Preparation of a Coating, Adhesive, Film or Sheet

Abstract

The present invention relates to a process for the preparation of a coating, a coated substrate, an adhesive, film or sheet, which process comprises the application of a formulation mixture containing a reactive system onto a substrate. According to the invention a low VOC formulation mixture is used, wherein more than 40% of the carbon in the combined amount of the formulation mixture is modern carbon according to ASTM D6866.

Claims

1. A process for the preparation of a coating, coated substrate, adhesive, film or sheet, in which process a formulation mixture having a-content of non volatile organic compounds of at least 80 wt %, comprising: (a) applying onto a substrate a reactive system of a polyisocyanate-functional, polyketone-functional, polyepoxide-functional, polyanhydride-functional and/or polycyclic carbonate-functional compound or polymer and a dispersion or fine powder of a compound containing reactive hydrogen, resulting in a substrate coated with the formulation mixture; and (b) reacting the compounds mentioned above by elevating the temperature, wherein more than 40% of the carbon in the combined amount of the formulation mixture is modern carbon according to ASTM D6866.

2. The process according to claim 1, wherein the compound containing reactive hydrogen is present in the mixture in step (a) at ambient temperature as a fine powder or as a dispersion in a material which is non-reactive towards the reactive hydrogen.

3. The process according to claim 1, wherein the compound containing the reactive hydrogen is a compound which is crystalline at a temperature below 30° C.

4. The process according to claim 1, wherein the compound containing reactive hydrogen is a polyhydrazide and/or polysemicarbazide and/or piperazine.

5. The process according to claim 1, wherein the material which is non-reactive towards the compound containing reactive hydrogen contains modern carbon according to ASTM D6866.

6. The process according to claim 1, wherein the polyisocyanate functional, or polyepoxide functional, polyanhydride functional or polyketone functional compound or polymer are prepared using one or more polyol components that contain modern carbon according to ASTM D6866.

7. The process according to claim 1, wherein the polyisocyanate functional or polyepoxide functional, polyanhydride functional or polyketone functional compound or polymer are prepared using polytrimethylene ether polyol (PO3G) from bio-derived propanediol, polyols derived from fatty acids, castor oil-based polyols, polyester polyols derived from succinic acid, polyester polyols derived from sebacic acid, polyester polyols derived from azelaic acid or bio-based polycarbonate polyols, polyols synthesized from captured carbon dioxide if the source of the carbon dioxide is, in whole or in significant part, of biological products or renewable agricultural materials or forestry materials, or a combination thereof as one or more polyol components that contain modern carbon according to ASTM D6866.

8. The process according to claim 1, wherein the amount of polyester polyol containing modern carbon according to ASTM D6866 in the total amount of polyols used to prepare the polyisocyanate functional or polyepoxide functional, polyanhydride functional or polyketone functional compound or polymer is below 90 wt %.

9. The process according to claim 6, wherein a combination of polyether polyol preferably containing modern carbon according to ASTM D6866 and polyester polyol containing modern carbon according to ASTM D6866 is used in a weight ratio from 90/10 to 10/90.

10. A process for the preparation of a coating, coated substrate, adhesive, film or sheet, in which process a formulation mixture comprising: (a) applyinq onto a substrate a reactive system of a blocked prepolymer or blocked polymer, in which the isocyanate functional groups have been blocked, and a dispersion or fine powder of a compound containing a reactive hydrogen, resulting in a substrate coated with the coating mixture; and (b) reacting the compounds mentioned above by elevating the temperature to a temperature high enough to deblock the blocked prepolymer or blocked polymer to liberate the isocyanate groups so that the isocyanate groups can react with the compound containing a reactive hydrogen, wherein more than 40% of the carbon in the combined amount of the polymer mixtures is modern carbon according to ASTM D6866.

11. The process according to claim 1, wherein the temperature is elevated to between 110° C. and 180° C.

12. The process according to claim 1, wherein the total formulation mixture does not contain solvent and is thus free of volatile organic compounds (VOC).

13. The process according to claim 1, wherein more than 45% of the carbon in the combined amount of the formulation mixture is modern carbon according to ASTM D6866.

14. A coating, coated substrate, adhesive, film or sheet obtainable by the process as defined in claim 1.

15. A layered structure of which at least one layer comprises a coating, coated substrate, adhesive, film or sheet as defined in claim 14.

16. The layered structure according to claim 15, further comprising one or more layers that do not contain modern carbon according to ASTM D6866.

17. The process according to claim 4, wherein the compound containing reactive hydrogen is adipic acid dihydrazide and/or malonic acid dihydrazide and/or carbodihydrazide.

18. The process according to claim 5, wherein the material which is non-reactive towards the compound containing reactive hydrogen contains castor oil.

19. The process according to claim 9, wherein a combination of polyether polyol preferably containing modern carbon according to ASTM D6866 and polyester polyol containing modern carbon according to ASTM D6866 is used in a weight ratio from 65/35 to 35/65.

20. The process according to claim 10, wherein the temperature is elevated to between 110° C. and 180° C.

21. The process according to claim 10, wherein the total formulation mixture does not contain solvent and is thus free of volatile organic compounds (VOC).

22. The process according to claim 10, wherein more than 45% of the carbon in the combined amount of the formulation mixture is modern carbon according to ASTM D6866.

23. A coating, coated substrate, adhesive, film or sheet obtainable by the process as defined in claim 10.

24. A layered structure of which at least one layer comprises a coating, coated substrate, adhesive, film or sheet as defined in claim 23.

25. The layered structure according to claim 24, further comprising one or more layers that do not contain modern carbon according to ASTM D6866.

Description

EXAMPLES

Example 1: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0043] Under a nitrogen atmosphere, 152.7 g (688 mmol) 3-isocyanato-methyl-3,5,5-trimethylcyclohexylisocyanate (in the following indicated as IPDI) and 80.0 g (381 mmol) 2,2,4-trimethyl hexamethylene diisocyanate (in the following indicated as TMDI) were added to a mixture at 70° C. of 359.3 g (180 mmol) of Relca Bio PO 2056 (bio-polyester with a molecular weight of 2000; obtainable from Stahl Polymers), 160.0 g (160 mmol) of Velvetol H1000 (a bio-polyether polyol with a molecular weight of 1000; obtainable from Allyssa Chemical) and 48.0 g (329 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.05 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 100° C. and was reacted for three hours at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 3.98%.

Example 2: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0044] Under a nitrogen atmosphere, 151.8 g (684 mmol) IPDI and 80.0 g (381 mmol) TMDI were added to a mixture at 70° C. of 360.2 g (180 mmol) of Relca Bio PO 1056 (bio-polyester with a molecular weight of 2000; obtainable from Stahl Polymers), 160.0 g (160 mmol) of Velvetol H1000 (a bio-polyether polyol with a molecular weight of 1000; obtainable from Allyssa Chemical) and 48.0 g (329 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.05 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 100° C. and was reacted for three hours at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 3.84%.

Example 3: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0045] Under a nitrogen atmosphere, 163.6 g (737 mmol) IPDI and 89.6 g (427 mmol) TMDI were added to a mixture at 70° C. of 498.8 g (249 mmol) of Relca Bio PO 1056 (bio-polyester with a molecular weight of 2000; obtainable from Stahl Polymers) and 48.0 g (329 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.01 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 100° C. and was reacted for one hour at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 5.73%.

Example 4: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0046] Under a nitrogen atmosphere, 162.9 g (734 mmol) IPDI and 89.6 g (427 mmol) TMDI were added to a mixture at 70° C. of 355.5 g (178 mmol) of Relca Bio PO 1056 (bio-polyester with a molecular weight of 2000; obtainable from Stahl Polymers), 144.0 g (72 mmol) of Velvetol H2000 (a bio-polyether polyol with a molecular weight of 2000; obtainable from Allyssa Chemical) and 48.0 g (329 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.01 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 100° C. and was reacted for one hour at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 5.65%.

Example 5: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0047] Under a nitrogen atmosphere, 178.6 g (805 mmol) IPDI and 112.0 g (381 mmol) TMDI were added to a mixture at 70° C. of 293.4 g (309 mmol) of Bio-Hoopol 11920 (bio-polyester with a molecular weight of 950; obtainable from Synthesia Technology), 160.0 g (160 mmol) of Velvetol H1000 (a bio-polyether polyol with a molecular weight of 1000; obtainable from Allyssa Chemical) and 56.0 g (384 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.05 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 80° C. and was reacted for three hours at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 5.10%.

Example 6: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0048] Under a nitrogen atmosphere, 207.1 g (1233 mmol) of hexamethylene diisocyanate was added to a mixture at 70° C. of 288.9 g (289 mmol) of Relca Bio PO 1120 (bio-polyester with a molecular weight of 1000; obtainable from Stahl Polymers), 256.0 g (256 mmol) of Velvetol H1000 (a bio-polyether polyol with a molecular weight of 1000; obtainable from Allyssa Chemical) and 48.0 g (329 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.01 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 80° C. and was reacted for two hours at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 4.82%.

Example 7: Preparation of Films and Measuring Modern Carbon Content According to ASTM D6866

[0049] 50 g of the product of Examples 1 to 6 were each mixed with an stoichiometric amount (with respect to the remaining NCO content) of a 1:1 dispersion of adipic dihydrazide in castor oil. Films of a thickness of 200 m were prepared and they were heated for 2 min at 160° C. The films obtained were flexible and dry (non-tacky).

[0050] The content of modern carbon according to ASTM D6866 was measured to be 53% for the film from Example 1, 52% for the film made from Example 2, 45% for the film made from Example 3, 50% for the film made from Example 4, 44% for the film made from Example 5, 57% for the film made from Example 6.

Comparative Example 8: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0051] Under a nitrogen atmosphere, 192 g (1142 mmol) hexamethylene diisocyanate was added to a mixture at 70° C. of 304 g (304 mmol) of Voranol PPG1000 (polypropylene glycol with a molecular weight of 1000; obtainable from Dow), 80 g (40 mmol) of Voranol PPG2000 (polypropylene glycol with a molecular weight of 2000; obtainable from Dow), 4.0 g (30 mmol) of trimethylolpropane, 16 g (154 mmol) of 2,2-dimethyl-1,3-propanediol and 204 g (219 mmol) of Hoopol S1015-120 (a polyester, obtainable from Synthesia), while stirring. Next, 0.01 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 100° C. and was reacted for one hour at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 3.85%.

Comparative Example 9: Preparation of an Isocyanate Functional Polyurethane Prepolymer

[0052] Under a nitrogen atmosphere, 186 g (1106 mmol) hexamethylene diisocyanate was added to a mixture at 70° C. of 48 g (24 mmol) of Voranol PPG2000 (polypropylene glycol with a molecular weight of 2000; obtainable from Dow), 4.0 g (30 mmol) of trimethylolpropane, 8 g (77 mmol) of 2,2-dimethyl-1,3-propanediol and 554 g (595 mmol) of Hoopol S1015-120 (a polyester, obtainable from Synthesia), while stirring. Next, 0.01 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 100° C. and was reacted for one hour at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 3.70%.

Example 10: Hydrolysis Resistance Tests

[0053] Films were made of the product of Examples 1 to 6, as described in the first part of Example 7. In a similar manner, films were made of the products of Comparative Example 8 and Comparative Example 9. Mechanical properties of the films were measured with a dynamometer model AG/MC from Acquati Guiseppe, before and after hydrolysis test. Hydrolysis test was done according to ISO-1419 method C by subjecting specimens to a temperature of 70° C. and 95% relative humidity during 28 days. The value at M-100, expressed in MPa (10.sup.6 N/m.sup.2), is the strain of the film when stretched at 100%. If a film becomes too weak upon hydrolysis, then this will be made apparent when comparing the M-100 value before and after hydrolysis.

[0054] The results are collected in the Table below.

TABLE-US-00001 M-100 M-100 after hydrolysis test for Film from original 28 days, in % vs M-100 % Polyester on Example (MPa) original total of polyols 1 1.4 150 63 2 0.7 150 63 3 3.1 84 91 4 2.5 104 64 5 1.8 94 57 6 1.5 147 49 Comp. 8 1.1 164 34 Comp. 9 2.7 60 90

[0055] Films from Examples 1 to 6 and from the Comparative Example 8 remained a film upon the completion of the hydrolysis test and did not deteriorate too much, and the M-100 could be measured after hydrolysis test. The film from Comparative Example 9 had deteriorated more upon the hydrolysis test and only 60% of the original M-100 remained. Examples 1, 2, 4 and 6 were made with between 49 weight % and 64 weight % of the total mass of polyol components consisting of biobased-fatty-acid based polyester polyol. Example 3 was made with 91 weight % of the total mass of polyol components consisting of biobased-fatty-acid based polyester polyol. Comparative Example 8 was made with 34 weight % of the total mass of polyol components consisting of polyester polyol from hexane-diol, 2,2-dimethyl-1,3-propanediol and hexanedioic acid. Comparative Example 9 was made with 90 weight % of the total mass of polyol components consisting of polyester polyol from hexane-diol, 2,2-dimethyl-1,3-porpanediol and hexanedioic acid.

[0056] The hydrolysis resistance of the film from Example 3 is better than the hydrolysis resistance of the film from Comparative Example 9, although the weight % of the polyester on the total mass of polyol components is similar, while the polyester in Example 3 is a biobased-fatty-acid based polyester polyol.

[0057] The hydrolysis resistances of films from Examples 1, 2, 4 and 6 were good and also the hydrolysis resistance of Comparative Example 8 was good, although the weight % of the polyester on the total mass of polyol components was higher, being between 49 weight % and 64% weight % for Examples 1, 2, 4 and 6, than in Comparative Example 8, which was only 34 weight %, while the polyester in Example 1, 2, 4 and 6 is a biobased-fatty-acid based polyester polyol.

Example 11: Preparation of a Blocked Isocyanate Functional Polyurethane Prepolymer

[0058] Under a nitrogen atmosphere, 195.0 g (1161 mmol) of hexamethylene diisocyanate was added to a mixture at 70° C. of 257.5 g (257 mmol) of Relca Bio PO 1120 (bio-polyester with a molecular weight of 1000; obtainable from Stahl Polymers), 233.6 g (117 mmol) of Velvetol H2000 (a bio-polyether polyol with a molecular weight of 2000; obtainable from Allyssa Chemical) and 43.8 g (300 mmol) of 2,2,4-trimethyl pentanediol, while stirring. Next, 0.01 g of K-Kat 348 (obtainable from King Industries) was added as a catalyst. The mixture was maintained at 80° C. and was reacted for two hours at this temperature under formation of a polyurethane prepolymer. The reaction mixture was cooled down. The remaining NCO-content was measured and was 5.25%. Next, 70.1 g (959 mmol) of acetone oxime was added and the mixture was maintained at 70° C. for one hour. The absence of isocyanate signal in the infrared spectrum was checked.

Example 12: Preparation of Film from Blocked Isocyanate Functional Polyurethane Prepolymer

[0059] 100 g of the product of Example 11 was mixed with an stoichiometric amount (with respect to the NCO content after deblocking) of 13.1 g of a 1:1 dispersion of adipic dihydrazide in castor oil. Films of a thickness of 250 jm were prepared and heated for 3 min at 190° C. The films obtained were flexible and dry (non-tacky). The M-100 of a fresh film, measured as described in Example 10, was 0.8 MPa.

The hydrolysis resistance was tested in the same manner as described in Example 10. The M-100 of the film after 4 weeks of exposure in the hydrolysis test, was 160% of the original value.
The content of modern carbon according to ASTM D6866 was extrapolated to be 55%, upon comparing the composition with Example 6.