Ethylene-vinyl alcohol copolymer resin composition and method for producing same

Patent metadata

Field	Value
Publication number	US-9951199-B2
Application number	US-201214131301-A
Country	US
Kind code	B2
Filing date	Jul 5, 2012
Priority date	Jul 7, 2011
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

Provided by the present invention is an ethylene-vinyl alcohol copolymer resin composition having superior appearance characteristics (particularly decreased coloring and unevenness of the hue), and is accompanied by suppressed occurrence of yellowing, etc., in melt molding. An ethylene-vinyl alcohol copolymer resin composition containing an ethylene-vinyl alcohol copolymer (A) and a compound having an enediol structure (B), in which a molar ratio of the compound (B) to vinyl alcohol units of the ethylene-vinyl alcohol copolymer (A) is 2.70×10 −9 or greater and 2.70×10 −5 or less.

First claim

The invention claimed is:

1. An ethylene-vinyl alcohol copolymer resin composition, comprising:
(A) an ethylene-vinyl alcohol copolymer;
(B) a compound, which is gallic acid, methyl gallate, ethyl gallate, propyl gallate, isoamyl gallate, tannic acid, pyrogallol, catechol, epicatechin, epigallocatechin, epigallocatechin gallate, ellagic acid, a salt thereof, or a combination thereof;
a monocarboxylic acid or a salt thereof, which is acetic acid, lactic acid, capric acid, or a salt thereof, in an amount of 0 μmol/g or greater and 12.0 μmol/g or less in terms of carboxylic acid radical equivalent;
a multivalent carboxylic acid or a salt thereof, which is tartaric acid, aspartic acid, succinic acid, ethylenediamine tetraacetic acid, or a salt thereof, in an amount of 0 μmol/g or greater and 8.0 μmol/g or less in terms of carboxylic acid radical equivalent;
an alkali metal ion, which is a sodium ion or a potassium ion, in an amount of 0 μmol/g or greater and 21.0 mol/g or less; and
an alkaline earth metal ion, which is a calcium ion or a magnesium ion, in an amount of 0 μmol/g or greater and 8.50 μmol/g or less,
wherein a total amount of metal ions is 22.0 μmol/g or less,
wherein the molar ratio of the compound to vinyl alcohol units of the ethylene-vinyl alcohol copolymer is 2.96×10 −9 or greater and 2.64×10 −5 or less,
wherein an ethylene content of the ethylene-vinyl alcohol copolymer (A) is 20 mol % or greater and 60 mol % or less.

2. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , wherein a ratio ϵ2/ϵ1 that is a ratio of an extinction coefficient ϵ2 at 225 nm after a heat treatment in an air at 120° C. for 24 hrs to an extinction coefficient ϵ1 at 225 nm before the heat treatment is 2.0 or less.

3. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , wherein the compound (B) is gallic acid, methyl gallate, ethyl gallate, propyl gallate, isoamyl gallate, or a combination thereof.

4. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , wherein the compound (B) is pyrogallol, catechol, or a combination thereof.

5. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , wherein the compound (B) is epicatechin, epigallocatechin, epigallocatechin gallate, or a combination thereof.

6. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , wherein the compound (B) is tannic acid.

7. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , wherein the ethylene-vinyl alcohol copolymer (A) has a degree of saponification of 95 mol % or more.

8. The ethylene-vinyl alcohol copolymer resin composition according to claim 1 , further comprising:
a phosphoric acid compound, which is phosphoric acid, in an amount of 0 ppm or greater and 510 ppm or less in terms of phosphate radical equivalent; and
a boron compound, which is boric acid, in an amount of 0 ppm or greater and 996 ppm or less in terms of boron element equivalent,
wherein an ethylene content of the ethylene-vinyl alcohol copolymer (A) is 24 mol % or greater and 55 mol % or less.

9. A method for producing the ethylene-vinyl alcohol copolymer resin composition according to claim 1 , the method comprising:
saponifying an ethylene-vinyl ester copolymer to obtain the ethylene-vinyl alcohol copolymer (A), wherein an ethylene content of the ethylene-vinyl alcohol copolymer (A) is 20 mol % or greater and 60 mol % or less; and
mixing the ethylene-vinyl alcohol copolymer (A) after the saponification with:
the compound (B), which is gallic acid, methyl gallate, ethyl gallate, propyl gallate, isoamyl gallate, tannic acid, pyrogallol, catechol, epicatechin, epigallocatechin, epigallocatechin gallate, ellagic acid, a salt thereof, or a combination thereof;
the monocarboxylic acid or a salt thereof, which is acetic acid, lactic acid, capric acid, or a salt thereof;
the multivalent carboxylic acid or a salt thereof, which is tartaric acid, aspartic acid, succinic acid, ethylenediamine tetraacetic acid, or a salt thereof;
the alkali metal ion, which is a sodium ion or a potassium ion; and
the alkaline earth metal ion, which is a calcium ion or a magnesium ion,

to obtain the ethylene-vinyl alcohol copolymer resin composition,
wherein the molar ratio of the compound to vinyl alcohol units of the ethylene-vinyl alcohol copolymer is 2.96×10 −9 or greater and 2.64×10 −5 or less,
wherein the monocarboxylic acid or a salt thereof is in an amount of 0 μmol/g or greater and 12.0 μmol/g or less in terms of carboxylic acid radical equivalent,
wherein the multivalent carboxylic acid or a salt thereof is in an amount of 0 μmol/g or greater and 8.0 μmol/g or less in terms of carboxylic acid radical equivalent,
wherein the alkali metal ion is in an amount of 0 μmol/g or greater and 21.0 μmol/g or less,
wherein the alkaline earth metal ion is in an amount of 0 μmol/g or greater and 8.50 μmol/g or less, and
wherein a total amount of metal ions is 22.0 μmol/g or less.

10. The method according to claim 9 , further comprising:
pelletizing the ethylene-vinyl alcohol copolymer (A) obtained in the saponification by a granulating operation to obtain hydrous pellets comprising the ethylene-vinyl alcohol copolymer (A) and drying the hydrous pellets,
wherein the mixing comprises immersing the hydrous pellets in a solution comprising the compound (B), the monocarboxylic acid or a salt thereof, the multivalent carboxylic acid or a salt thereof, the alkali metal ion, and the alkaline earth metal ion, and
wherein the mixing is carried out after the pelletizing and before the drying.

11. The method according to claim 9 , further comprising:
pelletizing the ethylene-vinyl alcohol copolymer (A) obtained in the saponification and the compound (B) by a granulating operation to obtain hydrous pellets comprising the ethylene-vinyl alcohol copolymer (A) and the compound (B); and
drying the hydrous pellets.

12. A molded product formed from the ethylene-vinyl alcohol copolymer resin composition according to claim 1 .

13. A multilayer structure, comprising a layer formed from the ethylene-vinyl alcohol copolymer resin composition according to claim 1 .

Assignees

• Nonaka Yasuhiro
• Yamamoto Yoshio
• Yamasaki Yoshikazu
• Kuraray Co

Inventors

• Nonaka Yasuhiro
• Yamamoto Yoshio
• Yamasaki Yoshikazu

Classifications

• C08F8/12

  Hydrolysis · CPC title

• C08K5/13 Primary

  Phenols; Phenolates · CPC title

• C08K5/1535

  Five-membered rings · CPC title

• C08L29/04

  Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids · CPC title

• C08K5/1345

  Carboxylic esters of phenolcarboxylic acids · CPC title