Aqueous bio-based likelyhood cured polyurethane composition

Abstract

The present invention relates to an aqueous, bio-based, photocalcifiable polyurethane composition comprising at least one ethylenically unsaturated polyurethane prepolymer (A) obtained from the reaction of at least one aliphatic, cycloaliphatic or aromatic polyisocyanate compound (Ai); at least one hydrophilizing compound (Aii) containing at least one reactive group capable of reacting with isocyanate and capable of dispersing the polyurethane prepolymer in an aqueous medium either directly or after reaction with an organic or inorganic neutralizing agent to provide a salt thereof; at least one ethylenically unsaturated compound (Aiii) containing essentially one reactive group capable of reacting with isocyanate; at least one ethylenically unsaturated compound (Aiv) containing at least two reactive groups capable of reacting with isocyanate.

Description

[0001] This invention relates to water-based bio-based polyurethane compositions that may cure in quantities, coatings, inks or overprinting varnishes containing such compositions, and methods of coating surfaces with such compositions.

[0002] In recent years, with the development of novel mass-curable polyurethane dispersions (often referred to as UV-PUDs), water-based mass-curable polymers have gradually disappeared. These products reintegrate the substantial benefits of their parent technologies in a single basket, raising coating sustainability to the next level of requirements. Due to their water-based nature and low volatile organic compound (VOC) levels, they comply with environmental regulations. They have low minimum film-forming temperatures (MFFTs) and do not require the use of additional coalescing solvents that would lead to increased atmospheric emissions.

[0003] Most UV-PUDs on the market are still based on raw materials from fossil resources. To obtain more environmentally friendly compounds, petrochemical resources are being replaced by natural raw materials. Bio-based compounds, or compounds based on raw materials from renewable sources, are materials that contain biomass and can be continuously replenished through short- to medium-term regeneration. Biomass is biologically derived material, excluding material buried in geological strata and / or fossilized; it is often related to plants.

[0004] In addition to their strong contribution to the cycle, the use of biopolymers provides a significant reduction in the material's carbon footprint, which can be expressed as g CO2 / kg of polymer. A major concern is the massive increase in atmospheric greenhouse gases (particularly from carbon dioxide from human-induced transformation of fossil resources, which takes approximately one million years to re-enter the soil). The use of renewable carbon addresses the cycle imbalance using a neutral carbon footprint proposal, taking into account that the amount of CO2 released into the atmosphere comes from the same amount fixed by plants during their photosynthesis.

[0005] Some UV PUDs with bio-based raw materials are already available on the market. However, there is a desire for UV PUDs with very high bio-derived carbon content that impart strong sustainability and provide good coating performance with high durability and improved continuous impact resistance.

[0006] Furthermore, it is hoped that safer raw materials can be used to achieve more sustainable UV-PUD by, for example, avoiding the use of tin catalysts, bisphenol A, or alkoxylated alkylphenol emulsifiers.

[0007] Therefore, the object of this invention is to obtain a bio-based UV-PUD to solve some or all of the problems mentioned herein.

[0008] The applicant has now surprisingly discovered a water-based, quantity-curable polyurethane with a high bio-derived carbon content, capable of providing coatings with high performance, such as resistance to nail scratches and solvents, while maintaining low MFFT and low VOC.

[0009] Therefore, the first aspect of the present invention relates to an aqueous bio-based potentially curable polyurethane composition comprising:

[0010] At least one olefinically unsaturated polyurethane prepolymer (A) obtained by the reaction of the following substances:

[0011] ● At least one aliphatic, alicyclic, or aromatic polyisocyanate compound (Ai),

[0012] ● At least one hydrophilic compound (Aii) containing at least one reactive group capable of reacting with isocyanate and capable of dispersing polyurethane prepolymer in an aqueous medium directly or after reacting with an organic or inorganic neutralizing agent to provide its salt.

[0013] ● At least one olefinic unsaturated compound (Aiii) containing essentially a reactive group capable of reacting with isocyanates.

[0014] ● At least one olefinically unsaturated compound (Aiv) containing at least two reactive groups capable of reacting with isocyanates.

[0015] Optionally, at least one olefinic unsaturated compound (B), different from (Aiii) and (Aiv), does not contain a reactive group capable of reacting with isocyanate.

[0016] The olefinic unsaturated compounds (Aiii), (Aiv) and (B) have a biocarbon content of more than 20 wt% of the total carbon content, and are obtained by reacting the olefinic unsaturated compounds with compounds derived from bio-based sources, wherein the biocarbon content is determined using ASTM D6866 standard.

[0017] The olefinic unsaturated compound (Aiv) is prepared using 0-40 wt% bisphenol A, preferably without bisphenol A, based on the weight of the compound (Aiv); and

[0018] The composition comprises polymerizable olefinic unsaturated groups in a total amount of at least 0.5 meq / g based on the total weight of the polyurethane composition, preferably at least 1 meq / g, more preferably at least 2 meq / g, most preferably at least 3 meq / g, and most preferably at least 4 meq / g.

[0019] A second aspect of the present invention relates to a method for preparing the aqueous bio-based potentially curable polyurethane composition, comprising the following steps:

[0020] (a) An unsaturated polyurethane is formed from compounds (Ai), (Aii), (Aiii), (Aiv) and optionally (Av) and (Avi) in the presence of compound (B) and optionally in the presence of a solvent;

[0021] (b) Optionally, neutralize the unsaturated polyurethane;

[0022] (c) Disperse the composition formed in step (a) or (b) in water to form a dispersed unsaturated polyurethane;

[0023] (d) Optionally, chain extension of a dispersed unsaturated polyurethane containing residual isocyanate groups by reaction with compound (Avi); and

[0024] (e) Optionally, the process solvent is stripped under vacuum.

[0025] In another aspect, the present invention relates to a coating, ink or overprinting varnish prepared from the water-based bio-based polyurethane composition that may be cured in a certain amount.

[0026] In another aspect, the present invention relates to a method for coating or printing a surface with a water-based bio-based quantitatively curable polyurethane composition, comprising the following steps:

[0027] • Apply the composition to the surface,

[0028] • The composition applied by heat drying,

[0029] • Use low-energy ultraviolet light (LED) or high-energy ultraviolet light, including excimer light, in the presence of a photoinitiator and / or exposure to a high-energy electron beam to energy-cur the dried composition.

[0030] The terms “bio-based compound” or “compound derived from biological sources” or “compound having carbon content derived from natural or renewable resources” or “compound having carbon content derived from biological sources” or “compound having bio-carbon content” used in this article are used interchangeably and all refer to compounds derived from or made from natural renewable resources such as biomass or plant-based sources.

[0031] The presence of 14C carbon atoms can be used to detect the use of bio-based compounds. Carbon is obtained as a mixture of three isotopes (12C, 13C, and 14C). Compared to renewable raw materials that introduce carbon from atmospheric carbon dioxide through photosynthesis, fossil raw materials contain a negligible percentage of the 14C isotope due to their relatively short radioactive decay (half-life of 5,730 years). Due to cosmic rays in the upper atmosphere, this new carbon delivers a higher and more defined percentage of the 14C isotope at a given time. Based on the total carbon content, the amount of 14C relative to 12C indicates the percentage of biologically derived carbon in a sample, ranging from zero to 100%.

[0032] Currently, at least two different techniques exist for determining the 14C content of samples: (i) by liquid scintillation counting or (ii) by mass spectrometry, in which the sample is converted in CO2 and then reduced to graphite for analysis in a mass spectrometer to separate 14C atoms from 12C atoms and determine their ratio. All these methods for determining the 14C content of substances are clearly described in American Standards ASTM D 6866 or ASTM D 7026 and European Standards EN 16785 or EN 16640.

[0033] The value of the bio-based carbon content of this invention was determined using the accelerated mass spectrometry procedure described in standard ASTM D 6866.

[0034] According to the present invention, when it is mentioned that a compound has, for example, at least 20 wt% bio-carbon, it means that, based on the total carbon content, 20 wt% of the carbon comes from a bio-based source.

[0035] Within the framework of this invention, the aqueous bio-based quantitatively curable polyurethane composition may also be biodegradable and / or compostable and / or biocompatible.

[0036] Biodegradability is the ability of a material, either on its own or after energy solidification, to break down into smaller molecules, such as water, carbon dioxide, methane, and biomass, as a result of its interaction with naturally occurring microorganisms (such as bacteria, algae, or fungi) in the ecological environment.

[0037] Compostability is the ability of a material, either on its own or after energy solidification, to be used as compost (i.e., assimilated into stable decomposing material for fertilization and soil conditioning during the aerobic biological process of converting organic waste).

[0038] Biocompatibility is the ability of a material, either by itself or after energy curing, to be compatible with living tissue. Biocompatible materials do not produce toxic or immunological reactions when exposed to human or animal bodies or body fluids and can be used as implants, prostheses, or any other functional substitutes in living organisms (or in part).

[0039] The biodegradability and compostability of products can be tested. For example, products bearing the "OK compos t indus trial" label from TUV AUSTRIA, according to the harmonized standard EN 13432:2000, are guaranteed to be biodegradable in industrial composting plants. Similarly, the "OK biodegradable" label can be attributed to soil, water, and marine environments based on specific testing protocols.

[0040] As used herein, "olefin unsaturated compound" refers to a compound containing a polymerizable olefin unsaturated group. A polymerizable olefin unsaturated group means a carbon-carbon double bond that, under the influence of an initiator and / or irradiation, can ultimately undergo free radical polymerization in the presence of a photoinitiator. The polymerizable olefin unsaturated group is typically selected from (meth)acrylic acid groups, preferably (meth)acrylic acid groups, and most preferably acrylic acid groups. In this invention, the term "(meth)acrylic acid" should be understood to encompass acrylic and methacrylic acid groups present individually or as a mixture thereof on the compound.

[0041] "Mainly contains" is intended to specifically specify that the sum of the weight percentages of these compounds is at least 95 wt%, preferably at least 97 wt%, more preferably at least 99 wt% up to 100 wt%.

[0042] The term "alcohol" as used in this article refers to both monohydric and polyhydric alcohols. A "monohydric alcohol" is a compound containing one hydroxyl (OH) group; a "polyhydric alcohol" is a compound containing at least two hydroxyl (OH) groups.

[0043] Aqueous bio-based compositions that may be solidified

[0044] Aqueous bio-based, potentially curable compositions comprising a polyurethane prepolymer (A) and optionally an alkenyl unsaturated compound (B) may be aqueous dispersions (i.e., solid particles in water) or aqueous emulsions (i.e., droplets in water). They may also exist simultaneously as mixtures between dispersions and emulsions.

[0045] The aqueous bio-based composition that may be quantitatively cured contains at least 0.5 meq / g of polymerizable olefinic unsaturated groups based on the total weight (g) of the composition. Preferably, the number of polymerizable olefinic unsaturated groups is at least 1 meq / g, more preferably at least 2 meq / g, even more preferably at least 3 meq / g, and most preferably at least 4 meq / g based on the total weight (g) of the composition.

[0046] The amount of olefinic unsaturated groups, by total weight, is calculated from the known composition of the polymer (bill of materials). It often refers to the amount of (meth)acrylic acid or glycidyl (meth)acrylate present in the overall polymer composition. It can also be determined by titration. It is expressed as meq of unsaturated groups per g of polymer composition.

[0047] The aqueous bio-based composition of the present invention typically has a total solids content of about 30-65 wt%, preferably about 35-50 wt%, and most preferably about 35-40 wt%.

[0048] The aqueous bio-based composition that may be quantitatively cured typically has a viscosity of 10-1,000 mPa·s, preferably 10-200 mPa·s, and most preferably 10-100 mPa·s, measured at 25°C; a pH value of 6-9, preferably 7-8; and an average particle size of about 10-1000 nm, preferably 50-150 nm, and most preferably 50-100 nm.

[0049] In one embodiment, the bio-carbon content of the aqueous bio-based potentially curable polyurethane composition is greater than 20 wt%, preferably greater than 40 wt%, more preferably greater than 50 wt%, even more preferably greater than 60 wt%, most preferably greater than 70 wt%, and most preferably greater than 80 wt%, based on the total carbon content of the polyurethane composition. At least compounds (Aiii) and (Aiv) have a bio-carbon content of at least 20 wt%. Preferably, other compounds used to prepare the polyurethane prepolymer (A) also have a bio-carbon content of at least 20 wt%. Furthermore, the optional olefinically unsaturated compound (B) has a bio-carbon content of greater than 20 wt%.

[0050] The carbon footprint of the aqueous bio-based composition of the present invention is reduced to at least 250 g CO2 / g, preferably at least 500 g CO2 / kg, more preferably at least 750 g CO2 / kg, most preferably at least 1000 g CO2 / kg, and most preferably at least 1500 g CO2 / kg.

[0051] The aqueous bio-based composition of the present invention has a low MFFT, preferably 0-20°C, more preferably 0-10°C, and most preferably 0-5°C.

[0052] The polyurethane prepolymer (A) of the present invention preferably has a weight-average molecular weight of less than 100,000 Daltons, typically less than 20,000 Daltons, and more typically less than 10,000 Daltons. Typically, the weight-average molecular weight (Mw) is at least 1,000 Daltons, often at least 2,000 Daltons, and typically at least 3,000 Daltons. The molecular weight is typically determined by gel permeation chromatography (GPC) using polystyrene standards covering the determination range. The sample is typically dissolved in tetrahydrofuran before filtration and injection into the column.

[0053] The following parameters describe implementation schemes for different compounds that can be used to prepare prepolymer A.

[0054] Polyisocyanate compounds (Ai)

[0055] A polyisocyanate compound (Ai) refers to an organic compound containing at least two isocyanate groups. Preferably, the polyisocyanate compound contains no more than three isocyanate groups. The most preferred polyisocyanate compound (Ai) is a diisocyanate.

[0056] Polyisocyanate compounds are typically selected from aliphatic, alicyclic, aromatic, and / or heterocyclic polyisocyanates or combinations thereof.

[0057] Examples of aliphatic and alicyclic polyisocyanates are 1,6-diisocyanohexane (HDI), 1,1'-methylenebis[4-isocyanocyclohexane] (H12MDI), 5-isocyano-1-isocyanomethyl-1,3,3-trimethylcyclohexane (isophorone diisocyanate, IPDI), and 1,3-diisocyanomethylcyclohexane (H6XDI). Aliphatic polyisocyanates containing more than two isocyanate groups are cyclic derivatives of the diisocyanates mentioned above, such as 1,6-diisocyanohexane biuret and isocyanurate.

[0058] Examples of aromatic polyisocyanates are 2,4-toluene diisocyanate (TDI), 1,1'-methylenebis[4-isocyanatophenyl] (MDI), m-xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 1,5-naphthalene diisocyanate (NDI), 4,4'-dibenzyl diisocyanate (DBDI), bitoluidine diisocyanate (TODI), and 1,4-phenylene diisocyanate (PPDI).

[0059] The polyisocyanate is preferably selected from aliphatic and alicyclic polyisocyanates. An example is 1,1'-methylenebis[4-isocyanocyclohexane](H12MDI).

[0060] More preferably, the polyisocyanate (Ai) is bio-based and has a bio-carbon content greater than 20 wt%. The preferred bio-based polyisocyanate (Ai) used is pentane diisocyanate or a pentane diisocyanate derivative. The pentane diisocyanate derivative may be a trimerization or oligomerization of pentane diisocyanate, such as isocyanurate, biuret, urethane, or oligomer, all of which are linear or partially end-capped.

[0061] Such examples are commercially available polyisocyanates (Ai) based on bio-based pentane diisocyanates. ECO N 7300 D-370N or D-376N. Another example of a polyisocyanate is Tolonate. TM X FLO 100.

[0062] Preferably, the polyisocyanate (Ai) is provided by a partial reaction of an alcohol compound (Aia) having an average of one hydroxyl functional group per molecule with a polyisocyanate (Aib). The alcohol compound (Aia) contains preferably more than 20 wt% bio-based content. The preferred polyisocyanate (Aib) used is a bio-based pentane diisocyanate. The most preferred polyisocyanate (Aib) is... ECO N7300 D-370N or D-376N.

[0063] Prior to reaction with (Aii), (Aiii), (Aiv), and optionally (Av) and (Avi), the alcohol compound (Aia) is preferably used to reduce the functionality of the polyisocyanate to a level of two isocyanate functional groups per molecule. Each molecule of the alcohol compound (Aia) has an average of one hydroxyl functional group and can be a primary, secondary, or tertiary alcohol. The structure of (Aia) is R-OH, wherein the R group can be aliphatic, alicyclic, or aromatic.

[0064] Preferably, the alcohol compound (Aia) is bio-based and has a renewable carbon content of greater than 20 wt%. Preferred examples of such bio-based alcohol compounds (Aia) are bio-based methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, undecanol, dodecanol, or octadecanol.

[0065] The amount of polyisocyanate compound (Ai) used in the synthesis of polyurethane prepolymer (A) is typically 10-60 wt%, preferably 20-50 wt%, and more preferably 30-40 wt% of polyurethane prepolymer (A).

[0066] Hydrophilic compounds (Aii)

[0067] The hydrophilic compound (Aii) contains at least one reactive group capable of reacting with isocyanate and capable of dispersing polyurethane prepolymer A in an aqueous medium directly or after reacting with an organic or inorganic neutralizing agent to provide its salt.

[0068] Hydrophilic compounds (Aii) are typically monools or polyols containing functional groups that can exhibit ionic or nonionic hydrophilic properties. Preferably, they are polyols containing one or more anionic salt groups (e.g., carboxylates, sulfonates, and phosphonates) or acid groups (e.g., carboxylic acids, sulfonic acids, or phosphonates) that can be converted into anionic salt groups. Preferred are hydroxycarboxylic acids represented by the general formula (HO)xR(COOH)y, where R represents a straight-chain or branched hydrocarbon residue having 1-36 carbon atoms, preferably 2-6 carbon atoms, and x and y are independently integers 1-3. Examples of these hydroxycarboxylic acids include bio-based citric acid, malic acid, glycolic acid, lactic acid, and tartaric acid. Another example is bio-based 10,16-dihydroxyhexadecanoic acid. Preferred hydroxycarboxylic acids are α,α-dihydroxymethylalkanoic acids, where x = 2 and y = 1 in the above general formula, such as 2,2-dihydroxymethylpropionic acid and 2,2-dihydroxymethylbutyric acid. Most preferred is 2,2-dihydroxymethylpropionic acid.

[0069] The hydrophilic compound (Aii) may be a nonionic component selected from hydroxylated polyethylene oxide polymers or hydroxylated polyethylene oxide-co-propylene oxide block copolymers, preferably bio-based. Examples of such hydroxylated polyethylene oxide polymers are... N120.

[0070] Preferably, based on the total carbon content of compound (Aii), the hydrophilic compound (Aii) has a biocarbon content of greater than 20 wt%.

[0071] The amount of hydrophilic compound (Aii) used in the synthesis of polyurethane prepolymer (A) is typically 1-30 wt%, preferably 2-10 wt%, and most preferably 3-6 wt%, based on the total weight of polyurethane prepolymer (A).

[0072] Bio-based alkenes (Aiii), (Aiv), and (B)

[0073] An olefinically unsaturated compound containing essentially one reactive group capable of reacting with isocyanates (Aiii) means a compound in this invention containing at least one unsaturated functional group (e.g., an acrylic or methacrylic group) and a nucleophilic functional group (preferably a hydroxyl group) capable of reacting with isocyanates. Preferred are (meth)acryloyl monohydroxy compounds, more particularly poly(meth)acryloyl monohydroxy compounds. Acrylates are particularly preferred. An allyl group is an option.

[0074] An olefinically unsaturated compound (Aiv) containing at least two reactive groups capable of reacting with an isocyanate group means a compound comprising at least one unsaturated functional group (e.g., an acrylic or methacrylic group) and at least two nucleophilic functional groups (preferably hydroxyl groups) capable of reacting with an isocyanate. Preferred are (meth)acryloyl polyhydroxy compounds, more particularly poly(meth)acryloyl polyhydroxy compounds. Acrylates are particularly preferred. An allyl group is an option.

[0075] According to the invention, the olefinic unsaturated compounds (Aiii) and (Aiv) are bio-based and each contains at least 20 wt% biocarbon content, preferably at least 25 wt%, more preferably at least 40 wt%, still more preferably at least 60 wt%, and most preferably at least 80 wt%.

[0076] The olefinic unsaturated compounds (Aiii) and (Aiv) and / or (B) can be obtained by reacting a compound containing at least one olefinic unsaturated functional group with a reactive bio-based compound to form an olefinic unsaturated compound (Aiii) having substantially one nucleophilic functional group capable of reacting with isocyanates, to form an olefinic unsaturated compound (Aiv) having at least two nucleophilic functional groups capable of reacting with isocyanates, or to form an olefinic unsaturated compound (B) without any nucleophilic functional groups capable of reacting with isocyanates. Furthermore, the compound containing at least one unsaturated functional group may be bio-based. Preferably, the reactive bio-based compound is a hydroxyl or epoxy compound.

[0077] Compounds containing at least one olefinically unsaturated functional group may be carboxylic acids or their esters or olefinically unsaturated epoxides.

[0078] The reaction is usually a direct esterification reaction. When esters of olefinically unsaturated carboxylic acids are used, the reaction is an transesterification reaction.

[0079] Preferably, the olefinic unsaturated carboxylic acid compound is selected from acrylic acid, methacrylic acid, malic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, aconitic acid, or mixtures thereof.

[0080] Preferably, the olefinic unsaturated epoxide is glycidyl (meth)acrylate.

[0081] The reactive bio-based compounds are preferably selected from organic oils or organic oil derivatives, carboxylic acid compounds, fatty acids and their derivatives, fatty acid dimers and their derivatives, and bio-based polyols and their derivatives.

[0082] Bio-based polyols can be aliphatic, alicyclic, or aromatic polyols. They include fatty alcohols, fatty alcohol dimers, carbohydrates, sugar alcohols, and their derivatives. Examples of other types of bio-based polyols are rosin polyols, (poly)farnesene polyols, (poly)alkylene glycols, and (poly)alkylene polyols. Other bio-based polyols may also be trimethylolpropane, bis(trimethylolpropane), pentaerythritol, and dipentaerythritol. Examples of (poly)alkylene glycols are diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and tetraethylene glycol.

[0083] Bio-based polyol derivatives are preferably glycolide, lactide, lactone, or poly(epoxide), such as poly(ethylene oxide) or poly(propylene oxide) derivatives. A real example is sorbitol poly(propylene oxide).

[0084] The organic oil or organic oil derivative is preferably a bio-based epoxidized oil, preferably selected from 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 nut shell oil, or their bio-based epoxidized fatty acids. Typically, the bio-based epoxidized oil is reacted with an olefinically unsaturated molecule carrying at least one carboxylic acid, such as (meth)acrylic acid.

[0085] Preferably, the organic oil derivative is a cashew nut shell extract derivative. Known examples include epoxidized cashew nut shell extract derivatives, such as... Ultralite 513 or NC514SG. Other examples of bio-based polyol derivatives are epoxidized rosin, for example... RTE. Other alternatives to these organic oil derivatives are, for example, glycidyl esters of tert-carbonate, such as... E10P, or glycerol-based bio-based epoxy-functionalized polyethers such as DY-S.

[0086] Bio-based fatty acids or fatty acid dimers are preferably bio-based aliphatic, alicyclic, or aromatic carboxylic acid compounds. Examples are monocarboxylic fatty acids such as butyric acid, hexanoic acid, octanoic acid, and decanoic acid, and polycarboxylic fatty acids such as succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, and dodecanoic acid.

[0087] Suitable bio-based carboxylic acid compounds preferably contain more than one carboxylic acid. Examples include maleic acid, fumaric acid, pentenoic acid, phthalic acid, isophthalic acid, terephthalic acid, citric acid, or trimesic acid.

[0088] Bio-based fatty acids or fatty acid dimers can be saturated fatty acids such as butyric acid, lauric acid, palmitic acid, stearic acid, monounsaturated fatty acids such as oleic acid, or polyunsaturated fatty acids such as linoleic acid.

[0089] Bio-based fatty acid dimers are obtained from the above fatty acids, especially from monounsaturated fatty acids such as oleic acid.

[0090] Special types of bio-based fatty acid derivatives or fatty acid dimer derivatives are fatty alcohols or fatty alcohol dimers, which can be obtained directly from the chemical transformation of parent fatty acids or fatty acid dimers. They can also be formed by the reaction of fatty acids or fatty acid dimers with polyols such as bio-based polyols. Preferred polyols are trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and tetraethylene glycol.

[0091] Preferably, the bio-based olefinic unsaturated compounds (Aiii), (Aiv), and (B) based on fatty acids or fatty acid derivatives are prepared by reacting fatty acids or fatty acid dimers with polyols in the presence of acrylic acid and methacrylic acid. Those skilled in the art know which stoichiometry to use to provide the desired hydroxyl functionality of compounds (Aiii) or (Aiv).

[0092] Bio-based fatty acids or fatty acid dimers can also react with olefinic unsaturated molecules carrying at least one epoxy group. An example of such a molecule is glycidyl methacrylate. For instance, lauric acid can be stoichiometrically reacted with glycidyl methacrylate or with Cardolite 513 to provide an unsaturated compound (Aiii). Alternatively, a C36 dimer of stearic acid can be stoichiometrically reacted with glycidyl methacrylate or with Cardolite 513 to provide an unsaturated compound (Aiv).

[0093] Itaconic acid can be stoichiometrically reacted with glycidyl methacrylate or with Cardolite 513 to provide an unsaturated compound (Aiv).

[0094] Citric acid can be partially or completely reacted with glycidyl methacrylate or with Cardolite 513 to provide an unsaturated compound (Aiv); if one or more residual carboxylic acids are present on the molecule, it is also an instance of a compound (Aii).

[0095] Alternatively, 10,16-dihydroxyhexadecanoic acid can be reacted partially or completely with glycidyl methacrylate or with Cardolite 513 to provide an unsaturated compound (Aiv); if one or more residual carboxylic acids are present on the molecule, that is also an example of a compound (Aii).

[0096] Bio-based sugar alcohols or their derivatives can be ethylene glycol, glycerol, diglycerol, triglyceride, erythritol, arabinitol, sorbitol, and their glycolide, lactide, lactone, and poly(epoxide) derivatives. Other examples of bio-based sugar alcohol derivatives are isosorbide, isomannitol, and iso-idylol.

[0097] Carbohydrates (or sugars) can be polyhydroxy biobased compounds, including sugars, starches, and cellulose. Sugars can be classified into four chemical groups: monosaccharides, disaccharides, oligosaccharides, and polysaccharides. Monosaccharides and disaccharides with low molecular weights are referred to as sugars and are preferred within the framework of this invention. Examples of monosaccharides include glucose, galactose, fructose, and xylose. Examples of disaccharides include sucrose, lactose, maltose, isomaltulose, and trehalose. Examples of oligosaccharides include maltodextrin, raffinose, and stachyose. Examples of polysaccharides include glycogen, cellulose, hemicellulose, pectin, amylose, amylopectin, and starch, as well as their derivatives, including the biotransformation of these products in a bioreactor in the presence of enzymes.

[0098] The olefinic unsaturated compound (Aiii) has a certain amount of reactive groups capable of reacting with isocyanates, also known as nucleophilic functional groups, or a functionality of essentially 1. The nucleophilic functional group is preferably a hydroxyl group.

[0099] Examples of such compounds are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylamide, isosorbide mono(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropionic acid di(meth)acrylate, bis(trimethylolpropionic acid di(meth)acrylate, glyceryl di(meth)acrylate (poly)propoxylated ester, diglyceryl tri(meth)acrylate (poly)propoxylated ester, and sorbitol penta(meth)acrylate (poly)propoxylated ester. Another example is hydroxyethyl acrylate (poly)lactide.

[0100] The olefinic unsaturated compound (Aiv) has a certain amount of reactive groups capable of reacting with isocyanates, also known as nucleophilic functional groups, or a functionality of at least 2 per compound, preferably 2-3, and most preferably 2. The nucleophilic functional group is preferably a hydroxyl group.

[0101] Examples of such compounds are pentaerythritol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropionic acid acrylate, di(meth)acrylate bis(trimethylolpropionic acid acrylate), glyceryl propoxylate (meth)acrylate, diglyceryl propoxylate (meth)acrylate, and sorbitol propoxylate (tetra(meth)acrylate).

[0102] Compounds (Aiii), A(iv) and (B) can be obtained from lignin as a bio-based raw material precursor after the required chemical transformation and functionalization within the framework of this invention.

[0103] The desired functionality of (Aiii) and (Aiv) is obtained by controlling the method and the correct stoichiometry between the compound containing at least one olefinic unsaturated functional group and the reactive bio-based compound.

[0104] In one embodiment, the amount of the isocyanate reactive group in the olefinic unsaturated compound (Aiv) can be controlled by reacting a portion of the isocyanate reactive group with a capping compound capable of reacting with the isocyanate reactive group and optionally generating another functional group in the molecule. Such a capping compound is preferably a cyclic anhydride that generates a carboxylic acid group. Succinic anhydride and maleic anhydride are particularly preferred.

[0105] This approach allows control over the nucleophilic functionality of compounds (Aiii) or (Aiv) and also yields polyurethane polymer A with desired molecular weight and branching levels without the risk of gel formation.

[0106] In a specific implementation, the bio-based olefinic unsaturated compound (Aiii) or (Aiv) and (B) can be obtained in the following manner:

[0107] ● React natural epoxidized oils with olefinic unsaturated carboxylic acid compounds to obtain olefinic unsaturated polyols;

[0108] ● React the olefinic unsaturated polyol with a cyclic anhydride to obtain an olefinic unsaturated polyol having at least one carboxylic acid functional group.

[0109] In this embodiment, the acid anhydride is preferably a cyclic acid anhydride, and more preferably succinic anhydride or maleic anhydride.

[0110] In one embodiment, the olefinic unsaturated compound (Aiii) has 20-500 mg KOH / g, for example 40-200 mg KOH / g.

[0111] In one embodiment, the olefinic unsaturated compound (Aiv) has 20-800 mg KOH / g, for example 40-200 mg KOH / g.

[0112] Preferably, each molecule of compound (Aiii) and / or (Aiv) carries 2-5 olefinic unsaturated groups.

[0113] In one embodiment, the waterborne bio-based, quantity-curable polyurethane composition comprises at least one olefinically unsaturated compound (B) different from (Aiii) and (Aiv) that does not contain reactive groups capable of reacting with isocyanates, and this fully olefinically unsaturated compound (B) is different from (Aiii) and (Aiv). This substance is typically added to the olefinically unsaturated polyurethane prepolymer (A) to provide additional desired properties.

[0114] Alternatively, during the esterification reactions leading to compounds (Aiii) and (Aiv), the reaction mixture in equilibrium contains portions of all reactive groups capable of reacting with isocyanates that have reacted with olefinic unsaturated acids and are no longer capable of reacting with isocyanate groups. These reaction products also constitute at least one olefinic unsaturated compound (B) that differs from (Aiii) and (Aiv) and does not contain reactive groups capable of reacting with isocyanates.

[0115] In another embodiment, compound (B) may also be a bio-based urethane acrylate different from prepolymer (A). Suitable bio-based urethane acrylates can be, for example, through... ECO N 7300 and Between NX7202 or ECO N 7300 It was obtained by a fully stoichiometric reaction between NX7202 and 2-ethyl-1,3-hexanediol.

[0116] Alternatively, compound (B) itself, or as a separately prepared emulsion, can be added to an aqueous bio-based polyurethane composition that may be cured in a certain amount.

[0117] The amount of compound (Aiii) is typically 10-50 wt% of the polyurethane prepolymer (A), preferably 25-40 wt%.

[0118] The amount of compound (Aiv) is typically 10-50 wt% of the polyurethane prepolymer (A), preferably 25-40 wt%.

[0119] The amount of compound (B) is typically 0-50 wt% of the polyurethane composition, preferably 0-25%.

[0120] The olefinic unsaturated compound (Aiv) is prepared from 0-40 wt% bisphenol A, preferably 0-20 wt% bisphenol A, and most preferably without bisphenol A. Bisphenol A is a common compound used as a starting material for UV-curable (meth)acrylate compositions (usually as bisphenol A diglycidyl ether diacrylate). Its use is avoided due to health and environmental pressures related to its toxicity and ecotoxicity. Instead, safer alternatives such as acrylates based on butylene glycol diglycidyl ether, vanillin diglycidyl ether, isosorbide diglycidyl ether, hexanediol diglycidyl ether, cyclohexanediethanol diglycidyl ether, or heterocyclic epoxy compounds such as triglycidyl isocyanurate or other similar alternatives can be used.

[0121] From a polymer structure perspective, compound (Aiii) introduces terminal olefinic unsaturated groups onto prepolymer (A) and acts as a capping molecule for prepolymer (A). Compound (Aiv), having at least two hydroxyl groups, provides chain extension and / or branching with side-attached olefinic unsaturated groups. The combination of only these two types of bio-based compounds ensures a higher level of olefinic unsaturation, resulting in a high-performance coating and complementing the highest level of bio-carbon in the polymer, thus providing the highest carbon footprint reduction.

[0122] Monools or polyols (Av)

[0123] In some embodiments, the aqueous bio-based curable polyurethane composition containing polyurethane prepolymer (A) can also be obtained by the reaction of compounds (Ai), (Aii), (Aiii), (Aiv) and (Av).

[0124] The monool or polyol (Av) is different from (Ai), (Aii), (Aiii), or (Aiv) and has a biochar content of greater than 20 wt%, preferably greater than 40 wt%, even more preferably greater than 60 wt%, most preferably greater than 80 wt%, and most preferably greater than 80 wt%, and contains at least one reactive group capable of reacting with isocyanate. Preferably, a polyol containing at least two hydroxyl groups is used.

[0125] Monools (Av) can be methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, terpineol, etc.

[0126] Preferably, the compound (Av) is selected from the following polyols: aliphatic, alicyclic or aromatic diols or polyols, bio-based sugars, bio-based sugar alcohols, fatty alcohols or fatty alcohol dimers, polycarbonate polyols, polyester polyols, polyether polyols, polyacrylate polyols, or mixtures thereof.

[0127] Preferably, the bio-based sugar alcohol or its derivative is ethylene glycol, glycerol, diglycerol, erythritol, arabinitol, sorbitol, isosorbide, isomannitol, or iso-idol.

[0128] The compound (Av) can be obtained from vegetable oil or starch.

[0129] The compound (Av) may also be a (poly)ethoxylated or (poly)propoxylated monool or polyol, or a (poly)lactone or (poly)lactide derivative.

[0130] The compound (Av) can be an aliphatic or alicyclic diol or polyol such as 1,2-ethylene glycol, 1,3-propanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, heptaethylenediol, octanediol, nonanediol, decanediol, dodecanediol, or cyclohexanediol. It can also be diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, or dipentaerythritol.

[0131] The compound (Av) may be a polyester polyol, preferably with a number average molecular weight of at least 400 Daltons and more preferably not more than 4000 Daltons, and most preferably not more than 1000 Daltons. The polyester polyol may also contain residual ethylene unsaturation suitable for oxidative air drying.

[0132] Polyester polyols can be reaction products of polyols such as those described above and polycarboxylic acids, preferably dicarboxylic acids. The polycarboxylic acids used to form these polyester polyols can be aliphatic, alicyclic, aromatic, and / or heterocyclic. Particularly preferred dicarboxylic acids are succinic acid, adipic acid, tartaric acid, lactic acid, glycolic acid, fumaric acid, maleic acid, itaconic acid, citric acid, citraconic acid, mesocarboxylic acid, glutaric acid, trimellitic acid, benzotriic acid, pyromellitic acid, phthalic acid, terephthalic acid, and important fatty acid dimers. Other polycarboxylic acids can be used, including cyclic esters (such as γ-butyrolactone or ε-caprolactone), cyclic diesters (such as glycolide or lactide), or cyclic anhydrides (such as phthalic anhydride or maleic anhydride).

[0133] In specific cases involving the use of polyester polyols, polyhydroxyalkanoates (PHAs) can be used. PHAs are polyesters produced by a variety of microorganisms, including bacteria, and thus encompass a wide range of different monomers. Carbohydrates and vegetable oils are commonly used as raw materials for fermentation that leads to PHAs. These polyesters can exhibit some crystallinity and are biodegradable and compostable. They generally have good water resistance and are thermally and UV-stable. Suitable hydroxylated derivatives within the framework of this invention can be obtained, for example, through further transesterification of the polyester.

[0134] In another particular case involving the use of polyester polyols, linear or branched polylactic acid and its derivatives exhibiting residual hydroxyl groups can be used. Polylactic acid is a biopolymer that is finding increasing use in industry.

[0135] In another particular case of using polyester polyols, linear or branched polymers made from 10,16-dihydroxyhexadecanoic acid and typically derived from keratin are also considered.

[0136] Within the framework of this invention, hydroxylated derivatives of PHA and polylactic acid can also be acryliced ​​to compounds (Aiii) and / or (Aiv).

[0137] The compound (Av) may be a polycarbonate polyol, preferably having a number average molecular weight of at least 400 Daltons and not more than 4,000 Daltons, and most preferably not more than 1,000 Daltons. Examples of polycarbonate polyols are therefore reaction products of polyols with phosgene, dialkyl carbonates (e.g., dimethyl carbonate), diaryl carbonates (e.g., diphenyl carbonate), or cyclic carbonates (e.g., ethylene and / or propylene carbonate).

[0138] The compound (Av) may be a polyether polyol, preferably having a number average molecular weight of at least 400 Daltons and not more than 4000 Daltons, and most preferably not more than 1000 Daltons. Examples of polyether polyols are polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and their random or block copolymers.

[0139] The compound (Av) may also be a polyacrylate polyol, preferably having a number average molecular weight of at least 400 Daltons and not more than 4000 Daltons, and most preferably not more than 1000 Daltons. It may include, for example, those polymers prepared by (living) radical polymerization of (meth)acrylic acid monomers and / or (meth)acrylamide monomers in the presence of a hydroxylating chain transfer agent such as 2-mercaptoethanol, initiated by a hydroxylating thermal free radical initiator.

[0140] The compound (Av) can also be a polyamide polyol.

[0141] The compound (Av) can be obtained from lignin as a bio-based raw material precursor after the chemical transformation and functionalization required within the framework of this invention.

[0142] The preferred compounds (Av) are polyester polyols and polycarbonate polyols.

[0143] Monools can be selected from methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, decanol, dodecanol, etc.

[0144] The total amount of polyol (Av) in the polyurethane prepolymer (A) is usually 0-50 wt%, preferably 0-30 wt%, and most preferably 0-15 wt%.

[0145] Monoamines or polyamines (Avi)

[0146] In some embodiments, the aqueous bio-based curable polyurethane composition comprises a polyurethane prepolymer (A), which can be obtained by reacting compounds (Ai), (Aii), (Aiii), (Aiv), optionally (Av) and (Avi).

[0147] Preferably, the mono- or polyamine compound (Avi) is an aliphatic, alicyclic, or aromatic amine, a diamine, or a polyamine.

[0148] The compound (Avi) contains an active amino group capable of chain end-capping or chain extension from the residual isocyanate end groups of the prepolymer. The chain extender is suitably a water-soluble aliphatic, alicyclic, aromatic, or heterocyclic primary or secondary polyamine having up to 36, preferably up to 12 carbon atoms. It may also be hydrazine. The total amount of compound (Avi) used is typically calculated based on the amount of residual isocyanate groups present in the polyurethane prepolymer. During chain extension, the ratio of isocyanate groups in the prepolymer to amine groups in the chain extender (Avi) is typically in the range of about 1:0.9 to 1:1, preferably about 1:0.95 to 1:1, based on equivalents. This ratio is more preferably 1:1 to obtain a fully reacted polyurethane polymer without residual isocyanate groups.

[0149] The average functionality of the polyamine used for chain extension is preferably 2-4, more preferably 2-3. A preferred average functionality of the polyamine is 2. Examples of such chain extenders (Avi) available herein include hydrazine, piperazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2-methylpentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, isophoronediamine, m-xylenediamine, bis(4-aminocyclohexyl)methane, polyoxyethylene amines and polyoxypropylene amines (e.g., Jeffamines from TEXACO), and mixtures thereof.

[0150] The amine used for chain capping has a functionality of 1. Examples of such amines are methylamine, dimethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, tert-butylamine, ditert-butylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, benzylamine, and dibenzylamine.

[0151] In another embodiment of the invention, the amine (Avi) may carry additional functional groups, such as in the case of using natural amino acids like glycine, alanine, or lysine. Another example is N-(3-sulfopropyl)polypropylene glycol diamine, sodium salt (from Rashig's Poly-EPS).

[0152] Preferably, the monoamine or polyamine (Avi) is bio-based and contains at least 20 wt%, preferably at least 40 wt%, more preferably at least 60 wt%, and most preferably at least 80% biocarbon content.

[0153] An example of such a bio-based monoamine or polyamine is 1,5-pentanediamine. Another example is Priamine 1073 from Croda.

[0154] Preferably, no chain extender compound (Avi) is used.

[0155] method

[0156] Another aspect of the present invention relates to a method for preparing the aqueous bio-based potentially curable polyurethane composition of the present invention, comprising the following steps:

[0157] (a) An unsaturated polyurethane is formed from compounds (Ai), (Aii), (Aiii), (Aiv) and optionally (Av) and / or (Avi) in the presence of compound (B) and optionally in the presence of a solvent.

[0158] (b) Optionally, neutralize the composition formed in step (a);

[0159] (c) Disperse the composition formed in step (a) or (b) in water to form a dispersed unsaturated polyurethane;

[0160] (d) Optionally, chain extension or chain termination is performed by reacting the dispersed unsaturated polyurethane with compound (Avi); and

[0161] (e) Optionally, the process solvent is stripped under vacuum.

[0162] The formation of unsaturated polyurethane in step (a) can be completed in a solvent. Then, after step (d), the solvent is removed by stripping it under vacuum at a suitable temperature below 100°C.

[0163] In the case where the olefinically unsaturated polyurethane prepolymer is made using a polyol (Av), (Av) is added in step (a) to react with compounds (Ai), (Aii), (Aiii) and (Aiv).

[0164] In the case where the olefinically unsaturated polyurethane prepolymer is made using a polyamine (Avi), (Avi) is added in step (a) to react with compounds (Ai), (Aii), (Aiii) and (Aiv) and optionally (Av).

[0165] The method may also include a reaction step (step b) using a neutralizing agent. This allows the hydrophilic group provided by compound (Aii) to be converted into an anionic salt.

[0166] The method can be accomplished by reacting an stoichiometric excess of isocyanate groups present in compound (Ai) with isocyanate reactive groups present in compounds (Aii), (Aiii), (Aiv), and optionally (Av) and (Avi).

[0167] The reactants from step (a) are typically used in a ratio corresponding to the equivalence ratio of isocyanate groups provided by compound (Ai) to isocyanate reactive groups provided by compounds (Aii), (Aiii), and (Aiv), and optionally (Av) and / or (Avi) in the reaction mixture, wherein the equivalence ratio is 0.8:1 to 1.2:1, preferably about 0.9:1 to 1.1:1, and most preferably 1:1.

[0168] In the event of further chain termination or chain elongation, the residual isocyanate may then react with an optional compound (Avi).

[0169] The reaction is preferably carried out under substantially anhydrous conditions and at a temperature of 30°C–100°C, more preferably 50°C–100°C, until the reaction between the isocyanate groups and the isocyanate reactive groups is substantially complete. The isocyanate content is determined by back titration with an amine (usually dibutylamine).

[0170] The reaction can be promoted by adding 5-40 wt%, preferably 15-30 wt%, of solvent to reduce the viscosity of the prepolymer and avoid side reactions that lead to undesirable branching or gel formation. The solvent is preferably water-soluble and has a low boiling point (<100°C). Acetone or methyl ethyl ketone is the preferred solvent.

[0171] Catalysts are commonly used to accelerate the reaction of isocyanates with their reactive groups. Bismuth neodecanoate is preferred over dibutyltin dilaurate. Specific inhibitors are typically added to prevent the olefinic unsaturated groups from reacting during the reaction and causing gelation. Butylhydroxytoluene is preferred over butyl hydroxyanisole, hydroquinone monomethyl ether, and hydroquinone. Those skilled in the art are fully aware of the types of catalysts and inhibitors that can be used to promote this reaction.

[0172] A sequential process can be used within the framework of this invention, wherein compounds (Ai) and / or compounds (Aiv), (Aii), (Aiii), (Av), and (Avi) are added sequentially and / or incrementally, or using a continuous feeding method, in two or more portions. This is because it allows for better control of the exothermic reaction, especially in the absence of a solvent. Another advantage is the ability to advantageously control the polymer's structure and molecular weight distribution, thereby limiting viscosity, for example.

[0173] In a particular embodiment of the invention, the residual free isocyanate groups provided by the reaction of compounds (Ai) to (Avi) are intentionally reacted to produce urethane and / or biuret groups. This provides increased molecular weight and chain branching, which can benefit the final properties of the polymer dispersion.

[0174] The prepolymer obtained after the reactions (Ai), (Aii), (Aiii), (Aiv), (Av), and (Avi) (if present) is first neutralized (if appropriate) and then dispersed in an aqueous medium by adding the prepolymer to water or, conversely, by adding water to the prepolymer. If compound (B) is present, it is usually present in the prepolymer prior to the neutralization and dispersion steps. Typically, this dispersion is carried out under high-shear mixing.

[0175] When dispersion requires initial neutralization of the hydrophilic groups (e.g., carboxylic acid groups, sulfonic acid groups, or phosphonic acid groups) provided by the compound (Aii) into anionic salts, this is preferably accomplished by adding an organic or inorganic neutralizing agent to the prepolymer or water. Suitable neutralizing agents include volatile organic tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, N,N-dimethylcyclohexylamine, N,N-dimethylaniline, N-methylmorpholine, N-ethylmorpholine, N-methylpiperazine, N-methylpyrrolidine, and N-methylpiperidine. Triethylamine is preferred. Suitable neutralizing agents include non-volatile inorganic bases containing a monovalent metal cation (preferably an alkali metal such as lithium, sodium, and potassium) and anions (e.g., hydroxide, hydroanion, carbonate, and bicarbonate ions) that are not retained in the dispersion. Sodium hydroxide is preferred.

[0176] The total amount of neutralizing agent can be calculated based on the total amount of acid groups to be neutralized. The molar ratio between acid groups and neutralizing agent is 1:0.5-1:1, preferably 1:0.8-1:1, and most preferably 1:0.9-1:1. Typically, a stoichiometric ratio of about 1:1 is used, unless a buffer is required by partially neutralizing the weak acid with a strong base.

[0177] Optionally, an additional compound (Avi) is added, which contains an active amino group capable of chain extension or chain capping of the residual isocyanate end groups of the prepolymer. This is typically carried out in an aqueous phase at a temperature of 5-90°C, preferably 15-30°C. Water can act as a chain extender after the free isocyanate has spontaneously hydrolyzed to the corresponding amine and continuously chain-extended with other residual isocyanates to provide urea.

[0178] The total amount of compound (Avi) used is typically calculated based on the amount of residual isocyanate groups present in the polyurethane prepolymer. During chain extension, the ratio of isocyanate groups in the prepolymer to amine groups in the chain extender (Avi) is typically in the range of about 1:0.7 to 1:1, preferably about 1:0.9 to 1:1, based on equivalents. This ratio is more preferably 1:1 to obtain a fully reacted polyurethane polymer without residual isocyanate groups.

[0179] Typically, the polymer dispersion is stripped after the formation of the prepolymer dispersion and when it contains a volatile solvent with a boiling point less than 100°C. This is usually done under reduced pressure and at a temperature of 20-90°C, preferably 40-60°C. Additional water is added to compensate for possible water loss during stripping and to fix the desired solids content of the dispersion.

[0180] coating

[0181] The aqueous bio-based quantitatively curable polyurethane composition of the present invention provides a coating after film formation and complete evaporation of water, followed by ultraviolet (UV) radiation curing or electron beam (EB) radiation curing. The radiation-curable composition of the present invention is preferably cured by ultraviolet radiation in the presence of a photoinitiator.

[0182] The coating has a high biocarbon content, resulting in a highly desirable reduction in the material's carbon footprint and its cyclical impact. In particular, the bio-based, quantity-curable polyurethane composition according to the invention provides a hard coating with a high level of performance for protecting and decorating a wide range of substrates. Furthermore, it provides excellent adhesion associated with good optical properties such as transparency, clarity, haze, and gloss. It also exhibits excellent mechanical and chemical resistance.

[0183] This invention also relates to the use of the described composition in the preparation of inks, varnishes, or coatings, and to a method for preparing inks, varnishes, or coatings, wherein the composition as described above is used. Digital printing (inkjet) and 3D printing are also particularly relevant to this invention.

[0184] The coatings, inks or overprinting varnishes prepared from the compositions of the present invention may also contain additives such as photoinitiators, thermal crosslinking agents, wetting and leveling agents, rheology modifiers, defoamers, waxes, colorants, pigments or inorganic fillers.

[0185] Within the framework of this invention, the use of bio-based additives is particularly suitable. A relevant example is the use of Bayhydur ECO701-90 as a water-dispersible bio-based polyisocyanate thermal crosslinking agent for 2K dual curing.

[0186] The polyurethane composition may also contain any other polymer dispersions or emulsions different from those of the present invention. Preferably, these polymer dispersions or emulsions are bio-based and contain more than 20%, preferably more than 40%, more preferably more than 60%, and most preferably more than 80% biocarbon content. Most preferably, these polymer dispersions or emulsions contain olefinically unsaturated functional groups such as (meth)acrylate groups.

[0187] For example, it is advantageous to add a bio-based aqueous emulsion based on the previously described natural epoxidized oil or natural epoxidized fatty acid. Epoxidized soybean oil is preferred. It is partially or completely reacted with (meth)acrylic acid after the opening of the epoxy ring to obtain an olefinic unsaturated alcohol or polyol. The hydroxyl groups are partially or completely reacted with an acid anhydride to obtain an olefinic unsaturated compound having at least one carboxylic acid functional group. The anhydride is preferably succinic anhydride. The product is then partially or completely neutralized with an organic or inorganic base. Sodium hydroxide is preferred. It is then optionally mixed with an emulsifier. A nonionic block copolymer emulsifier with an HLB value greater than 6, more preferably greater than 8, even more preferably greater than 10, still more preferably greater than 12, and most preferably greater than 14 is preferred. When water is added to the product under high shear stirring at ambient or moderate temperature, a stable emulsion is obtained, which has a solid content of 35-65% and a low droplet size of less than 500 nm, typically less than 150 nm.

[0188] The present invention also relates to a method for coating a surface with the composition described above, comprising the following steps:

[0189] • Apply the composition to the surface,

[0190] • The composition applied by heat drying,

[0191] • The dried composition is cured by using high-energy ultraviolet light, in the presence of a photoinitiator and / or by exposure to a high-energy electron beam.

[0192] Specifically, low-energy ultraviolet light (LED lamps) can be advantageously used. Ultraviolet light can also be provided by excimer lamps to provide the desired surface patterning and optical properties (including low gloss) for the curing process.

[0193] Alternatively, the curing mechanism may be partly or entirely thermal curing at the curing temperature in the presence of a thermal initiator known in the art (typically a peroxide or azo compound with a suitable decomposition half-life).

[0194] The compositions of the present invention are particularly suitable for preparing coatings for wooden furniture and plastic resilient flooring.

[0195] The following examples illustrate the invention but do not limit it. Example

[0196] raw materials

[0197] I PD I = I, isophorone diisocyanate from Coves tro. The product is used as a reactant.

[0198] HD I = H, hexane diisocyanate from Coves tro. The product is used as a reactant.

[0199] N7300 = ECO N7300 is a bio-based pentane diisocyanate trimer from Coves tro. The product is used as a reactant.

[0200] MOD1071 is a bio-based acrylated polyester diol with an IOH content of approximately 80 mg KOH / g, obtained by reacting epoxidized soybean oil with an ethylene oxide oxygen content of approximately 7% with acrylic acid and succinic anhydride. The product is used as a reactant.

[0201] MOD1010 is a bio-based acrylated polyether diol with an IOH content of approximately 231 mg KOH / g, obtained by reacting bisphenol A diglycidyl ether diacrylate with acrylic acid. The product is used as a reactant.

[0202] MOD450 is a bio-based acrylated polyester alcohol with an IOH concentration of approximately 60 mg KOH / g, obtained by reacting a fatty acid dimer with an AV concentration of approximately 193 mg KOH / g with pentaerythritol and acrylic acid. The product is used as a reactant.

[0203] MOD706 is a bio-based acrylic polyester alcohol with an IOH content of approximately 165 mg KOH / g, obtained by reacting glycerol propoxylate with acrylic acid and an IOH content of approximately 631 mg KOH / g. The product is used as a reactant.

[0204] MOD767 is a bio-based acrylated polyester alcohol with an IOH content of approximately 117 mg KOH / g, obtained through the reaction of hydroxyethyl acrylate with lactide. The product is used as a reactant.

[0205] AE532 = Bio-based methacrylated ether alcohol, with an IOH content of approximately 163 mg KOH / g, is obtained by the reaction of glycidyl methacrylate with lauric acid. The product is used as a reactant.

[0206] NX7202 = from Cardolite GX7202. A bio-based cashew nut shell acrylate monool with an IOH concentration of approximately 145 mg KOH / g. The product is used as a reactant.

[0207] NX7216 = from Cardolite NX7202. Bio-based cashew nut shell acrylate diol with an IOH concentration of approximately 125 mg KOH / g. The product is used as a reactant.

[0208] NX9201 = from Cardolite NX9201. A bio-based cashew nut shell-derived polyether glycol with an IOH concentration of approximately 72 mg KOH / g. This product is used as a reactant.

[0209] DMPA = Dimethylolpropionic acid from Perstorp. The product is used as a reactant.

[0210] BUTOH = Bio-based butanol from Green Biologics. The product is used as a reactant.

[0211] N120 = from Perstorp N120 is a polyethylene glycol diol with IOH = 120 mg KOH / g. The product is used as a reactant.

[0212] PDA = 1,2-Propanediamine from Lanxess. The product is used as a reactant.

[0213] BHT = Butyl hydroxytoluene from Merisol. The product is used as a free radical inhibitor.

[0214] BiND= Bi 2010, bismuth neodecanoate from Umicore. The product is used as a catalyst.

[0215] TEA = Triethylamine from Arkema. The product is used as a neutralizing agent.

[0216] NaOH 30% = Sodium hydroxide from Brenntag as a 30% solution in water. The product is used as a neutralizing agent.

[0217] SR4485 = SR4485 is a water-based biocide composition from Thor. The product is used as a biocide.

[0218] ACE = Acetone, available from Brenntag. The product is used as a process solvent.

[0219] H2O = softened water.

[0220] Example 1 LVL341

[0221] 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 were charged into the reactor. The products were mixed at ambient temperature with stirring at 130 rpm. The reactor jacket was heated to 70°C, and air injection was initiated at a level of 2 l / kg / h. 25.0 g of IPDI was added five times, and after each addition, the reactor jacket was maintained at 70°C under reflux for 1 hour. After the final maturation step, the reaction was maintained under reflux until I(NCO) reached a stable value of approximately 0.30 meq / g. The reaction mixture was cooled to 50°C, and air injection was stopped. 19.0 g of TEA was added to the reactor, and stirring was increased to 200 rpm for 15 minutes. 1029.0 g of H2O was added to a separate dispersion vessel at ambient temperature and mixed with a stirrer at 400 rpm. The prepolymer solution in acetone was transferred to the dispersion vessel at 50°C over a 15-minute period to prepare the polymer dispersion. Stirring was reduced to 150 rpm while the reactor jacket was heated to 60°C. The vacuum was gradually increased to 100 mbar using a vacuum pump while preventing excessive foam formation. Solvent stripping was continued for approximately 5 hours until the ACE level was determined to be less than 0.1%. The reactor was cooled to below 30°C. 1.6 g of SR4485 was added along with some additional H2O to adjust the solids content to a target of approximately 35% solids material. When completely homogeneous, the mixture was sieved from the reactor through a 100-micron sieve. The isocyanate content I (NCO) in the prepolymer reaction mixture was determined using a dibutylamine back-titration method and expressed as meq / g.

[0222] The following examples were prepared according to the adaptation method of Example 1, and their detailed weight composition is shown in Table 2.

[0223] Example 2 LVL342B

[0224] A variant of Example 1 uses 30% NaOH for neutralization.

[0225] Example 3 LVL354

[0226] A variant of Example 1, wherein MOD706 is replaced by NX7202.

[0227] Example 4 LVL366

[0228] A variant of Example 1, wherein MOD706 is replaced by MOD767.

[0229] Example 5 LVL377

[0230] A variant of Example 1, wherein MOD706 is replaced by AE532.

[0231] Example 6 LVL360

[0232] A variant of Example 1, wherein DMPA is partially replaced by N120.

[0233] Example 7 LVL368

[0234] A variant of Example 1, wherein MOD1071 is replaced by NX7216.

[0235] Example 8 LVL369

[0236] A variant of Example 1, wherein IPDI is partially replaced by N7300 and BUTOH; chain extension is caused by the reaction of residual isocyanate with PDA added to the fresh dispersion.

[0237] Example R1 ECO UV 2877

[0238] ECO UV 2877, a bio-based market reference from Covestro, contains 35% bio-carbon.

[0239] Example R2 7788

[0240] 7788, a bio-based market reference from Allnex, contains ~1% bio-carbon. This product is used as an internal benchmark for penetration performance in clear coating applications.

[0241] Example R3 7733

[0242] 7733, from Allnex, serves as a market reference for bio-based products and contains ~5% bio-carbon. This product is used as an internal benchmark for high-end performance in clear coatings or coloring applications.

[0243] Example R4 7999

[0244] 7999, a bio-based market reference from Allnex, contains ~22% bio-carbon. This resin is prepared based on an Aiv-type compound containing more than 40% bisphenol A. This product targets high-end performance levels with a high internal bio-carbon content and a strong sustainability positioning.

[0245] Example R5 LVL252

[0246] A variant of Example 1, wherein MOD1070 is replaced by MOD1010 and IPDI is partially replaced by N7300 and BUTOH. This resin is prepared based on a compound containing BPA.

[0247] Example R6 LVL272

[0248] A variant of Example 1, wherein the MOD1070 is replaced by the NX9201.

[0249] Example R7 LVL277

[0250] A variant of Example 1, wherein the MOD1070 is replaced by the NX9201 and the IPDI is partially replaced by the N7300 and BUTOH.

[0251] Example R8 LVL298

[0252] A variant of Example 1, wherein MOD1070 is replaced by NX9201; MOD706 is replaced by NX7202; IPDI is partially replaced by HDI; and TEA is replaced by 30% NaOH.

[0253] Test protocols for liquid dispersions

[0254] Solid content

[0255] The solids content of the aqueous polymer composition was determined by gravimetric analysis at 120°C over a period of 2 hours after drying 1 g of dispersion, and is expressed as a percentage (%).

[0256] Viscosity

[0257] The viscosity of the aqueous polymer composition was measured at 25°C using a cone-plate rotational viscometer (refer to Anton Paar MCR92) and is expressed in mPa·s.

[0258] pH

[0259] The pH of the aqueous polymer composition was determined according to DIN EN ISO 10390.

[0260] Average particle size

[0261] The average particle size of the aqueous polymer composition was determined using a dynamic light scattering apparatus (refer to Malvern Particulate Analyzer Processor Model 7027 / 4600SM). It is expressed in nm.

[0262] Minimum film formation temperature

[0263] The minimum film-forming temperature (MFFT) of the aqueous polymer composition is determined by applying a thin wet coating onto an automatically gradient-heated metal plate (refer to Rhopoint MFFT 90, which covers the desired temperature range). It is expressed in °C. A low value (<10 °C) is desired to allow for the preparation of a good, uniform film without the need for a coalescing agent (which increases VOCs).

[0264] Test plan for dry coating

[0265] Use 1.5% 500 (photoinitiator) and 2% VXW 6360 (pre-diluted in water at 50% concentration before application (thickener)) is used to formulate the waterborne resin as described in the examples of this invention. In the case of ECO UV 2877, an additional amount of 10% butyl solvent or 1,2-propanediol (co-solvent) and 0.5% is required. 028 (wetting agent) is used to obtain a coating with suitable film formation and quality.

[0266] Unsaturated level

[0267] The amount of unsaturation is calculated from the listed materials, and refers to the amount of acrylic acid or glycidyl methacrylate present in the polymer. It is expressed in meq / g of polymer composition.

[0268] In the case of Example R1, this information was not available and titration was used. The titration protocol typically involves the reaction of an activated double bond of azir-Michael addition with morpholine, followed by the reaction of excess morpholine with acetic anhydride (forming an amide derivative and acetic acid), and a double titration of acetic acid with sodium hydroxide and a tertiary amine with hydrochloric acid.

[0269] Adhesion before curing

[0270] The product was applied as a 50 μm wet layer on... The coating was applied to a sheet and dried at 50°C for 5 min. After cooling and stabilization at 23°C, the residual tack of the coating was determined by pressing a finger onto the coating and evaluating the ease with which the finger could be separated without adhesion; it was expressed on a scale of 1-5 (5 = no tack).

[0271] Gloss level 60°

[0272] A 50 μm wet coat was applied to a white Leneta substrate using a Meyer stick, dried at 50°C for 5 minutes, and then UV-cured with an 80 W / cm Hg lamp at a conveyor belt speed of 5 m / min. The gloss of the coating was then evaluated. Measurements were taken using a BYK Gardner Micro TRI gloss meter according to DIN-67530 standard with a light incidence of 60°. High gloss values ​​were desired to provide a good aesthetic appearance to the coated substrate.

[0273] Yellowing

[0274] A 50 μm wet coat was applied to a white Leneta substrate using a Meyer stick, dried at 50°C for 5 minutes, and then UV-cured with an 80 W / cm Hg lamp at a conveyor belt speed of 5 m / min. Yellowing (b-value) was evaluated. The yellowing was measured using a colorimeter before and one hour after curing. The difference in color (Δb) is reported. A low yellowing value protects the aesthetic appearance of the coated substrate.

[0275] Stain resistance

[0276] The stain resistance of the coating was evaluated after applying a 50 μm wet coat to a white Leneta board using a Meyer stick, drying at 50°C for 5 minutes, and then UV curing with an 80 W / cm Hg lamp at a conveyor belt speed of 5 m / min. Stains were applied using a black alcohol marker (reference N70) and a glass microfiber filter saturated with the test substance, which was then placed in contact with the coating for 16 hours. The test substances used were mustard, coffee, eosin, isobutanamine, 10% ammonia, and 50% ethanol. Stains were cleaned by rubbing several times with a paper towel saturated with water or isopropanol. Residual stains were visually evaluated using a scale of 1-5, with 5 = no residual stain. High stain resistance is expected to provide the best coating protection against any household product spills.

[0277] Solvent resistance

[0278] Solvent resistance of the coating was evaluated after a 50 μm wet coat was applied to a white Leneta board using a Meyer stick, dried at 50°C for 5 min, and then UV cured with an 80 W / cm Hg lamp at a conveyor belt speed of 5 m / min. It was evaluated by double-rubbing with acetone using a solvent-saturated cotton cloth until the coating was removed. One double-rubbing motion equals a forward and backward back-and-forth motion. The reported value is the number of double-rubbing motions required to penetrate the cured coating composition. High solvent resistance is expected to provide the best coating protection against any household product spills.

[0279] Persoz hardness

[0280] This method determines the surface hardness of a 120 μm wet coating applied to a glass plate. The coating was dried at 40°C for 20 minutes and finally cured at 5 m / min under an 80 W / cm UV-Hg lamp. The coated sample was stabilized in a conditioned chamber (20°C and 50% humidity) for 24 hours, and the Persoz impact hardness was measured at three different locations on the surface. The average value was calculated and expressed in seconds. High Persoz hardness is expected to provide the best coating protection against any warehouse or household deterioration.

[0281] Nail scratch resistance

[0282] A 120 μm wet coat was applied to a sandpaper-ground white melamine board using a Meyer stick, followed by evaporation at 40°C for 20 minutes. After UV curing with an 80 W / cm Hg lamp at a conveyor belt speed of 5 m / min, the coating's resistance to nail scratching was evaluated. After 24 hours in a conditioning chamber (20°C and 50% humidity), the coating was tested by firmly pressing a nail against it in a linear motion, and visual marks or damage resulting from loss of adhesion were evaluated using a scale of 1-5, with 5 = no visible marks or damage. High nail scratch resistance is expected to provide the best coating protection against any deterioration in warehouses or homes.

[0283] Pencil hardness

[0284] A 120 μm wet coat was applied to a white melamine board sanded with sandpaper using a Meyer stick. The coating was then allowed to evaporate at 40°C for 20 seconds, followed by UV curing with an 80 W / cm Hg lamp at a conveyor belt speed of 5 m / min. The pencil hardness of the coating was then evaluated. After 24 hours in a conditioned chamber (20°C and 50% humidity), the cured coating was tested by scratching it with a sharp pencil of increased hardness using a dedicated metal stand with a fixed right angle and uniform pressure. Test results were reported as pencil hardness greater than the hardness at which the coating was significantly damaged. The pencil hardness grades, from softest to hardest, were 9B–8B–7B–6B–5B–4B–3B–2B–1B–HB–F–1H–2H–3H–4H–5H–6H–7H–8H–9H. High coating hardness is expected to provide the best coating protection against any deterioration in warehouses or homes.

[0285] Reduced carbon content and material carbon footprint derived from biological sources

[0286] The biologically derived carbon content (%) was determined using ASTM D6866 standard. The sample was dried and catalytically converted to graphite at elevated temperatures, providing the total carbon content (%) of the sample. The C14 / C12 isotope ratio of the graphite was determined using accelerated mass spectrometry and then converted to biologically derived carbon content (%) using modern oxalic acid as a reference.

[0287] The biogenic carbon content is then further converted into a reduction in the material's carbon footprint (gCO2 / kg), corresponding to a substantial saving in atmospheric CO2 release, assuming a neutral viewpoint based on equivalent atmospheric CO2 uptake during plant photosynthesis. The reduction in the material's carbon footprint is used as a quantitative measure of the sustainability performance of biopolymers; higher values ​​indicate a stronger sustainability impact.

[0288] result

[0289] Table 1 shows each example of compounds containing biocarbon content that may be used to prepare waterborne bio-based quantitatively cured polyurethanes.

[0290] Table 1: Polymer Structure

[0291] 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

[0292] / = does not exist

[0293] O = Bio-based raw materials that exist but are not derived from claim 1

[0294] BIO = containing bio-based raw materials from claim 1

[0295] Tables 2a and 2b describe the amount of each compound used in each example and reference example (in addition to those commercially available).

[0296] Tables 2a-b: Detailed Composition

[0297]

[0298]

[0299]

[0300] Tables 3a and 3b show the product characteristics for each embodiment. It is clear that the bio-based polyurethane R1 has a high MFFT, which necessitates the use of a coalescing agent to achieve acceptable coating quality during application.

[0301] Tables 3a-b: Product Characteristics

[0302] Solid content (%) 39.6 40.0 38.5 33.9 34.3 34.4 34.3 34.7 Viscosity (mPa·s) 81 250 50 63 151 338 1150 168 pH 7.6 7.4 7.5 8.0 7.4 7.5 7.6 7.4 Average particle size (nm) 156 75 90 78 83 58 47 66 MFFT (°C) 42 ～0 ～0 ～0 ～0 ～0 ～0 ～0 Degree of unsaturation (meq / g polymer) 0,24 1,40 3,10 3,59 2,80 2,24 1,84 2,88

[0303] Solid content (%) 35.0 35.9 35.2 34.9 34.8 35.4 34.5 34.8 Viscosity (mPa·s) 23 153 24 17 18 66 38 47 pH 7.3 7.2 7.4 6.7 7.2 7.1 7.6 7.5 Average particle size (nm) 84 157 99 74 90 68 68 71 MFFT (°C) ～0 ～0 ～0 ～0 ～0 ～0 ～0 ～0 Degree of unsaturation (meq / g polymer) 3,02 3,02 2,86 2,80 2,92 2,94 3,26 2,38

[0304] Tables 4a and 4b show the coating characteristics and performance of the examples and reference examples. It is clear from the tables that the coatings made from the aqueous bio-based polyurethane of the present invention provide good to excellent coating performance. In particular, the results in resistance to nail scratching and acetone dual abrasion are surprisingly good.

[0305] Tables 4a-b: Coating characteristics and performance

[0306]

Claims

1. An aqueous bio-based, quantity-curable polyurethane composition comprising: At least one olefinically unsaturated polyurethane prepolymer (A) obtained from the reaction of the following substances: ● At least one aliphatic, alicyclic, or aromatic polyisocyanate compound (Ai), ● At least one hydrophilic compound (Aii) containing at least one reactive group capable of reacting with isocyanate and capable of dispersing polyurethane prepolymer in an aqueous medium directly or after reacting with an organic or inorganic neutralizing agent to provide its salt. ● At least one olefinic unsaturated compound (Aiii) containing a reactive group capable of reacting with isocyanates. ● At least one olefinic unsaturated compound (Aiv) containing at least two reactive groups capable of reacting with isocyanates. Optionally, at least one olefinic unsaturated compound (B), different from (Aiii) and (Aiv), does not contain a reactive group capable of reacting with isocyanate. The olefinic unsaturated compounds (Aiii), (Aiv) and (B) each have a biocarbon content greater than 20 wt% of the total carbon content of the compound, and are obtained by reacting the olefinic unsaturated compounds with compounds derived from bio-based sources, wherein the biocarbon content is determined using ASTM D6866 standard. The olefinically unsaturated compound (Aiv) mentioned above is prepared using 0-40 wt% bisphenol A; and The composition comprises polymerizable olefinic unsaturated groups in a total amount of at least 0.5 meq / g based on the total weight of the polyurethane composition.

2. The aqueous bio-based quantitatively curable polyurethane composition according to claim 1, wherein the at least one olefinically unsaturated polyurethane prepolymer (A) is obtained by reaction with the following substances: Unlike (Ai), (Aii), (Aiii) or (Aiv) monools or polyols (Av), it has a biochar content greater than 20 wt% and contains at least one reactive group capable of reacting with isocyanates; and / or At least one monoamine or polyamine (Avi), optionally having a biocarbon content of more than 20 wt% and capable of reacting with isocyanates.

3. The aqueous bio-based quantitatively curable polyurethane composition according to claim 1, wherein the MFFT of the polyurethane composition is 0-20°C.

4. The aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-3, wherein the bio-carbon content of the polyurethane composition is greater than 20 wt% of the total carbon content of the polyurethane composition.

5. The aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-3, wherein the olefinic unsaturated compounds (Aiii), (Aiv) and / or (B) are obtained by reacting a reactive bio-based compound with a compound comprising at least one olefinic unsaturated functional group, wherein the olefinic unsaturated functional group is selected from acrylic acid, methacrylic acid and glycidyl (meth)acrylate.

6. The aqueous bio-based quantitatively curable polyurethane composition according to claim 5, wherein the reactive bio-based compound is selected from organic oils and organic oil derivatives, fatty acids and fatty acid derivatives, fatty acid dimers and fatty acid dimer derivatives, and bio-based polyols and bio-based polyol derivatives.

7. The aqueous bio-based quantitatively curable polyurethane composition according to claim 6, wherein the bio-based polyol is selected from fatty alcohols, fatty alcohol dimers and sugar alcohols, and / or wherein the bio-based polyol derivative is glycolide, lactide, lactone and poly(epoxy) derivative.

8. The aqueous bio-based quantitatively curable polyurethane composition according to claim 6, wherein the organic oil derivative is selected from the following epoxidized oils: 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 nut shell oil and / or epoxidized fatty acids derived therefrom.

9. The aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-3, wherein the amount of reactive groups present in the olefinically unsaturated compound (Aiv) capable of reacting with isocyanates is controlled by: A portion of the isocyanate reactive groups are reacted with a capping compound capable of reacting with the isocyanate reactive groups, wherein the capping compound produces functional groups different from the isocyanate reactive groups.

10. The aqueous bio-based permeable curable polyurethane composition according to any one of claims 1-3, wherein the olefinic unsaturated compounds (Aiii), (Aiv) and / or (B) are obtained by means of: Natural epoxidized oils are reacted with olefinic unsaturated carboxylic acid compounds to obtain olefinic unsaturated polyols. The olefinic unsaturated polyol is reacted with a cyclic anhydride to obtain an olefinic unsaturated polyol having at least one carboxylic acid functional group.

11. The aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-3, wherein the olefinic unsaturated compounds (Aiii), (Aiv) and / or (B) are obtained by reacting a bio-based fatty acid or fatty acid dimer with a polyol and (meth)acrylic acid.

12. The aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-3, wherein the olefinic unsaturated compound (Aiii) has a hydroxyl number of 20-500 mg KOH / g.

13. The aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-3, wherein the olefinic unsaturated compound (Aiv) has a hydroxyl number of 20-800 mg KOH / g.

14. The aqueous bio-based permissible curing polyurethane composition according to any one of claims 1-3, wherein the polyisocyanate (Ai) has a biocarbon content of greater than 20 wt%, and / or wherein the polyisocyanate (Ai) is based on or derived from pentane diisocyanate.

15. The aqueous bio-based polyurethane composition that may be cured according to any one of claims 1-3, wherein the polyisocyanate (Ai) is added in a stoichiometric ratio of 0.8:1 to 1.2:1, comprising an isocyanate functional group capable of reacting with isocyanates present in compounds (Aii), (Aiii), (Aiv) and optionally (Av) and / or (Avi).

16. The aqueous bio-based permeable curable polyurethane composition according to any one of claims 1-3, wherein the hydrophilic compound (Aii) has a bio-carbon content of more than 20 wt% and / or a hydroxycarboxylic acid compound represented by the general formula (HO)xR(COOH)y, wherein R represents a straight-chain or branched aliphatic, alicyclic or aromatic hydrocarbon residue having 1-36 carbon atoms, and x and y are independently integers of 1-3.

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

18. The aqueous bio-based permeable curable polyurethane composition according to any one of claims 1-3, wherein the hydrophilic compound (Aii) is selected from the following nonionic components: mono- or poly-hydroxylated polyethylene oxide polymers or mono- or poly-hydroxylated polyethylene oxide-co-polypropylene oxide polymers.

19. The aqueous bio-based quantitatively curable polyurethane composition according to claim 2, wherein the compound (Av) is selected from the following bio-based polyols: aliphatic, alicyclic or aromatic diols or polyols, fatty alcohols or fatty alcohol dimers, polycarbonate polyols, polyester polyols, polyether polyols, polyacrylate polyols or mixtures thereof.

20. The aqueous bio-based quantitatively curable polyurethane composition according to claim 2, wherein the monoamine or polyamine compound (Avi) is an aliphatic, alicyclic, or aromatic monoamine, diamine, or polyamine.

21. A method for preparing an aqueous bio-based polyurethane composition that may be quantitatively cured according to any one of claims 1-20, comprising the following steps: (a) An unsaturated polyurethane is formed from compounds (Ai), (Aii), (Aiii), (Aiv) and optionally (Av) and / or (Avi) in the presence of compound (B) and optionally in the presence of a solvent. (b) Optionally, neutralize the composition formed in step (a); (c) Disperse the composition formed in step (a) or (b) in water to form a dispersed unsaturated polyurethane; (d) Optionally, chain extension of a dispersed unsaturated polyurethane containing residual isocyanate groups by reaction with compound (Avi); and (e) Optionally, the process solvent is stripped under vacuum.

22. A coating or ink prepared from the composition of any one of claims 1-20, optionally further comprising additives selected from: photoinitiators, thermal crosslinking agents, wetting agents, rheology modifiers, defoamers, waxes, cosolvents, colorants, inorganic fillers, and any other polymer dispersions or emulsions.

23. A method for coating a surface with the composition according to any one of claims 1-20, comprising the following steps: ● Apply the composition to the surface. ● The composition subjected to heat drying, ● The composition is energy-cured and dried using low-energy or high-energy ultraviolet light, including excimer light, in the presence of a photoinitiator and / or exposure to a high-energy electron beam.

24. Use of the aqueous bio-based quantitatively curable polyurethane composition according to any one of claims 1-20 for digital printing.

25. Use of the aqueous bio-based permeable curable polyurethane composition according to any one of claims 1-20 in 3D printing technology.

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