AQUEOUS BIO-BASED ENERGY CURABLE POLYURETHANE COMPOSITION

Abstract

An aqueous bio-based energy-curable polyurethane composition having at least one ethylenically unsaturated polyurethane pre-polymer (A) obtained from the reaction of at least one aliphatic, cycloaliphatic or aromatic polyisocyanate compound (Ai), at least one hydrophilic compound (Aii) containing at least one reactive group capable to react with an isocyanate and which is capable to render the polyurethane pre-polymer dispersible in an aqueous medium either directly or after the reaction with an organic or inorganic neutralizing agent to provide a salt therefrom, at least one ethylenically unsaturated compound (Aiii), containing essentially one reactive group capable to react with an isocyanate, at least one ethylenically unsaturated compound (Aiv), containing at least two reactive groups capable to react with an isocyanate.

Claims

1. An aqueous bio-based energy-curable polyurethane composition comprising: at least one ethylenically unsaturated polyurethane pre-polymer (A) obtained from the reaction of: at least one aliphatic, cycloaliphatic or aromatic polyisocyanate compound (Ai), at least one hydrophilic compound (Aii) containing at least one reactive group capable to react with an isocyanate and which is capable to render the polyurethane pre-polymer dispersible in an aqueous medium either directly or after the reaction with an organic or inorganic neutralizing agent to provide a salt therefrom, at least one ethylenically unsaturated compound (Aiii), containing essentially one reactive group capable to react with an isocyanate, at least one ethylenically unsaturated compound (Aiv), containing at least two reactive groups capable to react with an isocyanate, optionally, at least one ethylenically unsaturated compound (B) different from (Aiii) and (Aiv) having no reactive group capable to react with an isocyanate, wherein the ethylenically unsaturated compounds (Aiii), (Aiv) and (B) have each a biocarbon content of more than 20% by weight of total carbon content of the compound, and are obtained by reacting an ethylenically unsaturated compound with a compound derived from biobased sources, whereby the biocarbon content is determined using ASTM D6866 standard; wherein the ethylenically unsaturated compounds (Aiv) is prepared with from 0-40 wt % bisphenol A; preferably without bisphenol A; and wherein said composition comprises a total amount of polymerizable ethylenically unsaturated groups of at least 0.5 meq/g expressed per total weight of polyurethane composition, preferably at least 1 meq/g, more preferably at least 2 meq/g, even more preferably at least 3 meq/g and the most preferably at least 4 meq/g.

2. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the at least one ethylenically unsaturated polyurethane pre-polymer (A) is obtained from the reaction with a mono-alcohol or polyol (Av), different from (Ai), (Aii), (Aiii) or (Aiv), having a biocarbon content of more than 20% by weight and containing at least one reactive group capable to react with an isocyanate; and/or at least one mono-amine or polyamine (Avi), having optionally a biocarbon content of more than 20% by weight and capable to react with an isocyanate.

3. The aqueous bio-based energy curable polyurethane composition according to claim 1, wherein the polyurethane composition has a MFFT of between 0° C. and 20° C., more preferably between 0° C. and 10° C., most preferably between 0° C. and 5° C.

4. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the polyurethane composition has a biocarbon content of more than 20%, preferably above 40%, more preferably above 50%, even more preferably above 60%, most preferably above 70%, the most preferably above 80% by weight of the total carbon content of the polyurethane composition.

5. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein ethylenically unsaturated compound (Aiii), (Aiv) and/or (B) is obtainable by reacting a reactive biobased compound with a compound comprising at least one ethylenically unsaturated function, which is selected from the group consisting of acrylic acid, methacrylic acid, glycidyl (meth)acrylate.

6. The aqueous bio-based energy-curable polyurethane composition according to claim 5, wherein the reactive biobased compound is selected from the group consisting of organic oils or organic oil derivatives, carboxylic acid compounds, fatty acids and derivatives, fatty acid dimers and derivatives, and biobased polyols and derivatives thereof.

7. The aqueous bio-based energy-curable polyurethane composition according to claim 6, wherein the biobased polyol is an aliphatic, cycloaliphatic or aromatic polyols preferably selected from the group consisting of fatty alcohols, fatty alcohol dimers, carbohydrates, sugar alcohols, and/or wherein the biobased polyol derivatives are glycolide, lactide, lactone, poly(alkyleneoxide) derivatives.

8. The aqueous bio-based energy-curable polyurethane composition according to claim 6, wherein the organic oil derivative is an epoxidized oil selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized coconut oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized olive oil, epoxidized palm oil, epoxidized peanut oil, epoxidized sunflower oil, epoxidized safflower oil, epoxidized tall oil, epoxidized cashew shell oil, and/or the epoxidized fatty acid derived therefrom.

9. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the amount of reactive groups capable to react with an isocyanate present in the ethylenically unsaturated compound (Aiv) can be controlled by reacting a portion of the isocyanate reactive groups with a blocking compound capable to react with an isocyanate reactive group; whereby the blocking compound preferably generates a functionality different from the isocyanate reactive group functionality, preferably a carboxylic functionality; and whereby the blocking compound is preferably a cyclic anhydride, most preferably a succinic or maleic anhydride.

10. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the ethylenically unsaturated compounds (Aiii), (Aiv), and or (B) are obtainable by reacting a natural epoxidized oil with an ethylenically unsaturated carboxylic acid compound to obtain an ethylenically unsaturated polyol; reacting the ethylenically unsaturated polyol with a cyclic anhydride to obtain an ethylenically unsaturated polyol with at least one carboxylic acid functional group.

11. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the ethylenically unsaturated compound (Aiii), (Aiv) and/or (B) is obtainable by reacting a biobased fatty acid or fatty acid dimer with a polyol and a (meth) acrylic acid.

12. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the ethylenically unsaturated compound (Aiii) has a hydroxyl number of between 20 and 500 mgKOH/g, such as between 40-200 mg KOH/g.

13. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the ethylenically unsaturated compound (Aiv) has a hydroxyl number of between 20 and 800 mgKOH/g, such as between 40-200 mg KOH/g.

14. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the polyisocyanate (Ai) has a biocarbon content of more than 20% by weight, and/or wherein the polyisocyanate (Ai) is based on or derived from pentane diisocyanate.

15. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the polyisocyanate (Ai) is added in amount to provide a stoichiometric ratio of isocyanate functional groups in view of groups that are reactable with an isocyanate as present in compound (Aii), (Aiii), (Aiv) and if present (Av) and/or (Avi), from about 0.8:1 to 1.2:1, preferably from about 0.9:1 to 1.1:1, most preferably 1:1.

16. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the hydrophilic compound (Aii) has a biocarbon content of more than 20% by weight and/or is a hydroxyl-carboxylic acid compound represented by the general formula (HO)xR(COOH)y, wherein R represents a straight or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residue having 1 to 36 carbon atoms, and x and y independently are integers from 1 to 3.

17. The aqueous bio-based energy-curable polyurethane composition according to claim 16, wherein the hydrophilic compound (Aii) is selected from the group consisting of dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolhexanoic acid, glycolic acid, lactic acid, malic acid, tartaric acid or citric acid.

18. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the hydrophilic compound (Aii) is a nonionic component selected from the group consisting of a mono or poly-hydroxylated polyethyleneoxide polymer or a mono- or poly-hydroxylated polyethyleneoxide-co-polypropyleneoxide polymer.

19. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein compound (Av) is a biobased polyol selected from the group consisting of an aliphatic, cycloaliphatic or aromatic diol or polyol, a sugar, a sugar alcohol, a fatty alcohol or a fatty alcohol dimer, a polycarbonate polyol, a polyester polyol, a polyether polyol, a polyacrylate polyol or mixtures thereof.

20. The aqueous bio-based energy-curable polyurethane composition according to claim 1, wherein the mono or polyamine compound (Avi) is an aliphatic, cycloaliphatic or aromatic monoamine, diamine or polyamine.

21. A process for making an aqueous bio-based energy-curable polyurethane composition according to claim 1, comprising the steps of (a) formation of an unsaturated polyurethane from compounds (Ai), (Aii), (Aiii), (Aiv) and optionally (Av) and/or (Avi), optionally in the presence of (B), optionally in the presence of a solvent; (b) optionally, the neutralization of the composition formed in step (a); (c) dispersing the composition formed in step (a) or (b) in water to form a dispersed unsaturated polyurethane; (d) optionally, chain extending the dispersed unsaturated polyurethane containing residual isocyanate groups by reacting with compound (Avi); and (e) optionally, stripping the process solvent under vacuum.

22. A coating, ink or overprint varnish prepared from a composition according to claim 1, optionally further comprising additives such as photo-initiators, thermal crosslinkers, wetting agents, rheology modifiers, defoamers, waxes, co-solvents, colorants, pigments or inorganic fillers as well as any other polymer dispersions or emulsions different from the invention.

23. A method for coating a surface with the composition according to claim 1, comprising the steps of: applying said composition to the surface, thermally drying the applied composition energy curing the dried composition using either low energy ultraviolet light (LED) or high-energy ultraviolet light, including excimer light, in the presence of a photo-initiator and/or exposure to high-energy electron beam.

24. Use of the aqueous bio-based energy-curable polyurethane composition according to claim 1, for digital printing.

25. Use of the aqueous bio-based energy-curable polyurethane composition according to claim 1, for 3D printing technology.

Description

EXAMPLES

[0187] Raw Materials

[0188] IPDI=Desnnodur® I, isophorone diisocyanate from Covestro. Product is used as a reactant.

[0189] HDI=Desnnodur® H, hexane diisocyanate from Covestro. Product is used as a reactant.

[0190] N7300=Desnnodur® ECO N7300, biobased pentane diisocyanate trimer from Covestro. Product is used as a reactant.

[0191] MOD1071=biobased acrylated polyester diol with IOH ˜80 mg KOH/g which is obtained by the reaction of an epoxidized soybean oil having an oxirane oxygen content of ˜7% with acrylic acid and succinic anhydride. Product is used as a reactant.

[0192] MOD1010=biobased acrylated polyether diol with IOH ˜231 mg KOH/g which is obtained by the reaction of bisphenol A diglycidylether diacrylate with acrylic acid. Product is used as a reactant.

[0193] MOD450=biobased acrylated polyester alcohol with IOH ˜60 mg KOH/g which is obtained by the reaction of a fatty acid dinner having AV ˜193 mgKOH/g with pentaerythritol and acrylic acid. Product is used as a reactant.

[0194] MOD706=biobased acrylated polyester alcohol with IOH ˜165 mg KOH/g which is obtained by the reaction of glycerol propoxylate having IOH ˜631 mgKOH/g with acrylic acid. Product is used as a reactant.

[0195] MOD767=biobased acrylated polyester alcohol with IOH ˜117 mg KOH/g which is obtained by the reaction of hydroxyethyl acrylate with lactide. Product is used as a reactant.

[0196] AE532=biobased methacrylated ether alcohol with IOH ˜163 mg KOH/g which is obtained by the reaction of glycidyl methacrylate with lauric acid. Product is used as a reactant.

[0197] NX7202=Cardolite® GX7202 from Cardolite. Biobased cardanol-derived acrylated nono-alcohol with IOH ˜145 mg KOH/g. Product is used as a reactant.

[0198] NX7216=Cardolite® NX7202 from Cardolite. Biobased cardanol-derived acrylated diol with IOH ˜125 mg KOH/g. Product is used as a reactant.

[0199] NX9201=Cardolite® NX9201 from Cardolite. Biobased cardanol-derived polyether diol with IOH ˜72 mg KOH/g. Product is used as a reactant.

[0200] DMPA=dimethylolpropionic acid from Perstorp. Product is used as a reactant.

[0201] BUTOH=biobased butanol from Green Biologics. Product is used as a reactant.

[0202] N120=Ymer® N120, polyethyleneglycol diol with IOH=120 mg KOH/g from Perstorp. Product is used as a reactant.

[0203] PDA=1,2 propylene diamine from Lanxess. Product is used as a reactant.

[0204] BHT=butylate hydroxyl toluene from Merisol. Product used as a radical inhibitor.

[0205] BIND=Valikat® Bi 2010, bismuth neodecanoate from Umicore. Product is used as a catalyst.

[0206] TEA=triethylamine from Arkema. Product is used as a neutralizer.

[0207] NaOH 30%=sodium hydroxide as a 30% solution in water from Brenntag. Product is used as a neutralizer.

[0208] SR4485=Acticide® SR4485, water-based biocide composition from Thor. Product is used as a biocide.

[0209] ACE=acetone available from Brenntag. Product is used as a process solvent.

[0210] H2O=demineralized water.

Example 1 LVL341

[0211] Charge reactor with 184.7 g of ACE; 219.1 g of MOD1071; 25.1 g of DMPA; 140.3 g of MOD450; 44.6 g of MOD706; 0.39 g of BHT and 0.26 g of BIND. Mix the products at ambient temperature and under an agitation of 130 rpm. Heat the reactor jacket to 70° C. and start air-sparging at a level of 2 liters/kg/hour. Add five shots of 25.0 g of IPDI, each shot being followed by 1 hour of reaction under reflux with the reactor jacket maintained at 70′C. After the last maturation step, keep the reaction at reflux until the I(NCO) is reaching a plateau at ˜0.30 meq/g. Cool down the reaction mixture to 50′C and stop air-sparging. Add 19.0 g of TEA to the reactor and increase stirring at 200 rpm for 15 minutes. Charge a separate dispersion vessel with 1029.0 g of H2O at ambient temperature and mix with a stirrer at a speed of 400 rpm. Transfer the pre-polymer solution in acetone at 50′C into the dispersion vessel during a period of 15 minutes to make the polymer dispersion. Decrease the agitation to 150 rpm while heating the reactor jacket to 60° C. Increase progressively the vacuum to 100 mbar with the aid of a vacuum pump while preventing excessive foam formation. Continue the solvent stripping for about 5 hours until the ACE level is measured below 0.1%. Cool the reactor below 30° C. Add 1.6 g of SR4485 together with some additional H2O to adjust the solid content at a target of ˜35% solid material. When completely homogenous, drum-off the reactor over a 100 micron sieve. The isocyanate content I(NCO) in the prepolymer reaction mixture was measured using a dibutylamine back-titration method and is expressed in meq/g. The following examples were prepared according to the adapted process of Example 1 and their detailed weight composition refer to the table 2.

Example 2 LVL342B

[0212] Modification of Example 1 using neutralization with NaOH 30%.

Example 3 LVL354

[0213] Modification of Example 1 where MOD706 is replaced by NX7202.

Example 4 LVL366

[0214] Modification of Example 1 where MOD706 is replaced by MOD767.

Example 5 LVL377

[0215] Modification of Example 1 where MOD706 is replaced by AE532.

Example 6 LVL360

[0216] Modification of Example 1 where DMPA is partly replaced by N120.

Example 7 LVL368

[0217] Modification of Example 1 where MOD1071 is replaced by NX7216.

Example 8 LVL369

[0218] Modification of Example 1 where IPDI is partly replaced by N7300 and BUTOH; chain extension from the reaction of residual isocyanates with PDA added to the fresh dispersion.

Example R1 BAYHYDROL® ECO UV 2877

[0219] BAYHYDROL® ECO UV 2877 as biobased market reference from Covestro with 35% bio-carbon.

Example R2 UCECOAT® 7788

[0220] UCECOAT® 7788 as biobased market reference from allnex with ˜1% bio-carbon. This product is taken as an internal benchmark for an entry-performance in clear coat applications.

Example R3 UCECOAT® 7733

[0221] UCECOAT® 7733 as biobased market reference from allnex with ˜5% bio-carbon. This product is taken as an internal benchmark for high-end performance in clear coat or pigmented applications.

Example R4 UCECOAT® 7999

[0222] UCECOAT® 7999 as biobased market reference from allnex with ˜22% bio-carbon. This resin is made based on Aiv type of compound comprising more than 40% Bisphenol A. This product targets a high-end performance level with a significant amount of bio-carbon inside and a strong sustainability positioning.

Example R5 LVL252

[0223] Modification of Example 1 where MOD1070 is replaced by MOD1010 and IPDI is partly replaced by N7300 and BUTOH. This resin is made based on compounds comprising BPA.

Example R6 LVL272

[0224] Modification of Example 1 where MOD1070 is replaced by NX9201.

Example R7 LVL277

[0225] Modification of Example 1 where MOD1070 is replaced by NX9201 and IPDI is partly replaced by N7300 and BUTOH.

Example R8 LVL298

[0226] Modification of Example 1 where MOD1070 is replaced by NX9201; MOD706 is replaced by NX7202; IPDI is partly replaced by HDI; TEA is replaced by NaOH 30%.

[0227] Test Protocols for Liquid Dispersions

[0228] Solid Content:

[0229] The solids content of the aqueous polymer composition was measured by gravimetry after drying 1 g the dispersion during 2 h at 120′C. It is expressed in %.

[0230] Viscosity:

[0231] The viscosity of the aqueous polymer composition was measured at 25° C. with a cone and plate viscosimeter ref. Anton Paar MCR 92. It is expressed in mPa.Math.s.

[0232] pH:

[0233] The pH of the aqueous polymer composition was measured according to DIN EN ISO 10390.

[0234] Average Particle Size:

[0235] The average particle size of the aqueous polymer composition was measured by Dynamic Light Scattering equipment ref. Malvern Particle Analyzer Processor type 7027/4600SM. It is expressed in nm.

[0236] Minimum Film Formation Temperature:

[0237] The minimum film formation temperature (MFFT) of the aqueous polymer composition was measured by applying a thin wet coating on a automatic gradient-heated metal plate ref. Rhopoint MFFT 90 covering the desired temperature range. It is expressed in ° C. A low value (<10° C.) is desirable so that no coalescing agent (increasing VOC) is required to make a good homogenous film.

[0238] Test Protocols for Dry Coatings

[0239] The aqueous resins described as examples of the invention were formulated with 1.5% of Omnirad®500 (photo-initiator) and 2% of Additol® VXW 6360 pre-diluted at 50% in water (thickener) before application. In the case of BAYHYDROL® ECO UV 2877, an additional quantity of 10% butyl cellosolve or 1,2-propanediol (co-solvent) and 0.5% BYK® 028 (wetting agent) was required in order to get a coating with suitable film formation and quality.

[0240] Unsaturation Level

[0241] The amount of unsaturations in calculated from the bill of materials and refers to the amount of acrylic acid or glycidyl methacrylate present in the polymer. It is expressed in meq/g of the polymer composition.

[0242] In the case of Example R1, this information is not available and a titration was used. The titration protocol typically involves the reaction of the activated double bond with morpholine using an aza-Michael addition and followed by the reaction of the excess of morpholine with acetic anhydride (with formation of the amide derivative and acetic acid) and the dual titration of the acetic acid with sodium hydroxide and the tertiary amine with hydrochloric acid.

[0243] Tack Before Cure

[0244] The product is applied as a 50μ wet layer on Leneta® sheet and dried for 5 min at 50° C. After cooling and stabilization at 23° C., the residual tack of the coating is measured by pressing the finger on the coating and assessing the ease to separate the finger without adherence; it is expressed in a scale from 1-5 (5=no tack).

[0245] Gloss 60°

[0246] The gloss of the coating is assessed after application with a Meyer bar of a 50μ wet layer on white Leneta sheet followed by drying during 5 min at 50° C. and UV curing at 80 W/cm Hg lamp with 5 m/min conveyer speed. It is measured with a BYK Gardner Micro TRI-gloss gloss-meter in accordance with DIN-67530 standard with a light incidence of 60°. A high gloss value is desirable to provide good aesthetics of the coated substrates.

[0247] Yellowing

[0248] The yellowing of the coating is assessed after application with a Meyer bar of a 50μ wet layer on white Leneta sheet followed by drying during 5 min at 50° C. and UV curing at 80 W/cm Hg lamp with 5 m/min conveyer speed. The yellowing (b value) is measured using a colorimeter before curing and one hour after curing. The difference in coloration (delta b) is reported. A low yellowing value protects the good aesthetics of the coated substrates.

[0249] Stain Resistance

[0250] The stain resistance of the coating is assessed after application with a Meyer bar of a 50μ wet layer on white Leneta sheet followed by drying during 5 min at 50° C. and UV curing at 80 W/cm Hg lamp with 5 m/min conveyer speed. Stains are applied using a black alcohol marker ref. N70 as well as glass microfiber filter pieces saturated with a test substance placed in contact of the coating during 16 hours. The test substances used are mustard, coffee, eosine, isobetadine, 10% ammonia and 50% ethanol. The stains are washed with a couple of rubs using a tissue saturated with water or isopropanol. The remaining stains are assessed visually using a 1-5 scale, 5=no residual stain. A high stain resistance is expected to provide the best coating protection against any household product spillage.

[0251] Solvent Resistance

[0252] The solvent resistance of the coating is assessed after application with a Meyer bar of a 50μ wet layer on white Leneta sheet followed by drying during 5 min at 50° C. and UV curing at 80 W/cm Hg lamp with 5 m/min conveyer speed. It is evaluated with acetone double rubs using a cotton rag saturated with the solvent until the coating is being removed. One double rub is equal to a forward and backward stroke. The reported value is the number of double rubs required to break through the cured coating composition. A high solvent resistance is expected to provide the best coating protection against any household product spillage.

[0253] Persoz Hardness

[0254] The method measures the surface hardness of a wet coating of 120μ applied on glass plate. The coating is dried for 20 minute at 40° C. and finally cured under an UV-Hg lamp of 80 W/cm at 5 m/min. The coated samples are stabilized during 24 hours in a conditioned room (20′C and 50% humidity) and the Persoz pendulum hardness is determined at 3 different places on the surface. The mean value is calculated and expressed in seconds. A high Persoz hardness is expected to provide the best coating protection against any storehouse or household deterioration.

[0255] Nail Scratch Resistance

[0256] The nail scratch resistance of the coating is assessed after application with a Meyer bar of a 120μ wet layer on sanded white melamine board and followed by water evaporation for 20′ at 40° C. followed by UV curing using a 80 W/cm Hg lamp at a conveyer speed of 5 m/min. The test is performed after 24 hours in a conditioned room (20° C. at 50% humidity) by pressing firmly the nail with a linear movement on the coating and assessing the visual mark or damage resulting from an adhesion loss using a 1-5 scale, 5=no visible mark or damage. A high nail scratch resistance is expected to provide the best coating protection against any storehouse or household deterioration.

[0257] Pencil Hardness

[0258] The pencil hardness of the coating is assessed after application with a Meyer bar of a 120μ wet layer on sanded white melamine board and followed by water evaporation for 20′ at 40° C. followed by UV curing using a 80 W/cm Hg lamp at a conveyer speed of 5 m/min. The test is performed after 24 hours in a conditioned room (20° C. at 50% humidity) by scratching the cured coating with sharp pencils of increasing hardness using a dedicated metallic holder that fixes the right angle and the uniform pressure applied. The test result is reported as the pencil hardness above which the coating is clearly being damaged. The pencil hardness scale goes from soft to hard as 9B-8B-7B-6B-5B-4B-3B-2B-1B-HB-F-1H-2H-3H-4H-5H-6H-7H-8H-9H. A high coating hardness is expected to provide the best coating protection against any storehouse or household deterioration.

[0259] Biogenic Carbon Content and Material Carbon Footprint Reduction:

[0260] The biogenic carbon content (%) was determined using ASTM D6866 standard. The sample was dried and transformed catalytically at elevated temperature into graphite, providing the total carbon content of the sample (%). The C14/C12 isotope ratio of the graphite was measured using accelerated mass spectroscopy and then transposed into biogenic carbon content (%) using a standard of modern oxalic acid as a reference.

[0261] The biogenic carbon content is then further transposed into material carbon footprint reduction (g CO2/kg) corresponding to the equivalent savings of CO2 released in the atmosphere and assuming the neutrality proposition from equivalent atmospheric CO2 uptake during plant photosynthesis. Material carbon footprint reduction is used as a quantified sustainability performance of the biopolymer; a high value indicates a stronger sustainability impact.

[0262] Results

[0263] Table 1 shows for each of the examples whether the compounds used to make the aqueous bio-based energy-curable polyurethane comprises biocarbon content.

TABLE-US-00001 TABLE 1 POLYMER ARCHITECTURES Ai Aii Aiii Aiv Av Avi B R2 O O BIO O O / BIO R3 O O BIO O / / BIO R4 O O BIO O / / BIO R5 BIO O BIO O / / BIO R6 O O BIO / BIO / BIO R7 BIO O BIO / BIO / BIO R8 O O BIO O BIO / BIO 1 O O BIO BIO / / BIO 2 O O BIO BIO / / BIO 3 O O BIO BIO / / BIO 4 O O BIO BIO / / BIO 5 O O BIO BIO / / BIO 6 O O BIO BIO / / BIO 7 O O BIO BIO / / BIO 8 BIO O BIO BIO / BIO BIO / = not present O = present but not from biobased raw materials according to claim 1 BIO = present from biobased raw materials according to claim 1

[0264] Table 2 a and b describe for each example and reference example (except for those that are commercially available) the amount of each compound used.

TABLE-US-00002 TABLE 2a-b DETAILED COMPOSITIONS Corresponding R5 R6 R7 R8 EXAMPLE: compound LVL252 LVL272 LVL277 LVL298 ACE solvent 328.0 190.6 182.4 195.6 MOD1010 Aiv 76.2 — — 197.9 NX9201 Av — 218.4 149.8 158.5 DMPA Aii 23.50 25.12 24.5 31.6 MOD450 Aiii 156.9 170.2 134.6 — MOD706 Aiii 38.1 41.7 32.6 — NX7202 Aiii — — — 54.4 IPDI Ai 77.7 116.6 66.4 97.0 HDI Ai — — — 47.7 N7300 Ai 136.5 — 117.2 — BUTOH Av 25.9 — 22.2 — BHT Inhibitor 0.45 0.40 0.77 0.37 BIND Catalyst 0.35 0.32 0.30 1.05 TEA Neutralizer 17.69 18.95 18.52 — NaOH 30% Neutralizer — — — 30.5 PDA Avi 4.62 3.38 3.52 — SR4485 Biocide 1.60 1.70 1.63 3.00 H2O 996 1080 1031 1159

TABLE-US-00003 1 Corresponding IRR 2 3 4 5 6 7 8 EXAMPLE: compound 1070 LVL342 LVL354 LVL366 LVL377 LVL360 LVL368 LVL369 ACE solvent 184.7 119.7 176 165.2 172.5 154.0 141.0 150.7 IRR1071 Aiv 219.1 142.0 204.5 189.0 204.5 171.8 — 121.7 NX7216 Aiv — — — — — — 114.1 — DMPA Aii 25.10 16.30 23.47 21.80 23.47 21.58 19.72 20.12 N120 Aii — — — — — 14.80 — — MOD450 Aiii 140.3 90.9 130.9 121.6 130.9 121.6 130.9 93.5 MOD706 Aiii 44.6 28.9 — — — 38.7 41.7 38.3 NX7202 Aiii — — 52.5 — — — — — MOD767 Aiii — — — 54.1 — — — — AE532 Aiii — — — — 41.9 — — — IPDI Ai 124.9 80.9 116.6 108.2 116.6 108.2 116.5 62.4 N7300 Ai — — — — — — — 97.5 BUTOH Av — — — — — — — 18.5 BHT Inhibitor 0.39 0.25 0.37 0.33 0.34 0.31 0.28 0.30 BiND Catalyst 0.26 0.09 0.13 0.13 0.14 0.12 0.11 0.12 TEA Neutralizer 19.00 — 17.71 16.44 17.71 16.28 14.87 15.18 NaOH 30% Neutralizer — 16.20 — — — — — — PDA Avi — — — — — — — 5.20 SR4485 Biocide 1.60 1.04 1.53 1.43 1.50 1.34 1.83 1.96 H20 1029 667 980 920 961 858 785 840

[0265] Table 3 a and b show the product characteristics of each example. It is clear that the biobased polyurethane R1 has a high MFFT which is imposing the usage of coalescing agents in order to obtain an acceptable coating quality during application.

TABLE-US-00004 TABLE 3a-b PRODUCT CHARACTERISTICS EXAMPLE: R1 R2 R3 R4 R5 R6 R7 R8 Solid content (%) 39.6 40.0 38.5 33.9 34.3 34.4 34.3 34.7 Viscosity 81 250 50 63 151 338 1150 168 (mPa .Math. s) pH 7.6 7.4 7.5 8.0 7.4 7.5 7.6 7.4 Mean particle 156 75 90 78 83 58 47 66 size (nm) MFFT (° C.) 42 ~0 ~0 ~0 ~0 ~0 ~0 ~0 Unsaturations 0.24 1.40 3.10 3.59 2.80 2.24 1.84 2.88 (meq/g polymer) EXAMPLE: 1 2 3 4 5 6 7 8 Solid content (%) 35.0 35.9 35.2 34.9 34.8 35.4 34.5 34.8 Viscosity 23 153 24 17 18 66 38 47 (mPa .Math. s) pH 7.3 7.2 7.4 6.7 7.2 7.1 7.6 7.5 Mean particle 84 157 99 74 90 68 68 71 size (nm) MFFT (° C.) ~0 ~0 ~0 ~0 ~0 ~0 ~0 ~0 Unsaturations 3.02 3.02 2.86 2.80 2.92 2.94 3.26 2.38 (meq/g polymer)

[0266] Table 4a and b show the coating characteristics and the performances of the examples and the reference examples. It is clear from the table that the coating made with aqueous biobased polyurethane according to invention provides good to excellent coating performances. Especially results on the nail scratch resistance, and acetone double rubs are surprisingly good.

TABLE-US-00005 TABLE 4a-b COATING CHARACTERISTICS AND PERFORMANCE EXAMPLE: R1 R2 R3 R4 R5 R6 R7 R8 REFERENCE BA 2877 UC 7788 UC 7733 UC 7999 LVL252 LVL272 LVL277 LVL298 Biogenic carbon 35 1 2 22 34 44 49 41 content (%) Carbon footprint / 25 50 545 850 1100 1225 1025 reduction (g CO2/kg) Tack before 5.0 3.0 4.0 5.0 2.5 2.0 1.5 2.5 cure (1-5) Gloss 60° 92 93 93 93 93 90 94 94 Yellowing 0.2 0.5 0.5 0.5 0.8 2.0 0.4 0.9 (delta b) Stain 3.0 3.1 4.8 4.5 3.9 3.1 3.0 3.4 resistance (1-5) Acetone double ~90 >100 >100 >100 >100 ~60 ~30 ~100 rubs Persoz 211 247 325 330 280 122 103 92 hardness (s) Nail scratch 3 5 5 5 2 3 1 1 resistance (1-5) Pencil hardness HB HB/F 4H 2H 4H HB 2B 2B EXAMPLE: 1 2 3 4 5 6 7 8 REFERENCE IRR 1070 LVL342 LVL354 LVL366 LVL377 LVL360 LVL368 LVL369 Biogenic carbon 46 46 48 47 46 44 33 48 content (%) Carbon footprint 1150 1150 1200 1175 1150 1100 825 1200 reduction (g CO2/kg) Tack before 4.0 4.0 2.5 4.0 4.5 3.9 2.0 4.0 cure (1-5) Gloss 60° 91 88 92 90 91 91 97 92 Yellowing 0.6 0.6 0.6 0.5 0.6 0.4 0.9 0.5 (delta b) Stain 3.9 3.9 4.0 3.8 3.8 3.7 4.5 3.4 resistance (1-5) Acetone double >100 >100 >100 >100 >100 >100 >100 100 rubs Persoz 218 145 112 220 255 147 273 187 hardness (s) Nail scratch 5 5 5 5 5 5 5 5 resistance (1-5) Pencil harness 1H 4H 2H 1H 2H 2H 6H 1H