; for 300 mm width, 3 types, 5 layers (manufactured by Plastic Engineering Laboratory Co., Ltd.) Cooling roll temperature: 50 ° C, take-up speed: 4 m / min

Evaluation of stretchability: The above-prepared multilayer sheet was placed on a pantograph type biaxial stretching machine manufactured by Toyo Seiki Co., Ltd.
At the same time, biaxial stretching was carried out at a stretch 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 was free from unevenness and local uneven thickness, and the evaluation was A.

Example 2 As modified EVOH (C), modified E prepared in Synthesis Example 2 was used.
A monolayer film and a multilayer film were produced in the same manner as in Example 1 except that VOH (C) was used, and the oxygen permeation rate, carbon dioxide permeation rate, Young's modulus, tensile yield strength, tensile elongation at break and haze were measured. Was measured to evaluate bending resistance and stretchability. The evaluation results are shown in Table 1.

Example 3 As modified EVOH (C), modified E prepared in Synthesis Example 3 was used.
A monolayer film and a multilayer film were produced in the same manner as in Example 1 except that VOH (C) was used, and the oxygen permeation rate, carbon dioxide permeation rate, Young's modulus, tensile yield strength, tensile elongation at break and haze were measured. Was measured to evaluate bending resistance and stretchability. The evaluation results are shown in Table 1.

Example 4 As modified EVOH (C), the modified E prepared in Synthesis Example 4 was used.
A monolayer film and a multilayer film were produced in the same manner as in Example 1 except that VOH (C) was used, and the oxygen permeation rate, carbon dioxide permeation rate, Young's modulus, tensile yield strength, tensile elongation at break and haze were measured. Was measured to evaluate bending resistance and stretchability. The evaluation results are shown in Table 1.

Example 5 As modified EVOH (C), the modified E prepared in Synthesis Example 5 was used.
A monolayer film and a multilayer film were produced in the same manner as in Example 1 except that VOH (C) was used, and the oxygen permeation rate, carbon dioxide permeation rate, Young's modulus, tensile yield strength, tensile elongation at break and haze were measured. Was measured to evaluate bending resistance and stretchability. The evaluation results are shown in Table 1.

Comparative Example 1 Water-containing pellets (water content: 130% (dry base) of ethylene-vinyl alcohol copolymer having an ethylene content of 32 mol%, a saponification degree of 99.6%, and an intrinsic viscosity of 0.0959 L / g). 100 parts by weight) was dipped and stirred in 370 parts by weight of an aqueous solution containing 0.1 g / L of acetic acid and 0.044 g / L of potassium dihydrogen phosphate at 25 ° C. for 6 hours. The pellets obtained are dried at 105 ° C. for 20 hours and dried EVO
H pellets were obtained. The dry EVOH pellets had a potassium content of 8 ppm (metal element conversion) and an acetic acid content of 5
3 ppm, phosphoric acid compound content is 20 ppm (phosphoric acid radical conversion value), alkaline earth metal salt content is 0 ppm
Met. The dry pellet has an MFR of 4.5 g.
/ 10 minutes (190 ° C., under a load of 2160 g). A monolayer film and a multilayer film were produced in the same manner as in Example 1 except that the EVOH prepared above was used instead of the modified EVOH (C), and the oxygen permeation rate, carbon dioxide permeation rate, Young's The tensile strength, the tensile yield strength, the tensile elongation at break, and the haze were measured to evaluate the stretchability.
The evaluation results are shown in Table 1.

The flex resistance was evaluated as follows. Using the unmodified EVOH (A) pellets described above, 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 form a film having a thickness of 25 μm. Obtained. 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 times is 25 times, 30 times,
35 times, 40 times, 50 times, 60 times, 80 times and 100 times
After being bent once, 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. It was The Np1 of the film of this comparative example was 34 times.

Comparative Example 2 Water-containing pellets (water content: 130% (dry base) of ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol%, a saponification degree of 99.6% and an intrinsic viscosity of 0.0948 L / g). 100) parts by weight of acetic acid 0.12 g / L,
It was dipped and stirred in 370 parts by weight of an aqueous solution containing 0.044 g / L of potassium dihydrogen phosphate at 25 ° C. for 6 hours. The obtained pellets are dried at 105 ° C for 20 hours and dried EV
OH pellets were obtained. The dry EVOH pellets had a potassium content of 8 ppm (metal element conversion), an acetic acid content of 62 ppm, a phosphoric acid compound content of 20 ppm (phosphoric acid radical conversion value), and an alkaline earth metal salt content of 0 pp.
It was m. Also, the MFR of the dried pellet is 5.5.
It was g / 10 minutes (190 ° C., under a load of 2160 g).

In Example 1, except that the unmodified EVOH (A) was used in place of the modified EVOH (C),
A monolayer film and a multilayer film were produced in the same manner as in Example 1, and the oxygen permeability, the carbon dioxide permeability, the Young's modulus, the tensile yield strength, the tensile elongation at break and the haze were measured to evaluate the stretchability. In addition, bending resistance was evaluated in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

Comparative Example 3 EVO from the resin feed port of C1 in Synthesis Example 1
The feed amount of H (A) was set to 15 kg / hr, and bisphenol A was used instead of epoxy butane from the hydraulic inlet of C9.
120 g / hr of diglycidyl ether (manufactured by Tokyo Kasei)
Extrusion was performed under the same conditions as in Synthesis Example 1 except that the mixture was fed at a rate of MFR = 2.5 g / 10 min (190 ° C., 21 ° C.).
Bisphenol A diglycidyl ether under 60 g load)
Modified EVOH consisting of EVOH modified by tell
(C) was obtained. Using the modified EVOH (C) thus obtained, a monolayer film and a multilayer film were produced in the same manner as in Example 1, and the oxygen permeation rate, carbon dioxide permeation rate, Young's modulus, tensile yield strength, and tensile elongation at break were obtained. The haze was measured and the stretchability was evaluated. In addition, bending resistance was evaluated in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

Comparative Example 4 In Comparative Example 3, the ratio of bisphenol A diglycidyl ether fed from the hydraulic pressure inlet of C9 was 600.
Extrusion was performed under the same conditions as in Comparative Example 3 except that g / hr was used. However, during the reaction, the resin gelled in the extruder, and extrusion could not be performed.

[0211]

[Table 1]

As shown above, the modified EVOH (C) containing the structural unit (I) (Examples 1 to 5) has a higher oxygen content than the unmodified EVOH (A) (Comparative Examples 1 and 2). Although the transmission rate increases to some extent, the transparency, flexibility, bending resistance and stretchability are greatly improved. Further, since the melting point is lowered, it is possible to perform melt molding at a lower temperature. On the other hand, in Comparative Example 3 using bisphenol A diglycidyl ether, which is a polyfunctional epoxy compound, instead of the monovalent epoxy compound (B) having a molecular weight of 500 or less, the above-mentioned transparency, flexibility, bending resistance and The effect of improving stretchability was not obtained. As the content of the structural unit (I) increases, the bending resistance, flexibility and stretchability are improved, and the melting point is also lowered. Therefore, in consideration of the balance with the oxygen permeation rate, a structural unit suitable for each application. It is possible to set the content of (I).

Example 6 As a linear low-density polyethylene (LLDPE), "UE320" manufactured by Nippon Polychem (MFR at 190 ° C-2160g = 0.7g / 10 minutes), as an adhesive resin "Adma NF500" manufactured by Mitsui Chemicals, Inc. (230 ° C-2160
(MFR in g = 1.8 g / 10 min) with modified EVO
Modified EVOH (C) prepared in Synthesis Example 1 as H (C)
Was used. Suzu wooden factory blow molding machine TB-ST-6P
Extrusion temperature and die temperature of each resin are set to 210 ° C, and LLDPE / adhesive resin / modified EVOH (C) /
A three-kind five-layer parison having a layer structure of adhesive resin / LLDPE was extruded, blown in a mold at 15 ° C., and cooled for 20 seconds to obtain a 500 mL bottle composed of a multilayer blow molded product. The total layer thickness of the bottle is 500 μm, and the layer structure is (inside) LLDPE / adhesive resin / modified EV.
OH (C) / adhesive resin / LLDPE (outside) = 210
/ 20/20/30/20/220 μm. The bottle could be molded without any problems. The appearance of the bottle was good.

Example 7 Modified EV prepared in Synthesis Example 1 as modified EVOH (C)
Using OH (C) and a 4-layer 4-layer coextrusion device, a multilayer film (nylon 6 resin / modified EVOH) under the following conditions:
(C) / adhesive resin / LLDPE resin) was prepared. The film is composed of nylon 6 resin ("Ube nylon 1022B" manufactured by Ube Industries, Ltd.) of 10 μm and modified EVOH (C).
Is 20 μm, adhesive resin (“Adma-NF5 manufactured by Mitsui Chemicals, Inc.
00 ") is 10 μm, LLDPE resin (manufactured by Mitsui Chemicals,
“Ultozex 3520L”) is 60 μm. (Coextrusion molding conditions) Layer structure: Nylon 6 resin / modified EVOH (C) / adhesive resin / LLDPE resin (thickness 10/20/10/60:
Unit is μm) Extrusion temperature of nylon 6 resin: C1 / C2 / C3 / C4 =
230/240/250/250 ° C. Extrusion temperature of adhesive resin: C1 / C2 / C3 = 170/1
Extrusion temperature of 70/220/220 ° C. modified EVOH (C): C1 / C2 / C3 / C4 = 175/210/230
Extrusion temperature of / 230 ° C. LLDPE resin: C1 / C2 / C3 = 170
/ 170/220/220 ° C Adapter temperature: 250 ° C Die temperature: 250 ° C Extruder for each resin, T-die specifications: Nylon 6 resin; 40φ extruder UT-40-H type (Plastic Engineering Laboratory Co., Ltd.) Made) Adhesive resin; 40φ extruder 10VSE-40-2
Type 2 (manufactured by Osaka Seiki Kogyo Co., Ltd.) Modified EVOH (C); 40φ extruder VSVE-
40-24 type (manufactured by Osaka Seiki Kogyo Co., Ltd.) LLDPE resin; 65φ extruder 20VS-65-22
Mold (manufactured by Osaka Seiki Kogyo Co., Ltd.) T-die; 650 mm width, 4 types, 4 layers (manufactured by Plastic Engineering Laboratory) Cooling roll temperature: 30 ° C, take-up speed: 8 m / min

Using a thermoforming machine (R530 manufactured by Multivac Co.) so that the LLDPE resin is on the inner layer side of the container,
A thermoformed container was obtained by thermoforming the obtained multilayer film. That is, by heating at a mold temperature of 100 ° C. for 2 seconds, the mold shape (vertical: 130 mm, horizontal: 110 mm
Depth: 60 mm rectangular parallelepiped) with compressed air (atmospheric pressure 5 kg)
The multilayer film was molded using f / cm ² ) to obtain a thermoformed container. When the appearance of the obtained thermoformed container was visually observed, it was found that the thermoformed container was uniformly stretched without unevenness and local uneven thickness, was excellent in transparency, and had good appearance.

Example 8 Modified EV prepared in Synthesis Example 1 as modified EVOH (C)
Using OH (C) and a three-kind five-layer coextrusion device, a multilayer sheet (polypropylene resin / adhesive resin / modified EVO)
H (C) / adhesive resin / polypropylene resin) was prepared. The layer structure of the film is a polypropylene resin for inner and outer layers (“Idemitsu Polypropylene E-20” manufactured by Idemitsu Petrochemical Co., Ltd.).
3G ”) is 420 μm, adhesive resin (“ Adma-QF551 ”manufactured by Mitsui Chemicals Inc.) is 40 μm each, and modified EVO of the intermediate layer
H (C) was 80 μm.

The obtained multi-layered sheet was heated by a thermoforming machine (manufactured by Asano Seisakusho Co., Ltd .: vacuum pressure air deep drawing machine FX-0431-3 type) to a sheet temperature of 160 ° C. and compressed air (atmospheric pressure 5 k).
Round cup shape (mold shape: upper part 7) by gf / cm ²
5mmφ, lower 60mmφ, depth 75mm, aperture ratio S =
A thermoformed container was obtained by thermoforming to 1.0).
The molding conditions are shown below. Heater temperature: 400 ° C Plug: 45φ x 65mm Plug temperature: 150 ° C Mold temperature: 70 ° C

When the appearance of the obtained cup-shaped thermoformed container was visually observed, it was uniformly stretched without unevenness and local uneven thickness, and it was excellent in transparency and good in appearance. It was

Example 9 Modified EV prepared in Synthesis Example 1 as modified EVOH (C)
Multi-layer sheet (polystyrene resin / adhesive resin / modified EVOH) using OH (C) and a three-kind five-layer coextrusion device.
(C) / adhesive resin / polystyrene resin) was prepared.
The layer structure of the film is the polystyrene resin layer of the inner and outer layers (HIPS manufactured by Idemitsu Petrochemical Co., Ltd. “Idemitsu Styrol ET-
61 ”) was 425 μm, the adhesive resin (“ Mersen M-5420 ”manufactured by Toso Co., Ltd.) was 50 μm each, and the modified EVOH (C) of the intermediate layer was 50 μm.

The obtained multilayer sheet was heated at 150 ° C. with a thermoforming machine (manufactured by Asano Seisakusho Co., Ltd .: vacuum pressure deep drawing machine FX-0431-3 type) to obtain compressed air (atmospheric pressure 5 k).
Round cup shape (mold shape: upper part 7) by gf / cm ²
5mmφ, lower 60mmφ, depth 75mm, aperture ratio S =
A thermoformed container was obtained by thermoforming to 1.0).
The molding conditions are shown below. Heater temperature: 400 ℃ Plug: 45φ × 65mm Plug temperature: 120 ℃ Mold temperature: 70 ℃

Visual observation of the appearance of the obtained thermoformed container revealed that it was uniformly stretched without cracks, unevenness and local uneven thickness, and it was excellent in transparency and good in appearance. .

Example 10 Modified EV prepared in Synthesis Example 1 as modified EVOH (C)
OH (C), maleic anhydride modified polyethylene (“Adma-NF500” manufactured by Mitsui Chemicals) as an adhesive resin,
Water-crosslinkable polyethylene (“Moldex S-141” manufactured by Sumitomo Becklite Co., Ltd.) was used as the crosslinkable polyolefin. Each of the above resins is a coextrusion molding machine (“M50 / 28” manufactured by Leonard Co.
D type ”) to produce a multi-layer pipe having an outer diameter of 20 mm composed of (outer layer) modified EVOH (C) / adhesive resin layer / crosslinkable polyolefin (inner layer). The thickness of the outer layer / adhesive resin layer / inner layer in the obtained multilayer pipe was 100 μm / 50 μm / 1850 μm, respectively. Water vapor (temperature 150 ° C .; pressure 4 kg / cm ² ) was passed through the obtained multi-layer pipe for 3 minutes to water-crosslink the inner layer,
The oxygen barrier property of this multilayer pipe was measured by the following method.

Oxygen Barrier Property of Multilayer Pipe (Measurement of Increasing Rate of Dissolved Oxygen): The oxygen barrier property was evaluated by the increasing rate of dissolved oxygen. The smaller the increase rate of dissolved oxygen, the better the oxygen barrier property. The obtained pipe circulates water from which dissolved oxygen has been removed using a packed tower filled with metal tin,
Increase the rate of dissolved oxygen in water at a temperature of 70 ° C at 20 ° C, 65
It was measured under the condition of% RH. Here, increase rate μg /
Liter / hr is μ per 1 liter of water in the pipe
It shows that there is an increase in dissolved oxygen at a rate of g / hr. That is, the volume of water in the entire system including the pipe is V1cc, the volume of water in the pipe is V2cc, and the oxygen concentration increase in the circulating water in the unit per unit time is B μg / liter · h.
When r is set, the above-mentioned rate of increase in dissolved oxygen (A μg / liter · hr) indicates a value calculated by A = B (V1 / V2).

The rate of increase in dissolved oxygen of the obtained multi-layer pipe was 25 μg / liter · hr, which showed a good oxygen barrier property.

Example 11 Polyester thermoplastic polyurethane (“Kuramiron U-2190” manufactured by Kuraray Co., Ltd.) was used as the thermoplastic polyurethane elastomer, and the modified EVOH (C) prepared in Synthesis Example 1 was used as the modified EVOH (C). 70 parts by weight of an ethylene-vinyl acetate copolymer (“Eva Flex EV-460” manufactured by DuPont Mitsui Polychemicals) as a sealant layer and a maleic anhydride-modified ethylene-vinyl acetate copolymer-based adhesive resin (“Adma manufactured by Mitsui Chemicals” -VF50
0 ") 30 parts by weight of each resin composition was used. Using the above resin and resin composition, coextrusion molding was performed under the following conditions to obtain thermoplastic polyurethane elastomer (50 μm) / modified EVOH (C) (10 μm)
A multilayer film having a layer structure of / sealant material (30 μm) was obtained. (Coextrusion molding conditions) Layer composition: thermoplastic polyurethane elastomer / modified EV
OH (C) / sealant layer (thickness 50/10/30: unit is μm) Extrusion temperature of thermoplastic polyurethane elastomer: C1 /
C2 / C3 = 195/200/200 ° C. Extrusion temperature of modified EVOH (C): C1 / C2 / C3 = 1
Extrusion temperature of 75/210/210 ° C sealant material: C1
/ C2 / C3 = 150/200/210 ° C. Die temperature: 210 ° C. Extruder for each resin, T die specifications: Thermoplastic polyurethane elastomer; 20φ extruder Lab machine ME type CO-EXT (manufactured by Toyo Seiki Co., Ltd.) Modified EVOH (C); 25φ Extruder P25-18AC
(Osaka Seiki Co., Ltd.) Sealant material; 32φ extruder GT-32-A type (manufactured by Plastic Engineering Laboratory Co., Ltd.) T die; for 300 mm width 3 types 3 layers (manufactured by Plastic Engineering Laboratory Co., Ltd.) Cooling roll temperature: 50 ° C, take-up speed: 4 m / min

The above-prepared multilayer film was placed at 20 ° C.-6.
The humidity was adjusted to 5% RH for 5 days. MOCO manufactured by Modern Control Co. is used by using the two samples whose humidity has been adjusted as described above.
Using NOX-TRAN 2/20 type, 20 ° C-65% R
Under H condition, the oxygen permeation rate was measured according to the method described in JIS K7126 (isobaric method), and the average value was obtained. The oxygen transmission rate of the multilayer film of this example is 4.5.
It was cc / m ² · day · atm.

Next, the suitability for skin pack packaging was evaluated using the multilayer film. The cover material 4 has a thickness of 100 μm
Polyethylene terephthalate film (“Lumira # 100” manufactured by Toray Industries, Inc.) with a thickness of 40 μm of ethylene
A content (slice ham) 5 was placed on a two-layer film obtained by laminating a vinyl acetate copolymer film (“Lamiron SR-L10” manufactured by Sekisui Film West Japan Co., Ltd.) by the dry lamination method, and then (ethylene-acetic acid Vinyl copolymer layer is on the sliced ham side), skin pack packaging tester (manufactured by Asano Seisakusho: vacuum pressure air deep drawing machine FX-04)
31-3 type) was used to perform skin pack packaging of the film to be evaluated (see FIG. 7).

The film was preheated using the preheating heater-1 set at 100 ° C., and then the multilayer film 3 was vacuum formed by the upper mold 2 (temperature control equipment) kept at 90 ° C. Subsequently, the upper die 2 and the lower die 7 were joined together, and the inside of the die was evacuated. After the inside of the mold is evacuated, the heat sealer 6 is activated to circularly seal the periphery of the sliced ham. Then, the inside of the mold was returned to atmospheric pressure to obtain a skin pack in which the film to be evaluated was closely adhered to the surface of the sliced ham, which was the content.

With respect to the molded skin pack package, the appearance of the package was evaluated with respect to the moldability of the contents (degree of collapse of the contents) and the occurrence of wrinkles. As a result, in the skin pack package made of the multilayer film of this example, the shape of the contents was almost unchanged, and it was in a good shape. In addition, no wrinkles were generated at all and good adhesion was exhibited.

Example 12 Modified EV prepared in Synthesis Example 1 as modified EVOH (C)
OH (C) was used, "Eva Flex EV-340" manufactured by DuPont Mitsui Chemicals was used as the EVA resin, and "Adma-VF-600" manufactured by Mitsui Chemicals was used as the adhesive resin. Using each of the above resins,
EVA resin / adhesive resin /
Modified EVOH (C) / Adhesive resin / EVA resin (= 30
A multilayer sheet having a layer structure of 0/50/50/50/300 μm) was produced. (Coextrusion molding conditions) Layer structure: EVA resin / adhesive resin / modified EVOH (C)
/ Adhesive resin / EVA resin (thickness 300/50/50 /
50/300: Unit is μm) Extrusion temperature of each resin: C1 / C2 / C3 / die = 170 /
170/220/220 ° C. Extruder of each resin, T die specification: EVA resin; 32φ extruder GT-32-A type (manufactured by Plastic Engineering Laboratory Co., Ltd.) Adhesive resin; 25φ extruder P25-18AC (Osaka Seiki) Kosaku Co., Ltd.) Modified EVOH (C); 20φ extruder Lab machine ME type C
O-EXT (manufactured by Toyo Seiki Co., Ltd.) T-die; for 300 mm width 3 types 5 layers (manufactured by Plastic Engineering Laboratory Co., Ltd.) Cooling roll temperature: 50 ° C. Take-up speed: 4 m / min

The above-prepared multilayer sheet was put into a pantograph type biaxial stretching machine manufactured by Toyo Seiki Co., Ltd., at 70 ° C. and a stretching ratio of 3 × 3.
Simultaneously biaxially stretched by a factor of 2 to obtain a multilayer stretched film. The above-mentioned multilayer sheet shows good stretchability, and after stretching, the obtained multilayer stretched film has few cracks, unevenness and uneven thickness,
The appearance (transparency, gel, lump) was also good.

[0232] The multilayer stretched film produced above was placed at 20 ° C.
Humidification was carried out at -100% RH for 5 days. Humidified 2 above
Modern control M using one sample
OCON OX-TRAN2 / 20 type is used, 20 ° C-
Described in JISK7126 (isobaric method) under 100% RH conditions
The oxygen transmission rate was measured according to the method described above, and the average value was calculated.
I asked. Oxygen transmission rate of the multilayer stretched film of this example
Is 6.8 cc / m ^Two・ Day ・ atm, good
It showed gas barrier properties.

Further, the heat shrinkability of the above-prepared multilayer stretched film when used as a heat shrink film was evaluated according to the following method. That is, the above-mentioned multilayer stretched film was immersed in hot water at 90 ° C for 1 minute, and the area shrinkage ratio was determined. The area-shrinkage ratio of the multilayer stretched film of this example was 58%, which showed good heat-shrinkability.

[0234]

The modified EVOH (C) of the present invention is excellent in barrier properties, transparency, stretchability, flexibility and flex resistance.

[Brief description of drawings]

FIG. 1 is a diagram showing one of the preferred screw configuration embodiments of an extruder used in the present invention.

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

FIG. 3 ¹ H—N of ¹ -isopropoxy-2-trifluoroacetoxy-butane, one of the model compounds.
It is a figure which shows an MR chart.

FIG. 4 is a diagram showing a ¹ H-NMR chart of 1- (1-isopropoxy-2-butoxy) -2-trifluoroacetoxy-butane, which is one of model compounds.

FIG. 5: Modified EVOH (C) obtained in Synthesis Example 4
It is a figure which shows the < ¹ > H-NMR chart of.

FIG. 6 shows one of model compounds, 1-isopropoxy-2,3-ditrifluoroacetoxy-propane.
It is a figure which shows a < ¹ > H-NMR chart.

FIG. 7 is a diagram showing an outline of a manufacturing process of a skin pack package.

[Explanation of symbols]

1: Preheat heater 2: Upper mold 3: Multi-layer film 4: Lid material 5: Contents 6: Heat sealer 7: Lower mold 8, 9: Vacuum tubes 10: Stand for heat sealer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 8/00 C08F 216/14 4J100 216/14 C08J 5/00 CES C08J 5/00 CES F16L 11/04 F16L 11/04 C08L 23:08 // C08L 23:08 B65D 1/00 AF term (reference) 3E033 AA09 BA15 BB08 CA03 CA07 CA09 DD01 FA03 3E086 AB01 AD01 BA04 BA15 BB01 BB85 BB90 CA01 3H111 AA02 BA15 BA34 EA04 4F071 A29 4F071AA AF07 AF30 AH04 AH19 BA01 BB05 BB06 BC01 BC02 BC03 BC04 4F100 AK01B AK03B AK12B AK15B AK16B AK27B AK41B AK45B AK46B AK51B AK68A AK68K AL09B BA02 DA01 DA02 DA11 EH20 GB16 JD02 JK08 JK17 JN01 4J100 AA02P AD02Q AE09Q BA03H BA05H BA06H BC02H BC03H BC04H BC21H BC22H BC23H BC43H CA04 DA36 DA62 HA19 HC39 HE17 HF00 JA58

Claims (39)

[Claims] 1. A modified ethylene-vinyl alcohol copolymer (C) containing 0.3 to 40 mol% of the following structural unit (I) and having an ethylene content of 5 to 55 mol%. [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. R ¹ , R ² , R ³ and R ⁴ may be the same or different, and R ³ and R ⁴ may be bonded to each other. (The above R ¹ , R ² , R ³ and R ⁴ may have a hydroxyl group, a carboxyl group or a halogen atom.) 2. The modified ethylene-vinyl alcohol copolymer (C) according to claim 1, wherein both R ¹ and R ² are hydrogen atoms. 3. The modified ethylene-vinyl alcohol copolymer according to claim 1, wherein one of R ³ and R ⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms and the other is a hydrogen atom. Combined (C). 4. One of R ³ and R ⁴ is (C
H ₂ ) _i OH is a substituent (where i is an integer of 1 to 8) and the other is a hydrogen atom.
The modified ethylene-vinyl alcohol copolymer (C) described. 5. The modified ethylene-vinyl alcohol copolymer according to claim 1, which has an oxygen permeation rate at 20 ° C. and 65% RH of 100 cc · 20 μm / m ² · day · atm or less. (C). 6. A carbon dioxide gas permeation rate at 20 ° C. and 65% RH is 500 cc · 20 μm / m ² · day · atm.
The modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 5, which is as follows. 7. The modified ethylene according to claim 1, wherein the Young's modulus in tensile strength / elongation measurement at 23 ° C. and 50% RH is 140 kgf / mm ² or less.
Vinyl alcohol copolymer (C). 8. The tensile yield strength measured in tensile strength and elongation at 23 ° C. and 50% RH is 0.5 to 7 kgf / mm.
^2, and modified ethylene according to any one of the tensile elongation at break according to claim 1 to 7 is 150% or more - vinyl alcohol copolymer (C). 9. An ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound (B) having a molecular weight of 500 or less.
A method for producing a modified ethylene-vinyl alcohol copolymer (C), which comprises reacting with 10. The modified ethylene-vinyl alcohol copolymer according to claim 9, wherein 100 parts by weight of the ethylene-vinyl alcohol copolymer (A) is reacted with 1 to 50 parts by weight of a monovalent epoxy compound (B) having a molecular weight of 500 or less. Method for producing polymer (C). 11. The ethylene-vinyl alcohol copolymer (A) has an ethylene content of 5 to 55 mol% and a saponification degree of 9
The method for producing a modified ethylene-vinyl alcohol copolymer (C) according to claim 9 or 10, which is 0% or more of an ethylene-vinyl alcohol copolymer. 12. The ethylene-vinyl alcohol copolymer (A) has an alkali metal salt content of 5 in terms of metal element.
It is an ethylene-vinyl alcohol copolymer which is 0 ppm or less, The manufacturing method of the modified ethylene-vinyl alcohol copolymer (C) of any one of Claims 9-11. 13. The ethylene-vinyl alcohol copolymer (A) is an ethylene-vinyl alcohol copolymer having an alkaline earth metal salt content of 20 ppm or less in terms of a metal element. 2. The method for producing the modified ethylene-vinyl alcohol copolymer (C) according to Item 1. 14. The modified ethylene-vinyl alcohol copolymer according to claim 9, wherein the monovalent epoxy compound (B) having a molecular weight of 500 or less is an epoxy compound having 2 to 8 carbon atoms. The manufacturing method of (C). 15. An ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound (B) having a molecular weight of 500 or less.
10. The reaction with is carried out in an extruder.
15. The method for producing the modified ethylene-vinyl alcohol copolymer (C) according to any one of items 1 to 14. 16. The modified ethylene-vinyl alcohol copolymer according to claim 15, wherein the monovalent epoxy compound (B) having a molecular weight of 500 or less is added to the ethylene-vinyl alcohol copolymer (A) in a molten state in the extruder. Method for producing polymer (C). 17. A modified ethylene-vinyl alcohol copolymer (C) containing 0.3 to 40 mol% of the following structural unit (I) and having an ethylene content of 5 to 55 mol%. It is a polymer and is a polymer.
The method for producing the modified ethylene-vinyl alcohol copolymer (C) according to any one of 1. [Chemical 2] (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. R ¹ , R ² , R ³ and R ⁴ may be the same or different, and R ³ and R ⁴ may be bonded to each other. (The above R ¹ , R ² , R ³ and R ⁴ may have a hydroxyl group, a carboxyl group or a halogen atom.) 18. A barrier material comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 19. A gas barrier material comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 20. A composition comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 21. An extrusion molded article comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 22. A film or sheet comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 23. A stretched film comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 24. A thermoformed product comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 25. A heat-shrinkable film comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 26. A wallpaper or a decorative plate comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 27. A pipe or hose comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 28. A shaped article comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 29. An extrusion blow-molded article comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1-8. 30. A flexible packaging material comprising the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8. 31. A laminate of the modified ethylene-vinyl alcohol copolymer (C) according to any one of claims 1 to 8 and a resin other than the modified ethylene-vinyl alcohol copolymer (C). Multi-layered structure. 32. The resin other than the modified ethylene-vinyl alcohol copolymer (C) is selected from the group consisting of polyolefin, polyamide, polyester, polystyrene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile and polycarbonate. The multilayer structure according to claim 31, which is at least one kind. 33. The multilayer structure according to claim 31, wherein the resin other than the modified ethylene-vinyl alcohol copolymer (C) is an elastomer. 34. A coextruded film or sheet comprising the multilayer structure according to claim 31. 35. A multi-layer pipe comprising the multi-layer structure according to any one of claims 31 to 33. 36. A fuel pipe or hot water circulation pipe comprising the multilayer pipe according to claim 35. 37. A multi-layer hose made of the multi-layer structure according to claim 31. 38. A fuel hose comprising the multi-layer hose of claim 37. 39. A co-extrusion blow-molded container comprising the multilayer structure according to any one of claims 31 to 33.