# US 8,772,392 B2 · Melt-molded article containing an ethylene-vinyl alcohol copolymer resin composition of low carboxylic acid content

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- Number: US 8,772,392 B2
- Document ID: US8772392B2
- Status: Granted
- Kind: B2
- Application number: 12/393,532
- Filed: 2009-02-26
- Published: 2009-08-27
- Granted: 2014-07-08
- Earliest claimed: 2002-02-18
- Assignees: Kuraray Co., Ltd.
- Applicants: Kaoru Ikeda; Noriyuki Kida; Hiroyuki Shindome; Naohiko Uchiumi
- Inventors: Kaoru Ikeda; Noriyuki Kida; Hiroyuki Shindome; Naohiko Uchiumi
- Web page: https://patentgrep.com/patent/US8772392B2

## CPC

- C08L 23/0861: Saponified copolymers, e.g. ethylene vinyl alcohol copolymers
- B29B 9/12: characterised by structure or composition
- C08J 3/12: Powdering or granulating
- C08J 3/2053: {the additives only being premixed with a liquid phase}
- C08K 3/24: Acids; Salts thereof {(C08K3/16 takes precedence)}
- C08K 3/38: Boron-containing compounds
- C09J 123/08: Copolymers of ethene (C09J123/16 takes precedence)
- B29B 9/06: in the form of filamentary material, e.g. combined with extrusion
- C08J 2323/08: Copolymers of ethene (C08J2323/16 takes precedence)
- C08J 2329/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
- Y10T 156/10: Methods of surface bonding and/or assembly therefor
- Y10T 428/1352: Polymer or resin containing [i.e., natural or synthetic]
- Y10T 428/1393: Multilayer [continuous layer]
- Y10T 428/31681: Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
- Y10T 428/31692: Next to addition polymer from unsaturated monomers
- Y10T 428/31699: Ester, halide or nitrile of addition polymer
- Y10T 428/31909: Next to second addition polymer from unsaturated monomers
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29B: PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A melt-molded article containing an EVOH resin composition of low acetic acid odor and good long run workability is provided.

## Claims

### Claim 1

A melt-molded article comprising an ethylene-vinyl alcohol copolymer resin composition which comprises:
an ethylene-vinyl alcohol copolymer resin; and
a phosphoric acid compound (D);
wherein
a ratio (d/t) of the content (d: μmol/g) of the phosphoric acid compound (D) in terms of phosphate radical to a content (t: μmol/g) of phosphorus element is 0.4 or less,
wherein
the content (d) of the phosphoric acid compound (D) is determined by ion chromatography analysis of a solution obtained by extraction of the melt-molded article with 0.01 N aqueous HCL solution at 95° C. for 4 hours, and
the content (t) of phosphorous element is determined by high-frequency plasma emission spectrochemical analysis of a solution of combustion ash, the combustion ash being obtained by complete burning of the melt-molded article by an oxygen-flask combustion technique.

### Claim 2 (depends on 1)

The melt-molded article according to claim 1, further comprising an alkali metal salt (A), wherein
a content of alkali metal in the melt-molded article is from 0.1 to 20 μmol/g.

### Claim 3 (depends on 2)

The melt-molded article according to claim 2, wherein the alkali metal salt (A) is a potassium salt.

### Claim 4 (depends on 2)

The melt-molded article according to claim 2, wherein a content a (μmol/g) of the alkali metal is described by formula (1):
0.95×exp(0.039×ET)−2≦a≦0.95×exp(0.039×ET)+2 (1)
wherein ET is the ethylene content (mol %) of the ethylene-vinyl alcohol copolymer resin.

### Claim 5 (depends on 1)

The melt-molded article according to claim 1, further comprising a boron compound (B), wherein
a content of boron in the melt-molded article is from 1 to 200 μmol/g.

### Claim 6 (depends on 1)

The melt-molded article according to claim 1, wherein a content of ethylene in the ethylene-vinyl alcohol copolymer resin is 5 to 60 mol %.

### Claim 7

A method for producing a film comprising:
melt molding an ethylene-vinyl alcohol copolymer resin composition,
wherein the ethylene-vinyl alcohol copolymer resin composition is obtained by contacting an ethylene-vinyl alcohol copolymer resin with an aqueous solution comprising carbon dioxide gas, a phosphoric acid compound and at least one additive selected from the group consisting of an alkali metal salt (A) and a boron compound (B);
drying the phosphoric acid compound-containing ethylene-vinyl alcohol resin to obtain a dried phosphoric acid compound-containing ethylene-vinyl alcohol resin; and
heating the dried phosphoric acid compound-containing ethylene-vinyl alcohol resin in a molten state;
wherein
a ratio (d/t) of the content (d: μmol/g) of the phosphoric acid compound (D) in terms of phosphate radical to a content (t: μmol/g) of phosphorus element in the ethylene-vinyl alcohol copolymer resin composition is 0.4 or less in the ethylene-vinyl alcohol resin, and
wherein
the content (d) of the phosphoric acid compound (D) is determined by ion chromatography analysis of a solution obtained by extraction of the melt-molded article with 0.01 N aqueous HCL solution at 95° C. for 4 hours, and
the content (t) of phosphorous element is determined by high-frequency plasma emission spectrochemical analysis of a solution of combustion ash, the combustion ash being obtained by complete burning of the melt-molded article by an oxygen-flask combustion technique.

### Claim 8

A method for producing a multilayer structure comprising:
laminating an ethylene-vinyl alcohol copolymer resin composition with a thermoplastic resin,
wherein the ethylene-vinyl alcohol copolymer resin composition is obtained by contacting an ethylene-vinyl alcohol copolymer resin with an aqueous solution comprising carbon dioxide gas, a phosphoric acid compound and at least one additive selected from the group consisting of an alkali metal salt (A) and a boron compound (B);
drying the phosphoric acid compound containing ethylene-vinyl alcohol resin to obtain a dried phosphoric acid compound containing ethylene-vinyl alcohol resin; and
heating the molten dried phosphoric acid compound containing ethylene-vinyl alcohol resin in a molten state;
wherein
a ratio (d/t) of the content (d: μmol/g) of the phosphoric acid compound (D) in terms of phosphate radical to a content (t: μmol/g) of phosphorus element in the ethylene-vinyl alcohol copolymer resin composition is 0.4 or less in the ethylene-vinyl alcohol resin, and
wherein
the content (d) of the phosphoric acid compound (D) is determined by ion chromatography analysis of a solution obtained by extraction of the melt-molded article with 0.01 N aqueous HCL solution at 95° C. for 4 hours, and
the content (t) of phosphorous element is determined by high-frequency plasma emission spectrochemical analysis of a solution of combustion ash, the combustion ash being obtained by complete burning of the melt-molded article by an oxygen-flask combustion technique.

### Claim 9

A film comprising an ethylene-vinyl alcohol copolymer resin composition, wherein the ethylene-vinyl alcohol copolymer resin composition comprises:
an ethylene-vinyl alcohol copolymer;
a phosphoric acid compound (D); and
phosphorous element;
wherein
a ratio (d/t) of the content (d: μmol/g) of the phosphoric acid compound (D) in terms of phosphate radical to the content (t: μmol/g) of the phosphorus element is 0.4 or less, and
wherein
the content (d) of the phosphoric acid compound (D) is determined by ion chromatography analysis of a solution obtained by extraction of the melt-molded article with 0.01 N aqueous HCL solution at 95° C. for 4 hours, and
the content (t) of phosphorous element is determined by high-frequency plasma emission spectrochemical analysis of a solution of combustion ash, the combustion ash being obtained by complete burning of the melt-molded article by an oxygen-flask combustion technique.

### Claim 10

A multilayer structure comprising
at least one layer comprising an ethylene-vinyl alcohol copolymer resin composition, the resin composition comprising:
an ethylene-vinyl alcohol copolymer resin,
a phosphoric acid compound (D) and
phosphorous element,
wherein a ratio (d/t) of the content (d: μmol/g) of the phosphoric acid compound (D) in terms of phosphate radical to the content (t: μmol/g) of phosphorous element is 0.4 or less, and
wherein
the content (d) of the phosphoric acid compound (D) is determined by ion chromatography analysis of a solution obtained by extraction of the melt-molded article with 0.01 N aqueous HCL solution at 95° C. for 4 hours, and
the content (t) of phosphorous element is determined by high-frequency plasma emission spectrochemical analysis of a solution of combustion ash, the combustion ash being obtained by complete burning of the melt-molded article by an oxygen-flask combustion technique.