Biobased polyurethane resin composition, manufacturing method and use in particular in the doming technique
Patent Information
- Application Number
- EP2022801508
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2022-10-07
- Publication Date
- 2025-08-13
AI Technical Summary
Conventional polyurethane resins used in doming are petrochemical-based, posing toxicity and environmental concerns, and there is a lack of biosourced options that meet the necessary criteria for transparency, polymerization time, hardness, and viscosity for effective doming applications.
A biosourced polyurethane resin composition is developed by mixing a polyisocyanate phase with at least 70% biosourced carbons and a polyol phase with at least 80% biosourced carbons, using isocyanate-terminated prepolymers and polyols like pentamethylene diisocyanate and poly(1,3-propanediol), with optional components such as diisocyanate isocyanurate and castor oil, to achieve the desired properties.
The composition achieves the required transparency, polymerization time, and viscosity, while significantly reducing toxicity and environmental impact, meeting the criteria for doming applications and potentially other fields like electronics and construction.
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Figure 1.1
Abstract
Description
DESCRIPTION TITLE: Bio-sourced polyurethane resin composition, manufacturing process and application, particularly to the doming technique TECHNICAL FIELD OF THE INVENTION
[0001] The invention relates to the field of polyurethane resins, and more particularly to bio-sourced polyurethane resins.
[0002] The invention finds particular application in the field of doming. TECHNOLOGICAL BACKGROUND OF THE INVENTION
[0003] Applying a resin dome to a printed substrate is a well-known technique for giving a two-dimensional image a three-dimensional character. To achieve this, a transparent or translucent two-component liquid polyurethane resin is deposited on a non-porous printed substrate. The resin's progression on the substrate stops at the cutting edge of the substrate, and the surface tension of the resin keeps it in place on the substrate. Once dry, the resin takes the form of a dome, giving a lens effect to the printed substrate. This is why doming is also presented as a technique for creating three-dimensional labels.
[0004] As is well known, the resins used in this field are polyurethane resins obtained by mixing two phases: one containing polyols, and the other polyisocyanates. A polyol / polyisocyanate is a chemical compound carrying at least two alcohol / isocyanate functions (-OH / -OCN). A transparent liquid is obtained after mixing these two phases. This liquid, once deposited on the support, hardens in a few minutes, giving rise to a more or less flexible and translucent material.
[0005] The polyurethane resins conventionally used are resins synthesized from raw materials (polyisocyanates and polyols) of petrochemical origin.
[0006] In addition to the petrochemical nature of the derivatives, isocyanate compounds are hazardous. They are most often classified as toxic, mutagenic, carcinogenic, reprotoxic, and environmentally hazardous.
[0007] Without being limited to the sole application of doming, the polyurethane resin must, in the field of doming, meet a certain number of criteria. The resin must be transparent to allow the print of the support to appear, the resin must polymerize at room temperature, its gel time must be greater than 1 hour, as a precaution greater than or equal to 3 hours, and its Shore A hardness must be similar to that of synthetic resins, i.e. between 40 and 90 ShA. For doming applications, a viscosity of the polyol and polyisocyanate phases less than 900 mPa.s at 25°C is preferred, this limitation not applying to other applications.
[0008] There are currently few choices of bio-sourced polyisocyanates, and none of them, when mixed with a polyol, can produce a polyurethane resin that meets the criteria set out above. SUMMARY OF THE INVENTION
[0009] In this context, the invention relates to a new polyurethane resin formulation made from bio-sourced polyol and polyurethane compounds.
[0010] The invention also relates to a method for manufacturing such resins, particularly adapted to the application constraints in the field of doming.
[0011] The invention further relates to a printed support covered with a dome made of such a resin.
[0012] For this purpose, the biosourced polyurethane resin composition of the invention is essentially characterized in that it is obtained by mixing a volume V1 of polyisocyanate phase, and a volume V2 of polyol phase, and in that: either the polyisocyanate phase comprises at least two polyisocyanates of which at least one is an isocyanate-terminated prepolymer which comprises at least 70% of biosourced carbons and the other comprises at least 60% of biosourced carbons, and the polyol phase comprises at least one polyol which comprises at least 80% of biosourced carbons, or the polyol phase comprises at least two polyols which each comprise at least 80% of biosourced carbons, and the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer which comprises at least 70% bio-sourced carbons.
[0013] The composition of the invention may also comprise the following optional characteristics considered in isolation or according to all possible technical combinations: the isocyanate-terminated prepolymer of the polyisocyanate phase has a polyether-type skeleton. - the number of isocyanate functions in the polyisocyanate phase is equal to the number of alcohol functions in the polyol phase. - the isocyanate-terminated prepolymer is obtained by reacting a polyol which comprises at least 80% bio-sourced carbons and a polyisocyanate which comprises at least 60% bio-sourced carbons. - polyol is a polyether polyol which contains 100% bio-sourced carbons. - the isocyanate-terminated prepolymer is obtained by reacting: either pentamethylene diisocyanate comprising at least 60% biosourced carbons with poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol comprising 100% biosourced carbons, or pentamethylene diisocyanate comprising at least 60% biosourced carbons with poly(1,3-propanediol) with a molar mass of between 900 and 1100g / mol comprising 100% biosourced carbons. - when the polyisocyanate phase comprises at least two polyisocyanates, the polyisocyanate which comprises at least 60% biosourced carbons is a diisocyanate, preferably a diisocyanate isocyanurate. - the polyol(s) in the polyol phase contain 100% bio-sourced carbons. - the polyol phase comprises a polyether polyol and / or castor oil. - the composition is obtained by mixing the same volume of polyisocyanate phase and polyol phase, and the number of isocyanate functions in the polyisocyanate phase is equal to the number of alcohol functions in the polyol phase. - the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% biosourced carbon with poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% biosourced carbon in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% biosourced carbon and castor oil in a ratio between 40:60 and 70:30 comprising 100% biosourced carbon. - the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% biosourced carbon with poly(1,3-propanediol) of molar mass between 900 and 1100g / mol comprising 100% biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% biosourced carbon in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% biosourced carbon or poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% biosourced carbon bio-sourced, and castor oil in a ratio of between 20:80 and 60:40 comprising 100% bio-sourced carbon. - the composition comprises at least 80% bio-sourced carbons, preferably at least 85% bio-sourced carbons.
[0014] Another aspect of the invention relates to the method of manufacturing the aforementioned composition, which is essentially characterized in that it comprises at least the steps of: supply or preparation of a polyisocyanate phase of volume V1 and supply or preparation of a polyol phase of volume V2, for which phases: either the polyisocyanate phase comprises at least two polyisocyanates, at least one of which is an isocyanate-terminated prepolymer which comprises at least 70% bio-sourced carbons and the other comprises at least 60% bio-sourced carbons, and the polyol phase comprises at least one polyol which comprises at least 80% bio-sourced carbons, or the polyol phase comprises at least two polyols which each comprise at least 80% bio-sourced carbons, and the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer which comprises at least 70% bio-sourced carbons. mixture of the polyisocyanate and polyol phases.
[0015] The method of the invention may also comprise the following optional characteristics considered in isolation or according to all possible technical combinations: the isocyanate-terminated prepolymer is obtained by reacting a polyol which comprises at least 80% of biosourced carbons and a polyisocyanate which comprises at least 60% of biosourced carbons. the polyol phase comprises two different polyols which each comprise 100% of biosourced carbons and the polyisocyanate phase comprises two polyisocyanates, the polyisocyanate which comprises at least 60% of biosourced carbons being a diisocyanate isocyanurate. the method further comprises the steps of: evaluation of the equivalent volume as an isocyanate function (LEVi, LEVii,..., lEVin) of the isocyanate-terminated prepolymer including, where appropriate, excess polyisocyanate used for the manufacture of the isocyanate-terminated prepolymer or of the isocyanate-terminated prepolymer including, where appropriate, excess polyisocyanate and polyisocyanate which comprises at least 60% of biosourced carbons from the polyisocyanate phase. evaluation of the equivalent volume in alcohol function (HEVh, HEVhh HEVhn) of the polyol or of each of the at least two polyols of the polyol phase, and adjustment of the respective volume percentage (%Vli, %Vlii,... , %Vlin) of each of the at least two polyisocyanates in the isocyanate phase and / or and of the respective volume percentage (%VHh,%VHhh,... ,%VHhn) of each of the at least two polyols in the polyol phase by responding to the following formula: VI * IEV = V2 * HEV where IEV is the equivalent volume in isocyanate function of the polyisocyanate phase and corresponds to the following formula: IEV = (%VIi * lEVi) + (%7 / ii * IEVii) + ••• + (%7 / in * lEVin) and where HEV is the equivalent volume in alcohol function of the polyol phase and corresponds to the following formula: HEV = (%VHh * HEVh) + (%VHhh * HEVhh) + ••• + (%VHhn * HEVhn) the polyisocyanate phase is a mixture comprising at least the isocyanate-terminated prepolymer and the polyisocyanate which has at least 60% biosourced carbons, in that the polyol phase is a mixture of two polyols, and in that said method comprises the steps of: evaluation of the equivalent volume in isocyanate function (IEV1, IEV2) of the isocyanate-terminated prepolymer including, where appropriate, excess polyisocyanate, and of the polyisocyanate which has at least 60% biosourced carbons of the polyisocyanate phase and, evaluation of the equivalent volume in alcohol function (HEV1, HEV2) of each of the two polyols of the polyol phase, and adjustment of the respective volume percentage (%VI1, %VI2) of each of the isocyanate-terminated prepolymer including, where applicable, excess polyisocyanate, and of the polyisocyanate which comprises at least 60% biosourced carbons in the polyisocyanate phase, and of the respective volume percentage (%VH1, %VH2) of each of the two polyols in the polyol phase by responding to the following formula: VI * IEV = V2 * HEV where IEV is the equivalent volume in isocyanate function of the polyisocyanate phase and corresponds to the following formula: IEV = (%VI1 * IEV1) + (%VI2 * IEV2) and where HEV is the equivalent volume in alcohol function of the polyol phase and corresponds to the following formula: HEV = (%VH1 * HEV1) + (%VH2 * HEV2~) the volume V1 of polyisocyanate phase is equal to the volume V2 of polyol phase, and in that the adjustment of the respective volume percentage (%VI1,%VI2) of the two polyisocyanates of the isocyanate phase and the respective volume percentage (%VH1,%VH2) of the two polyols of the polyol phase is carried out by responding to the following formula: IEV(polyisocyanate phase) = HEV (polyol phase) where IEV is the equivalent volume in isocyanate function of the polyisocyanate phase and corresponds to the following formula: IEV = (%VI1 * IEV1) + (%VI2 * IEV2) and where HEV is the alcohol equivalent volume of the polyol phase and corresponds to the following formula: HEV = (%VH1 * HEV1) + (%VH2 * HEV2) the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% of biosourced carbon with poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% of biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% of biosourced carbons in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% of biosourced carbon and castor oil in a ratio between 40:60 and 70:30 comprising 100% bio-sourced carbon.the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% biosourced carbon with poly(1,3-propanediol) of molar mass between 900 and 1100g / mol comprising 100% biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% biosourced carbon in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% biosourced carbon or poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% biosourced carbon bio-sourced, and castor oil in a ratio of between 20:80 and 60:40 comprising 100% bio-sourced carbon. The process further comprises a step of adding catalyst to the polyol phase before mixing the polyisocyanate and polyol phases.
[0016] Finally, the invention also relates to a printed support covered at least in part with a resin dome which is essentially characterized in that the resin dome is made from the polyurethane resin composition as previously mentioned. BRIEF DESCRIPTION OF THE FIGURES
[0017] Other characteristics and advantages of the invention will emerge clearly from the description given below, for information purposes only and in no way limiting, with reference to the appended figures, among which: - Figure 1 is a schematic representation of the preparation of the isocyanate-terminated prepolymer of Example 1, and - Figure 2 is a schematic representation of the preparation of the isocyanate-terminated prepolymer of Example 2. DETAILED DESCRIPTION
[0018] The bio-sourced polyurethane resin composition of the invention comprises a mixture of a volume V1 of polyisocyanate phase, and a volume V2 of polyol phase. According to the invention, at least one of the two phases comprises two compounds making it possible to modulate the equivalent volume as a function of the reactive properties of these phases according to the intended applications and the constraints applied.
[0019] It can thus be provided that the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer which comprises at least 70% biosourced carbons, and the polyol phase comprises two polyols which each comprise at least 80% biosourced carbons,
[0020] Alternatively, it may be provided that the polyol phase comprises a polyol which comprises at least 80% bio-sourced carbons, and the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer which comprises at least 70% bio-sourced carbons and a polyisocyanate which comprises at least 60% bio-sourced carbons.
[0021] Under these assumptions and according to the invention, the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer. Preferably, the polyisocyanate phase also comprises a diisocyanate isocyanurate which comprises at least less than 60% bio-sourced carbons. The polyol phase comprises at least one polyether polyol which contains at least 80% bio-sourced carbons and preferably 100% bio-sourced carbons.
[0022] In the doming application, the composition includes at least one trifunctional compound, i.e. one with three reactive sites, in order to produce a three-dimensional resin. Diisocyanate isocyanurate (for the polyisocyanate phase) and castor oil (for the polyol phase) fulfill this function. For other applications where it is not necessary to obtain a crosslinked material, the presence of a trifunctional compound is not necessary.
[0023] In a first embodiment of the invention, the composition comprises an isocyanate-terminated prepolymer, and two polyols. In a second embodiment of the invention, the composition comprises an isocyanate-terminated prepolymer and another polyisocyanate, and a polyol.
[0024] In a preferred embodiment of the invention, the composition is a mixture of an isocyanate-terminated prepolymer and another polyisocyanate for the isocyanate phase, and two polyols for the polyol phase. The isocyanate-terminated prepolymer has at least 75% bio-sourced carbons, the other polyisocyanate more preferably at least 60% bio-sourced carbons, and the polyols each have at least 90% bio-sourced carbons, preferably 100% bio-sourced carbons. The use of at least two compounds in each of the phases makes it easier to modulate the equivalent volume as a function of reagents of each of the phases by using a wider spectrum of compounds in a field where the number of bio-sourced compounds is low.
[0025] The use of an isocyanate-terminated prepolymer offers a first advantage regarding the issue of toxicity reduction. Indeed, the toxicity of isocyanates is often linked to their high reactivity and volatility. However, an isocyanate-polyol-isocyanate prepolymer is both much less reactive than the isocyanate monomer, and also much more viscous and therefore less volatile.
[0026] The use of an isocyanate-terminated prepolymer in the polyisocyanate phase is also advantageous because it allows the percentage of bio-sourced carbons to be substantially increased. Indeed, in a formulation for which the polyisocyanate phase comprises one or two polyisocyanates (without prepolymer), the percentage of bio-sourced carbons in the resulting composition will be of approximately 70-80% then for the composition of the invention, the percentage of biosourced carbons will be close to 90%.
[0027] This is explained by the method of preparation of the prepolymer which is preferably made from a mixture of pentamethylene diisocyanate comprising at least 60% of biosourced carbons, with a polyol, for example poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol or poly(1,3-propanediol) with a molar mass of between 900 and 1100g / mol each comprising at least 80% of biosourced carbons, preferably 100% of biosourced carbons. Alternatively, as explained in Examples 1 and 2, the pentamethylene diisocyanate is used in excess in the mixture to ensure the preparation of the prepolymer with two opposite isocyanate ends, which results in obtaining the prepolymer and excess pentamethylene diisocyanate.The use of isocyanate-polyol-isocyanate prepolymers thus makes it possible to easily modulate the value of the equivalent volume of the polyisocyanate phase and in the composition since this value depends on both the molar mass of the isocyanate and the polyol.
[0028] The presence of an isocyanate-terminated prepolymer and a polyisocyanate in the polyisocyanate phase, and of at least two polyols in the polyol phase therefore makes it possible to modulate the number of reactive functions, respectively isocyanate and polyol, in each of the phases. Thus, depending on the intended application, it will be possible to produce a polyisocyanate phase comprising more or fewer reactive functions than in the polyol phase.
[0029] In certain fields, it may be desired to have a composition in which the number of isocyanate functions is greater than the number of alcohol functions. The composition of the invention makes it possible to manufacture such a composition.
[0030] In the field of doming, and more particularly when the addition of adjuvants in the composition is not planned, the number of reactive functions in the two phases must be equal, in particular to avoid any formation of air bubbles in the polyurethane resin. Indeed, an excess of isocyanate functions which would not react with the alcohol functions, could react with the water present in the ambient air leading to the formation of amine and carbon dioxide, and therefore bubbles in the dry composition. In this case, it is therefore a question of adjusting the mixture of polyisocyanates in the polyisocyanate phase, and the mixture of polyols in the polyol phase in order to ensure that no excess isocyanate function can react with the water.
[0031] To do this, one can use an isocyanate-terminated prepolymer and a polyisocyanate in the polyisocyanate phase and two polyols in the polyol phase, which allows both the number of reactive functions in each phase to be modulated, while reasonably limiting the evaluations to be carried out to do so.
[0032] In doming, the phases to be mixed are in a liquid state, and it is therefore a question of mixing a volume V1 of polyisocyanate phase and a volume V2 of polyol phase. The number of reactive functions in each of the phases must therefore be adjusted to be equal, taking into account the mixing of these phases in liquid form.
[0033] To do this, we work, according to the invention, in equivalent volume in reactive function.
[0034] It is known to use the equivalent mass, expressed in grams / equivalent, to define the mass of a compound allowing to obtain an equivalent of reactive site. The equivalent mass of a compound corresponds to the following formula: Formula 1 where M is the molar mass in grams per mole, W is the mass in grams, and f is the functionality (the number of reactive functions carried by a chemical compound)
[0035] Inspired by the equivalent mass and in view of the constraints imposed in the field of doming and in particular the use of phases in the liquid state, the inventors adapted the use of the equivalent mass to the equivalent volume in reactive function.
[0036] The equivalent volume is thus the volume of a compound allowing to obtain an equivalent of reactive site. The equivalent volume corresponds to the following formula: Formula 2 where p is the density in grams per cubic centimeter of the compound concerned.
[0037] It is therefore a question of developing a polyisocyanate phase of volume V1 and of equivalent volume in reactive site IEV which is equal to the equivalent volume in reactive site HEV of the polyol phase of volume V2. It will thus be a question of satisfying the following formula: IEV (polyisocyanate phase) = HEV (polyol phase) Formula 3
[0038] To do this, the isocyanate-based equivalent volume (IEV1, IEV2) of each of the isocyanate-terminated prepolymer, the excess pentamethylene diisocyanate, and the polyisocyanate in the polyisocyanate phase is evaluated, and the alcohol-based equivalent volume (HEV1, HEV2) of each of the two polyols in the polyol phase is evaluated in the same way. The respective volume percentage (%VI1, %VI2) of the isocyanate-terminated prepolymer and the polyisocyanate in the polyisocyanate phase and the respective volume percentage (%VH1, %VH2) of each of the two polyols in the polyol phase are then adjusted to satisfy the above equation, it being understood that the IEV reactive site equivalent volume of the polyisocyanate phase and the HEV reactive site equivalent volume of the polyol phase satisfy the following formulas: IEV(polyisocyanate phase) = (%VI1*IEV1)+(%Vl2*IEV2) Formula 4 Where IEV1 is the equivalent volume in isocyanate function of the isocyanate-terminated prepolymer and the excess polyisocyanate used to make the isocyanate-terminated prepolymer, pentamethylene diisocyanate in the examples presented. Where IEV2 is the equivalent volume in isocyanate function of the polyisocyanate which contains at least 60% biosourced carbons. HEV (polyol phase) =(%VH1*HEV1)+(%VH2*HEV2) Formula 5 Where HEV1 is the alcohol equivalent volume of the first polyol Where HEV2 is the alcohol equivalent volume of the second polyol
[0039] This method of evaluating the volume percentages of each of the compounds in the corresponding phase can of course be generalized to the use of more than one isocyanate-terminated prepolymer and one polyisocyanate in the polyisocyanate phase and to more than two polyols in the polyol phase.
[0040] In doming, volumes V1 of polyisocyanate phase and V2 of polyol phase are commonly used, which are identical. This therefore involves producing a polyisocyanate phase and a polyol phase for which, respectively, the equivalent volume in isocyanate function IEV and the equivalent volume in alcohol function HEV are equal. This therefore involves adjusting the respective volume percentage (%Vh, %Vl2) of each of the two polyisocyanates in the polyisocyanate phase and the respective volume percentage (%VH1, %VH2) of each of the two polyols in the polyol phase to satisfy the following formula: (%VI1*IEV1)+(%VI2*IEV2) = (%VH1*HEV1)+(%VH2*HEV2) Formula 6 This formula responds to the following more general formula: IEV (polyisocyanate phase) = HEV (polyol phase) Formula 3
[0041] In the case of the use of a single isocyanate-terminated prepolymer in the polyisocyanate phase or a single polyol in the polyol phase, formulae 4, 5 and 6 are adapted accordingly, in accordance with what is indicated in examples 5 and 6.
[0042] According to the process of the invention, a catalyst is added to the polyol phase. Preferably, the catalyst is dibutyltin dilaurate. The use of a catalyst makes it possible to modulate the gel time of the composition (setting time).
[0043] According to the process of the invention, each of the polyol and polyisocyanate phases is prepared in parallel. Each phase is stirred for approximately 30 seconds at approximately 2500 rpm. The two phases are then mixed for approximately 60 seconds at approximately 2500 rpm. Alternatively, the stirring may be mechanical and carried out in dedicated reactors. The composition is then cast onto a printed support to form a resin dome using doming techniques known to those skilled in the art.
[0044] The compounds used in each of the polyisocyanate and polyol phases are partially or totally bio-sourced.
[0045] For the polyisocyanate phase, an isocyanate-terminated prepolymer is preferably used, obtained by reacting: - either pentamethylene diisocyanate with poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol, - either pentamethylene diisocyanate with poly(1,3-propanediol) with a molar mass between 900 and 1100g / mol.
[0046] Alternatively, the polyol used to make the isocyanate-terminated prepolymer may be poly(1,3-propanediol) with a molar mass of between 150 and 350 g / mol.
[0047] The polyisocyanate used in the polyisocyanate phase is preferably a diisocyanate isocyanurate.
[0048] When the volumes V1 of isocyanate phase and V2 of polyol phase are identical in the polyurethane resin composition of the invention, the isocyanate-terminated prepolymer and the diisocyanate isocyanurate are present in the isocyanate phase in a volume ratio of between 30:70 and 70:30. These isocyanate compounds also have low toxicity.
[0049] For the polyol phase, a polyether polyol and castor oil are preferably used, each polyol comprising 100% bio-sourced carbons. The polyether polyol is preferably a poly(1,3-propanediol) with a molar mass between 400 and 600g / mol.
[0050] More preferably, and more particularly when the volumes V1 of polyisocyanate phase and V2 of polyol phase are identical in the polyurethane resin composition of the invention, the polyol phase is made from a mixture of castor oil and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol in a volume ratio of between 20:80 and 60:40.
[0051] An important criterion for the production of a polyurethane resin composition for doming is viscosity. To meet this criterion, each compound of the isocyanate phase and the polyol phase has a viscosity of less than 900 mPa.s at 20°C.
[0052] If the composition and the process of the invention are more particularly implemented within the framework and around the constraints of the field of doming, the polyurethane resin composition of the invention as well as its associated process can find application in numerous fields, in particular in the automobile sector, the naval sector, construction, furniture, architecture, sport or even adhesives.
[0053] In electronics, potting is a process of filling electronic components with a solid or gelatinous compound. This increases resistance to shock and vibration, and protects components from water, humidity, and corrosive agents. The components concerned may include, but are not limited to: electronic control units, electric motors, charging connectors, door handles, capacitors, batteries, sensors, printed circuit boards, or lighting.
[0054] In the electrical field, encapsulation is a process used to provide electrical insulation, flexibility, and good adhesion to most substrates. Some polyurethane resins offer exceptional resistance to saline environments and extreme temperatures. Components affected include, but are not limited to: igniters, submersible pumps, ignition coils, water shutoff valves, sensors, transformers, capacitors, electric motors, and printed circuit boards.
[0055] Finally, the composition of the invention can also find application for the encapsulation of LED luminaires exposed to the open air and which require protection against water infiltration.
[0056] Example 1 - Preparation of a first isocyanate-terminated prepolymer
[0057] With reference to Figure 1, prepolymer 3 is prepared by mixing poly(1,3-propanediol) 1 with a molar mass of between 400 and 600g / mol marketed under the name Velvetol® H500 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method) with pentamethylene diisocyanate 2 marketed under the name Stabio®PDI® by the company Mitsui Chemicals and presenting a percentage of biosourced carbon of 71%.
[0058] The mixture contains excess pentamethylene diisocyanate 2 to ensure the development of the prepolymer with two opposite isocyanate ends. In this example, 2.5 equivalents of pentamethylene diisocyanate are used for 1 equivalent of poly(1,3-propanediol) 1 .
[0059] Poly(1,3-propanediol) 1 is slowly added to pentamethylene diisocyanate 2 at a rate of approximately 10 mL / h and then the mixture is maintained at a temperature of 80°C for 4 hours. 1 equivalent of double-terminated isocyanate prepolymer and polyether backbone 3 is then obtained, and 0.5 equivalent of excess pentamethylene diisocyanate 2a.
[0060] The assembly formed by prepolymer 3 and excess pentamethylene diisocyanate has a percentage of biosourced carbon of 88%.
[0061] This assembly is used to produce the bio-sourced polyurethane resin composition of the invention as will be described in embodiments 3, 5 and 6.
[0062] Example 2 - Preparation of a second isocyanate-terminated prepolymer
[0063] With reference to Figure 2, the 3' prepolymer is prepared by mixing poly(1,3-propanediol) T with a molar mass of between 900 and 1100g / mol marketed under the name Velvetol® H500 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method) with pentamethylene diisocyanate 2 marketed under the name Stabio®PDI® and having a percentage of biosourced carbon of 71%.
[0064] The mixture contains excess pentamethylene diisocyanate 2 to ensure the development of the prepolymer with two opposite isocyanate ends. In this example, 2.5 equivalents of pentamethylene diisocyanate are used for 1 equivalent of poly(1,3-propanediol) T.
[0065] Poly(1,3-propanediol) T is slowly added to pentamethylene diisocyanate 2, and the mixture is then maintained at a temperature of 80°C for 4 hours. 1 equivalent of double-terminated isocyanate prepolymer and polyether backbone 3', and 0.5 equivalent of excess pentamethylene diisocyanate 2a, are then obtained.
[0066] The assembly formed by prepolymer 3 and excess pentamethylene diisocyanate has a percentage of biosourced carbon of 92%.
[0067] This assembly is used to produce the bio-sourced polyurethane resin composition of the invention as will be described in embodiments 4 and 6.
[0068] Example 3: Preparation of a composition of the invention
[0069] The polyisocyanate phase is a mixture of the assembly formed by prepolymer 3 of example 1 and excess pentamethylene diisocyanate, and pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by the company Mitsui Chemicals (67% biosourced carbons according to the ASTM D6866 method).
[0070] The polyol phase is a mixture of castor oil marketed by the company Alberdingk Boley (100% biosourced carbons according to the ASTM D6866 method) and poly(1,3-propanediol) with a molar mass between 150 and 250g / mol marketed under the name Velvetol® H250 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method).
[0071] The equivalent volumes in reactive function respectively of the prepolymer 3 and excess pentamethylene diisocyanate assembly (IEV1), of the pentamethylene diisocyanate isocyanurate (IEV2), of the castor oil (HEV1) and of the poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (HEV2) are evaluated and reported in Table 1 below.
[0072] To comply with industrial constraints in terms of doming, the volume V1 of the polyisocyanate phase is equal to the volume V2 of the polyol phase.
[0073] The respective volume percentage of the prepolymer 3 and excess pentamethylene diisocyanate (%Vh), of the pentamethylene diisocyanate isocyanurate (%V), of the castor oil (%VH1) and of the poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (%VH2) in each of the phases are adjusted so that the equivalent volume in isocyanate function of the polyisocyanate phase (IEV) is equal to the equivalent volume in alcohol function of the polyol phase (HEV).
[0074] The respective volume percentages of each compound thus correspond to the following formula: (%VI1*IEV1)+(%VI2*IEV2) = (%VH1*HEV1)+(%VH2*HEV2) Formula 6
[0075] Table 1 reports the equivalent volume in reactive function of each compound as well as the volume percentage of each compound in the phase considered to satisfy the above formula. The equivalent volume in reactive function of each phase is also indicated. Table 1: Equivalent volumes and volume percentages of each compound in compositions A, B and C. 5
[0076] Table 2 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases for the three compositions Table 2: Viscosity of each compound and resulting viscosity of each phase and 0 for each of the compositions
[0077] To prepare the polyol phase, depending on the composition manufactured, 51.5%, 45% or 39% by volume of castor oil is mixed with 48.50%, 55% or 61% by volume of Velvetol® H250 respectively. 0.065% by mass is added to this polyol phase dibutyltin dilaurate as a catalyst. The whole is stirred for 30 seconds at 2500 rpm.
[0078] To prepare the polyisocyanate phase, depending on the composition manufactured, 60%, 50% or 40% by volume of the prepolymer 3 and Stabio®PDI® combination in excess are mixed with, respectively, 40%, 50% or 60% by volume of Stabio D376N. The mixture is stirred for 30 seconds at 2500 rpm.
[0079] 50% by volume of polyol phase is then mixed with 50% by volume of polyisocyanate phase. The mixture is stirred for 60 seconds at 2500 rpm. The composition is then cast onto a printed support to form a resin dome.
[0080] Various parameters associated with the resin are evaluated and observed. Transparency is assessed visually; the ++ rating indicates total transparency. Table 3 below shows the results obtained as well as the percentage of bio-sourced carbon in the composition. Table 3: Physicochemical properties of compositions A, B and C
[0081] These compositions meet the criteria imposed in the field of doming.
[0082] Example 4: Preparation of a composition of the invention
[0083] The polyisocyanate phase is a mixture of the assembly formed by the 3' prepolymer of example 2 and the excess pentamethylene diisocyanate, and pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by Mitsui Chemicals (67% bio-sourced carbons according to ASTM D6866 method).
[0084] The polyol phase is a mixture of castor oil marketed by the company Alberdingk Boley (100% biosourced carbons according to the ASTM D6866 method) and poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol marketed under the name Velvetol® H500 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method) or poly(1,3-propanediol) with a molar mass of between 150 and 350g / mol marketed under the name Velvetol® H250 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method).
[0085] The equivalent volumes in reactive function respectively of the 3' prepolymer and excess pentamethylene diisocyanate (IEV1), of the pentamethylene diisocyanate isocyanurate (IEV2), of the castor oil (HEV1) and of the poly(1,3-propanediol) are evaluated and reported in Table 4 below.
[0086] To comply with industrial constraints in terms of doming, the volume V1 of the polyisocyanate phase is equal to the volume V2 of the polyol phase.
[0087] The respective volume percentage of the 3' prepolymer and excess pentamethylene diisocyanate (%Vh), pentamethylene diisocyanate isocyanurate (%VI2), castor oil (%VH1) and poly(1,3-propanediol) by mass (%VH2) in each of the phases are adjusted so that the equivalent volume in isocyanate function of the polyisocyanate phase (IEV) is equal to the equivalent volume in alcohol function of the polyol phase (HEV).
[0088] The respective volume percentages of each compound thus correspond to the following formula: (%VI1*IEV1)+(%VI2*IEV2) = (%VH1*HEV1)+(%VH2*HEV2) Formula 6
[0089] Table 4 reports the equivalent volume in reactive function of each compound as well as the volume percentage of each compound in the phase considered to satisfy the above formula. The equivalent volume in reactive function of each phase is also indicated. Table 4: Equivalent volumes and volume percentage of each compound in compositions D, E and F.
[0090] Table 5 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases for the three compositions Table 5: Viscosity of each compound and resulting viscosity of each phase and for each of the compositions
[0091] To prepare the polyol phase, 75%, 42% or 65% by volume of castor oil is mixed with 25%, 58% or 35% by volume of Velvetol® H500 or Velvetol® H250 respectively, depending on the composition being manufactured. 0.065% by mass of dibutyltin dilaurate is added to this polyol phase as a catalyst. The whole is stirred for 30 seconds at 2500 rpm.
[0092] To prepare the polyisocyanate phase, depending on the composition manufactured, 60%, 50% or 40% by volume of the 3' prepolymer and Stabio®PDI® combination in excess are mixed with, respectively, 40%, 50% or 60% by volume of Stabio D376N. The mixture is stirred for 30 seconds at 2500 rpm.
[0093] 50% by volume of polyol phase is then mixed with 50% by volume of polyisocyanate phase. The mixture is stirred for 60 seconds at 2500 revolutions per minute. The composition is then poured onto a printed support to form a resin dome.
[0094] Various parameters associated with the resin are evaluated and observed. Transparency is assessed visually; the ++ rating indicates total transparency. Table 6 below shows the results obtained as well as the percentage of bio-sourced carbon in the composition. Table 6: Physicochemical properties of compositions D, E and F
[0095] These compositions meet the criteria imposed in the field of doming.
[0096] Example 5: Preparation of a composition of the invention
[0097] In this example, the polyisocyanate phase consists of prepolymer 3 and excess pentamethylene diisocyanate from example 1.
[0098] The polyol phase is a mixture of castor oil marketed by the company Alberdingk Boley (100% biosourced carbons according to the ASTM D6866 method) and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol marketed under the name Velvetol® H500 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method).
[0099] The equivalent volumes in reactive function respectively of prepolymer 3 and excess pentamethylene diisocyanate (IEV1), castor oil (HEV1) and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (HEV2) are evaluated and reported in Table 7 below.
[0100] To comply with industrial constraints in terms of doming, the volume V1 of the polyisocyanate phase is equal to the volume V2 of the polyol phase.
[0101] The respective volume percentage of prepolymer 3 and excess pentamethylene diisocyanate (%Vh), castor oil (%VH1) and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (%VH2) in each of the phases are adjusted so that the equivalent volume in isocyanate function of the polyisocyanate phase (IEV) is equal to the equivalent volume in alcohol function of the polyol phase (HEV).
[0102] The respective volume percentages of each compound thus correspond to the following formula: (%VI1*lEV1) = (%VH1*HEV1)+(%VH2*HEV2) Formula 6
[0103] Table 7 reports the equivalent volume in reactive function of each compound as well as the volume percentage of each compound in the phase considered to satisfy the above formula. The equivalent volume in reactive function of each phase is also indicated. Table 7: Equivalent volumes and volume percentage of each compound in composition G.
[0104] Table 8 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases of composition G. Table 8: Viscosity of each compound and resulting viscosity of each phase
[0105] To prepare the polyol phase, 40% by volume of castor oil is mixed with 60% by volume of Velvetol® H500. 0.065% by mass of dibutyltin dilaurate is added to this polyol phase as a catalyst. The mixture is stirred for 30 seconds at 2500 rpm.
[0106] 50% by volume of polyol phase is then mixed with 50% by volume of polyisocyanate phase consisting of prepolymer 3 and excess pentamethylene diisocyanate. The mixture is stirred for 60 seconds at 2500 rpm. The composition is then cast onto a printed support to form a resin dome.
[0107] Various parameters associated with the resin are evaluated and observed. Transparency is assessed visually; the ++ rating indicates total transparency. Table 9 below shows the results obtained as well as the percentage of bio-sourced carbon in the composition. Table 9: Physicochemical properties of composition G
[0108] This composition meets the criteria imposed in the field of doming.
[0109] Example 6: Preparation of compositions of the invention
[0110] The polyisocyanate phase is either a mixture of the assembly formed by prepolymer 3 of example 1 and excess pentamethylene diisocyanate and pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by the company Mitsui Chemicals (67% biosourced carbons according to the ASTM D6866 method), or a mixture of the assembly formed by prepolymer 3' of example 2 and excess pentamethylene diisocyanate and Stabio D376N.
[0111] The polyol phase consists of either castor oil marketed by the company Alberdingk Boley (100% biosourced carbons according to the ASTM D6866 method), or poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol marketed under the name Velvetol® H500 by the company Allessa (100% biosourced carbons according to the ASTM D6866 method).
[0112] The equivalent volumes in reactive function respectively of the prepolymer 3' or prepolymer 3 and excess pentamethylene diisocyanate (IEV1), of the pentamethylene diisocyanate isocyanurate (IEV2), and of the castor oil (HEV1) or of the poly(1,3-propanediol) with a molar mass between 400 and 600g / mol are evaluated and reported in Table 10 below.
[0113] To comply with industrial constraints in terms of doming, the volume V1 of the polyisocyanate phase is equal to the volume V2 of the polyol phase.
[0114] The respective volume percentage of the prepolymer 3' or prepolymer 3 and excess pentamethylene diisocyanate (%Vh), of the pentamethylene diisocyanate isocyanurate (%Vh), and of the castor oil or poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol (%VH1) in each of the phases are adjusted so that the equivalent volume in isocyanate function of the polyisocyanate phase (IEV) is equal to the equivalent volume in alcohol function of the polyol phase (HEV).
[0115] The respective volume percentages of each compound thus correspond to the following formula: (%VI1*IEV1)+(%VI2*IEV2) = (%VH1*HEV1) Formula 6
[0116] Table 10 reports the equivalent volume in reactive function of each compound as well as the volume percentage of each compound in the phase considered to satisfy the above formula. The equivalent volume in reactive function of each phase is also indicated. Table 10: Equivalent volumes and volume percentage of each compound of compositions H and I.
[0117] Table 11 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases for the two compositions. Table 11: Viscosity of each compound and resulting viscosity of each phase for compositions H and I
[0118] To prepare the polyol phase, 0.065% by mass of dibutyltin dilaurate is added to castor oil or Velvetol® H500 as a catalyst. The mixture is stirred for 30 seconds at 2500 rpm.
[0119] To prepare the polyisocyanate phase, depending on the composition manufactured, 75% by volume of the prepolymer 3 and Stabio®PDI® combination in excess is mixed with 35% by volume of Stabio D376N, or 68% by volume of the prepolymer 3' and Stabio®PDI® combination in excess with 32% by volume of Stabio D376N. The mixture is stirred for 30 seconds at 2500 rpm.
[0120] 50% by volume of polyol phase is then mixed with 50% by volume of polyisocyanate phase. The mixture is stirred for 60 seconds at 2500 rpm. The composition is then cast onto a printed support to form a resin dome.
[0121] Various parameters associated with the resin are evaluated and observed. Transparency is assessed visually; the ++ rating indicates total transparency. Table 12 below shows the results obtained as well as the percentage of bio-sourced carbon in the compositions. Table 12: Physicochemical properties of compositions H and I
[0122] These compositions meet the criteria imposed in the field of doming.
Claims
CLAIMS
1. Bio-sourced polyurethane resin composition, characterized in that it is obtained by mixing a volume V1 of polyisocyanate phase, and a volume V2 of polyol phase, and in that: - either the polyisocyanate phase comprises at least two polyisocyanates, at least one of which is an isocyanate-terminated prepolymer which comprises at least 70% biosourced carbons and the other comprises at least 60% biosourced carbons, and the polyol phase comprises at least one polyol which comprises at least 80% biosourced carbons, - either the polyol phase comprises at least two polyols which each comprise at least 80% biosourced carbons, and the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer which comprises at least 70% biosourced carbons.
2. Composition according to claim 1, characterized in that the isocyanate-terminated prepolymer of the polyisocyanate phase has a polyether-type skeleton.
3. Composition according to any one of claims 1 and 2, characterized in that the number of isocyanate functions in the polyisocyanate phase is equal to the number of alcohol functions in the polyol phase.
4. Composition according to any one of the preceding claims, characterized in that the isocyanate-terminated prepolymer is obtained by reacting a polyol which comprises at least 80% biosourced carbons and a polyisocyanate which comprises at least 60% biosourced carbons.
5. Composition according to claim 4, characterized in that the polyol is a polyether polyol which comprises 100% biosourced carbons.
6. Composition according to any one of the preceding claims, characterized in that the isocyanate-terminated prepolymer is obtained by reacting: - either pentamethylene diisocyanate comprising at least 60% biosourced carbons with poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol comprising 100% biosourced carbons, - either pentamethylene diisocyanate comprising at least 60% biosourced carbons with poly(1,3-propanediol) with a molar mass of between 900 and 1100g / mol comprising 100% biosourced carbons.
7. Composition according to the preceding claim, characterized in that when the polyisocyanate phase comprises at least two polyisocyanates, the polyisocyanate which comprises at least 60% of biosourced carbons is a diisocyanate, preferably a diisocyanate isocyanurate.
8. Composition according to any one of the preceding claims, characterized in that the polyol(s) of the polyol phase comprise 100% biosourced carbons.
9. Composition according to claim 8, characterized in that the polyol phase comprises a polyether polyol and / or castor oil.
10. Composition according to any one of the preceding claims, characterized in that it is obtained by mixing the same volume of polyisocyanate phase and polyol phase, and in that the number of isocyanate functions in the polyisocyanate phase is equal to the number of alcohol functions in the polyol phase.
11. Composition according to claim 10, characterized in that the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% of biosourced carbon with poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% of biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% of biosourced carbons in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% of biosourced carbon and castor oil in a ratio between 40:60 and 70:30 comprising 100% bio-sourced carbon.
12. Composition according to claim 11, characterized in that the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% of biosourced carbon with poly(1,3-propanediol) of molar mass between 900 and 1100g / mol comprising 100% of biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% of biosourced carbons in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% of biosourced carbon or poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% bio-sourced carbon, and castor oil in a ratio of between 20:80 and 60:40 comprising 100% bio-sourced carbon.
13. Composition according to any one of the preceding claims, characterized in that it comprises at least 80% of biosourced carbons, preferably at least 85% of biosourced carbons.
14. A method of manufacturing a polyurethane resin composition according to any one of claims 1 to 13, characterized in that it comprises at least the steps of: - supply or preparation of a polyisocyanate phase of volume V1 and supply or preparation of a polyol phase of volume V2, for which phases: o either the polyisocyanate phase comprises at least two polyisocyanates of which at least one is an isocyanate-terminated prepolymer which comprises at least 70% biosourced carbons and the other comprises at least 60% biosourced carbons, and the polyol phase comprises at least one polyol which comprises at least 80% biosourced carbons, o or the polyol phase comprises at least two polyols which each comprise at least 80% biosourced carbons, and the polyisocyanate phase comprises at least one isocyanate-terminated prepolymer which comprises at least 70% biosourced carbons. - mixture of polyisocyanate and polyol phases.
15. Method according to the preceding claim, characterized in that the isocyanate-terminated prepolymer is obtained by reacting a polyol which comprises at least 80% biosourced carbons and a polyisocyanate which comprises at least 60% biosourced carbons.
16. Method according to any one of claims 14 and 15, characterized in that the polyol phase comprises two different polyols which each comprise 100% biosourced carbons and in that the polyisocyanate phase comprises two polyisocyanates, the polyisocyanate which comprises at least 60% biosourced carbons being a diisocyanate isocyanurate.
17. Manufacturing method according to any one of claims 14 to 16, characterized in that it further comprises the steps of: - evaluation of the equivalent volume in isocyanate function (IEVÏ, IEVH IEVi n) of the isocyanate-terminated prepolymer including, where applicable, excess polyisocyanate used for the manufacture of the isocyanate-terminated prepolymer or of the isocyanate-terminated prepolymer y including, where applicable, excess polyisocyanate and polyisocyanate which contains at least 60% bio-sourced carbons from the polyisocyanate phase, - evaluation of the equivalent volume in terms of alcohol (HEVh, HEVhh .... HEVh n ) of the polyol or of each of the at least two polyols of the polyol phase, and - adjustment of the respective volume percentage (%VIi, %VI ii , .... %VIi n ) of each of the at least two polyisocyanates in the isocyanate phase and / or and the respective volume percentage (%VHh,%VHhh,...,%VHh n ) of each of the at least two polyols in the polyol phase, corresponding to the following formula: V1 * IEV = V2 * HEV where IEV is the equivalent volume in isocyanate function of the polyisocyanate phase and corresponds to the following formula: IEV = (%VIi * IEVi) + (%VIii * IEV ii) + ••• + (% VIin * lEVin) and where HEV is the equivalent volume in alcohol function of the polyol phase and corresponds to the following formula: HEV = (%VHh * HEVh) + (%VHhh * HEVhh) + ••• + (%VHhn * HEVhh)
18. Manufacturing process according to claim 17, characterized in that the polyisocyanate phase is a mixture comprising at least the isocyanate-terminated prepolymer and the polyisocyanate which has at least 60% biosourced carbons, in that the polyol phase is a mixture of two polyols, and in that said process comprises the steps of: - evaluation of the equivalent volume in isocyanate function (IEV1. IEV2) of the isocyanate-terminated prepolymer including, where applicable, excess polyisocyanate, and of the polyisocyanate which has at least 60% of biosourced carbons from the polyisocyanate phase and, - evaluation of the equivalent volume in alcohol function (HEV1, HEV2) of each of the two polyols of the polyol phase, and - adjustment of the respective volume percentage (%VI1, %VI2) of each of the isocyanate-terminated prepolymer including, where applicable, excess polyisocyanate, and of the polyisocyanate which comprises at least 60% biosourced carbons in the polyisocyanate phase, and of the respective volume percentage (%VH1, %VH2) of each of the two polyols in the polyol phase by responding to the following formula: VI * IEV = V2 * HEV where IEV is the equivalent volume in isocyanate function of the polyisocyanate phase and corresponds to the following formula: IEV = (%VI1 * IEV1) + (%VI2 * IEV2) and where HEV is the equivalent volume in alcohol function of the polyol phase and corresponds to the following formula: HEV = (%VH1 * HEV1) + (%VH2 * HEV2~)
19. Manufacturing method according to claim 18, characterized in that the volume V1 of polyisocyanate phase is equal to the volume V2 of polyol phase, and in that the adjustment of the respective volume percentage (%VI1,%VI2) of the two polyisocyanates of the isocyanate phase and of the respective volume percentage (%VH1,%VH2) of the two polyols of the polyol phase is carried out by responding to the following formula: IEV(polyisocyanate phase) = HEV (polyol phase) where IEV is the equivalent volume in isocyanate function of the polyisocyanate phase and corresponds to the following formula: IEV = (%VI1 * IEV1) + (%VI2 * IEV2) and where HEV is the alcohol equivalent volume of the polyol phase and corresponds to the following formula: HEV = (%VH1 * HEV1) + (%VH2 * HEV2)
20. Method according to claim 19, characterized in that the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% of biosourced carbon with poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% of biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% of biosourced carbons in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% of biosourced carbon and castor oil in a ratio between 40:60 and 70:30 comprising 100% bio-sourced carbon.
21. Method according to claim 19, characterized in that the polyisocyanate phase is a mixture of isocyanate-terminated prepolymer obtained by reacting pentamethylene diisocyanate comprising at least 65% of biosourced carbon with poly(1,3-propanediol) of molar mass between 900 and 1100g / mol comprising 100% of biosourced carbon, and pentamethylene diisocyanate isocyanurate comprising at least 60% of biosourced carbons in a volume ratio between 30:70 and 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 400 and 600g / mol comprising 100% of biosourced carbon or poly(1,3-propanediol) of molar mass between 150 and 350g / mol comprising 100% bio-sourced carbon, and castor oil in a ratio of between 20:80 and 60:40 comprising 100% bio-sourced carbon.
22. Manufacturing method according to any one of claims 14 to 21, characterized in that it further comprises a step of adding catalyst to the polyol phase before mixing the polyisocyanate and polyol phases.
23. Printed support covered at least in part with a resin dome, characterized in that the resin dome is made from the polyurethane resin composition according to any one of claims 1 to 13.