Oxygen-absorbing film

Patent metadata

Field	Value
Publication number	US-11939495-B2
Application number	US-202016986470-A
Country	US
Kind code	B2
Filing date	Aug 6, 2020
Priority date	Jan 18, 2013
Publication date	Mar 26, 2024
Grant date	Mar 26, 2024

Abstract

An oxygen-absorbing film having an oxygen-absorbing adhesive agent layer including a cured oxygen-absorbing adhesive agent resin composition, wherein the oxygen-absorbing adhesive agent layer has at least two glass transition temperatures, and wherein the lowest glass transition temperature among the glass transition temperatures is lower than 0° C. The cured oxygen-absorbing adhesive agent resin composition preferably includes: (A) an oxygen-absorbing polyester resin having a glass transition temperature of −20 to 10° C. and (B) a saturated polyester resin having a glass transition temperature of −10° C. or lower. The oxygen-absorbing polyester-based resin (A) is made from a tetrahydrophthalic acid, a derivative thereof, a tetrahydrophthalic anhydride, or a derivative thereof, and the saturated polyester resin (B) containing a structural unit derived from a diol component and a structural unit derived from a dicarboxylic acid component is preferably selected from the group consisting of adipic acid, sebacic acid, isophthalic acid, and combinations thereof.

First claim

The invention claimed is:

1. An oxygen-absorbing film comprising an oxygen-absorbing adhesive layer made of an oxygen-absorbing adhesive resin composition cured at 35° C. in a nitrogen atmosphere, wherein:
the oxygen-absorbing adhesive resin composition has at least two glass transition temperatures after exposure to oxygen at 40° C. for two months, the lowest glass transition temperature thereof is less than 0° C., the oxygen-absorbing film has a single-phase compatible system prior to said oxygen exposure, the oxygen-absorbing adhesive resin composition comprises a cured oxygen-absorbing polyester-based resin (A) and a component containing a saturated polyester resin (B) having a glass transition temperature of −10° C. or less, a ratio A/B of the oxygen-absorbing polyester-based resin (A) to the saturated polyester resin (B) is 1 to 9, and a laminate strength of the film is not less than 1N/15 mm in a T-peel test at a peeling speed of 300 mm/min, the cured oxygen-absorbing adhesive resin composition is obtained by blending the oxygen-absorbing polyester-based resin (A) and the saturated polyester resin (B) with a polyisocyanate compound in an amount of 3 phr to 15 phr, wherein the polyisocyanate compound is an adduct or an isocyanurate comprising at least one of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and xylylene diisocyanate (XDI),
the oxygen-absorbing polyester-based resin (A) further comprises a transition metal catalyst, in an amount of 50 ppm to 1000 ppm with respect to an amount of the transition metal,
the oxygen-absorbing polyester-based resin (A) is made from a tetrahydrophthalic acid, a derivative thereof, a tetrahydrophthalic anhydride, or a derivative thereof, and a diol component selected from the group consisting of trimethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and derivatives thereof, and the saturated polyester resin (B) contains a structural unit derived from a diol component selected from the group consisting of trimethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and derivatives thereof and a structural unit derived from a dicarboxylic acid component selected from the group consisting of adipic acid, sebacic acid, isophthalic acid, and combinations thereof.

2. The oxygen-absorbing film according to claim 1 , comprising at least an oxygen barrier film layer, the oxygen-absorbing adhesive layer, and a sealant film layer.

3. The oxygen-absorbing film according to claim 1 wherein the cured oxygen-absorbing adhesive resin composition comprises: an oxygen-absorbing polyester-based resin (A) having a glass transition temperature of −20° C. to 10° C.; and wherein:
a ratio A/B of the oxygen-absorbing polyester-based resin (A) to the saturated polyester resin (B) is 1.5 to 9,
the glass transition temperature of the saturated polyester resin (B) is lower than the glass transition temperature of the oxygen-absorbing polyester-based resin (A), and the oxygen-absorbing adhesive resin composition has separate phases with glass transition temperatures of at least the oxygen-absorbing polyester-based resin (A) and the saturated polyester resin (B).

4. The oxygen-absorbing film according to claim 3 , wherein the saturated polyester resin (B) further comprises a structural unit derived from a hydroxycarboxylic acid component.

5. The oxygen-absorbing film according to claim 3 , wherein the saturated polyester resin (B) has an iodine value of 3 g/100 g or less measured in accordance with JIS K 0070.

6. The oxygen-absorbing film according to claim 3 , wherein the saturated polyester resin (B) has an iodine value of 1 g/100 g or less measured in accordance with JIS K 0070.

7. The oxygen-absorbing film according to claim 1 wherein the cured oxygen-absorbing adhesive resin composition comprises:
an oxygen-absorbing polyester-based resin (A) having a glass transition temperature of −20° C. to 10° C.; and;
wherein: a ratio A/B of the oxygen-absorbing polyester-based resin (A) to the saturated polyester resin (B) is 1.5 to 9,
the glass transition temperature of the saturated polyester resin (B) is lower than the glass transition temperature of the oxygen-absorbing polyester-based resin (A), and the oxygen-absorbing adhesive resin composition has a single-phase compatible system when the oxygen absorption starts, but has separated glass transition temperatures of two or more components due to reaction-induced phase separation following an oxygen absorption reaction.

8. The oxygen-absorbing film according to claim 1 wherein the polyisocyanate compound is an adduct of HDI/IPDI.

9. The oxygen-absorbing film according to claim 1 wherein the polyisocyanate compound is an adduct of IPDI/XDI.

10. The oxygen-absorbing film according to claim 1 wherein the polyisocyanate compound is an isocyanurate of XDI.

11. The oxygen-absorbing film according to claim 1 , wherein the amount transition metal catalyst is 50 ppm to 500 ppm with respect to the amount of the transition metal.

12. The oxygen-absorbing film according to claim 1 , wherein the amount transition metal catalyst is 50 ppm to 200 ppm with respect to the amount of the transition metal.

Assignees

• Toyo Seikan Group Holdings Ltd

Inventors

• Tadokoro Yoichi
• Ishizaki Yoichi
• Ohta Yoshihiro

Classifications

• C09J167/02 Primary

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09J167/06 takes precedence) · CPC title

• B65D81/266

  for absorbing gases, e.g. oxygen absorbers or desiccants (B65D51/244, B65D51/30 take precedence) · CPC title

• C08L67/00

  Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain (of polyester-amides C08L77/12; of polyester-imides C08L79/08); Compositions of derivatives of such polymers · CPC title

• C09J7/20

  characterised by their carriers · CPC title

• C09J11/08

  Macromolecular additives · CPC title