Thermoformed articles and compositions of poly(hydroxyalkanoic acid) and polyoxymethylene
View Patent ↗Disclosed are poly(hydroxyalkanoic acid) resin compositions comprising poly(hydroxyalkanoic acid), such as polylactic acid, and a polyoxymethylene. Also disclosed are articles such as films, sheets and thermoformed containers comprising the compositions.
1. An article comprising a composition wherein
the composition comprises or is produced from poly(hydroxyalkanoic acid) and 0.1 to 0.9 weight % of a polyoxymethylene, based on the total amount of the composition; and
the article is a thermoformed article.
2. The article of claim 1 wherein the article is optically transparent and the poly(hydroxyalkanoic acid) comprises hydroxyalkanoic acids having five or fewer carbon atoms.
3. The article of claim 2 wherein
the poly(hydroxyalkanoic acid) comprises glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, or combinations of two or more thereof;
the article has less than 5% haze, measured with 10 to 13 mil film or sheet using ASTM D1003-REV92; and
the article has less than 15% shrinkage when the article is heated to 60° C. for at least 2 seconds.
4. The article of claim 3 wherein
the poly(hydroxyalkanoic acid) comprises poly(glycolic acid, poly(lactic acid), polyhydroxy-butyric acid, polyhydroxybutyrate-hydroxyvalerate copolymer, copolymer of glycolic acid and lactic acid, or combinations of two or more thereof;
the article has less than 3% haze; and
the article has less than 10% shrinkage when the article is heated to 60° C. for at least 2 seconds.
5. The article of claim 1 wherein the poly(hydroxyalkanoic acid) is poly(lactic acid).
6. The article of claim 4 wherein the poly(hydroxyalkanoic acid) is poly(lactic acid).
7. The article of claim 6 having less than 2% haze.
8. The article of claim 1 wherein the composition has cool-down crystallization energy less than 5 J/g, where cool-down crystallization energy is determined by differential scanning calorimetry by heating a sample of the composition from ambient temperature to 220° C. at 10° C./minute and cooling to ambient temperature at 10° C./minute.
9. The article of claim 8 wherein
the poly(hydroxyalkanoic acid) comprises hydroxyalkanoic acids having five or fewer carbon atoms;
the article is oriented;
the article has less than 5% haze, measured with 10 to 13 mil film or sheet using ASTM D1003-REV92; and
the article has less than 15% shrinkage when the article is heated to 60° C. for at least 2 seconds.
10. The article of claim 9 wherein
the poly(hydroxyalkanoic acid) comprises poly(glycolic acid, poly(lactic acid), polyhydroxy-butyric acid, polyhydroxybutyrate-hydroxyvalerate copolymer, copolymer of glycolic acid and lactic acid, or combinations of two or more thereof;
the article has less than 3% haze; and
the article has less than 10% shrinkage when the article is heated to 60° C. for at least 2 seconds.
11. The article of claim 10 wherein the composition comprises from 0.1 to 0.9 weight % of the polyoxymethylene resin.
12. The article of claim 10 wherein the poly(hydroxyalkanoic acid) is poly(lactic acid).
13. The article of claim 11 wherein the poly(hydroxyalkanoic acid) is poly(lactic acid) and the article has less than 2% haze.
14. A poly(hydroxyalkanoic acid) composition comprising (i) poly(hydroxyalkanoic acid) and (ii) from 0.1 to 0.9 weight % of a polyoxymethylene resin.
15. The composition of claim 14 wherein the poly(hydroxyalkanoic acid) comprises 6-hydroxyhexanoic acid, 3-hydroxyhexanoic acid, 4-hydroxyhexanoic acid 3-hydroxyheptanoic acid, or combinations of two or more thereof and the composition has a glass transition temperature that is within 3% of the glass transition temperature of the poly(hydroxyalkanoic acid).
16. The composition of claim 15 wherein the poly(hydroxyalkanoic acid) is poly(lactic acid) and the composition has cool-down crystallization energy less than 5 J/g, where cool-down crystallization energy is determined by differential scanning calorimetry by heating a sample of the composition from ambient temperature to 220° C. at 10° C./minute and cooling to ambient temperature at 10° C./minute.
17. A process comprising compounding a composition to produce a compounded composition; producing a film or sheet from the composition; and thermoforming the film or sheet in a mold at a thermoforming temperature effective to form a shaped article wherein
the composition comprises or is produced from poly(hydroxyalkanoic acid) and 0.1 to 9 weight % of a polyoxymethylene, based on the total amount of the composition;
the article is thermoformed article; and
the composition has a glass transition temperature that is within 5% of the glass transition temperature of the poly(hydroxyalkanoic acid).
18. The process of claim 17 wherein
the poly(hydroxyalkanoic acid) is polylactic acid;
the composition comprises or is produced from poly(hydroxyalkanoic acid) and 0.1 to 0.9 weight % of the polyoxymethylene;
the film or sheet, before the thermoforming, is preheated for 5 to 200 seconds;
the thermoforming temperature is 90 to 200° C.;
the thermoforming is carried out for a period of 0.1 to 20 seconds; and
the process further comprises quenching the article to a temperature of about 50° C.
19. The process of claim 18 wherein
the film or sheet is preheated for 20 to 60 seconds;
the thermoforming temperature is at about the midpoint between the Tg and the melt point of the polylactic acid;
the thermoforming is carried out for a period of 0.5 to 6 seconds; and
the quenching is carried out in less than 5 minutes.