Biobased polyurethane resin composition, manufacturing method and use in particular in the technique of doming
Patent Information
- Application Number
- EP2022711577
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2022-02-18
- Publication Date
- 2024-12-25
AI Technical Summary
Conventional polyurethane resins used in doming techniques are petrochemical-based, posing toxicity and environmental hazards, and there is a lack of biosourced polyisocyanates that meet the necessary criteria for transparency, viscosity, polymerization time, and hardness required for effective doming applications.
A biosourced polyurethane resin composition is developed by mixing a polyisocyanate phase with at least 25% biobased carbons and a polyol phase with at least 80% biobased carbons, incorporating trifunctional compounds and polyether polyols, and adjusting the equivalent volumes of reactive functions to achieve the desired properties, along with a manufacturing process that includes preparing and mixing these phases to form a resin dome on printed media.
The biosourced polyurethane resin composition meets the criteria for transparency, viscosity, and hardness, providing a safe, environmentally friendly, and effective solution for doming applications while allowing for modulation of reactive functions to prevent bubble formation and ensure proper polymerization.
Smart Images
Figure IMGF000012_0001 
Figure IMGF000013_0001 
Figure IMGF000018_0001
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 reveal the print of the support, the viscosity of the polyol and polyisocyanate phases must be less than 900mPa.s at 25°C, 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.
[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 which each comprise at least 25% 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 polyisocyanate which comprises at least 25% of biosourced 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 composition comprises at least one trifunctional compound in its polyisocyanate phase and / or in its polyol phase, for example a diisocyanate isocyanurate which comprises at least 60% of biosourced carbons, the number of isocyanate functions in the polyisocyanate phase is equal to the number of alcohol functions in the polyol phase, the polyisocyanate phase comprises at least one diisocyanate isocyanurate which comprises at least 60% of biosourced carbons, and the polyol phase comprises at least one polyether polyol which comprises 100% of biosourced carbons. This composition advantageously makes it possible to combine the presence of a trifunctional compound for the doming field, and a compound comprising 100% of biosourced carbons.the composition is obtained by mixing a volume V1 of polyisocyanate phase comprising at least two polyisocyanates each comprising at least 25% biosourced carbons, and a volume V2 of polyol phase comprising at least two polyols each comprising at least 80% biosourced carbons. Such a composition advantageously makes it possible to easily modulate the number of isocyanate functions in the polyisocyanate phase and the number of alcohol functions in the polyol phase, given the limited choice of biosourced compounds on the market, in particular biosourced polyisocyanates. the composition is obtained by mixing a polyisocyanate phase comprising at least two polyisocyanates, one of which comprises at least 50% biosourced carbons, and a polyol phase comprising at least two polyols each comprising at least 90% biosourced carbons.the polyisocyanate phase is made from a mixture of isocyanurate diisocyanate which comprises at least 60% bio-sourced carbons and allophanate diisocyanate which comprises at least 25% bio-sourced carbons, the polyol phase is made from two different polyols which comprise 100% bio-sourced carbons, the polyol phase comprises either two polyether polyols, or one polyether polyol and castor oil,. the polyol phase comprises a poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and a poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol, 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 isocyanate phase is a mixture of diisocyanate isocyanurate which comprises at least 60% of biosourced carbons and diisocyanate allophanate which comprises at least 25% of biosourced carbons in a volume ratio of between 40:60 and 80:20, and the polyol phase is: either a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and a poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol in a volume ratio of between 30:70 and 45:55, i.e. a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and castor oil in a volume ratio of between 40:60 and 50:50, the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid in a ratio of 70:30, and the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol in a volume ratio of 38:62, the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid palmitic in a ratio of 50:50, and the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and castor oil in a volume ratio of 45:55, ,
[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 which each comprise at least 25% biosourced carbons, and the polyol phase comprises at least one polyol which comprises at least 80% biosourced carbons, 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 polyisocyanate which comprises at least 25% biosourced carbons, and mixture of the polyisocyanate and polyol phases.
[0015] The method of the invention may also comprise the following optional features considered in isolation or according to all possible technical combinations: the method comprises at least the steps of: providing or preparing a polyisocyanate phase of volume V1 comprising at least two polyisocyanates which each comprise at least 25% of biosourced carbons, providing or preparing a polyol phase of volume V2 comprising at least two polyols which each comprise at least 80% of biosourced carbons, and mixing the polyisocyanate and polyol phases. the polyisocyanate phase comprises at least two polyisocyanates, one of which comprises at least 50% of biosourced carbons, and the polyol phase comprises at least two polyols which each comprise at least 90% of biosourced carbons.the method further comprises the steps of: evaluating the equivalent volume as an isocyanate function (lEVi, lEVii lEVin) of the polyisocyanate or of each of the at least two polyisocyanates of 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 = 72 * 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 * IEV H) + ••• + (%7 / in * IEV in) 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 of two polyisocyanates, the polyol phase is a mixture of two polyols, and said method comprises the steps of: evaluating the equivalent volume in isocyanate function (IEV1, IEV2) of each of the two polyisocyanates of the polyisocyanate phase, evaluating the equivalent volume in alcohol function (HEV1, HEV2) of each of the two polyols of the polyol phase, and adjusting the respective volume percentage (%VI1, %VI2) 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 by responding to the following formula: VI * IEV = 72 * 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 * HEVV) + (%VH2 * HEV2~) the volume V1 of polyisocyanate phase is equal to the volume V2 of polyol phase, and 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 equivalent volume in alcohol function of the polyol phase and corresponds to the following formula: HEV = (%rai * HEV1) + (%VH2 * HEV2) the polyisocyanate phase is a mixture of diisocyanate isocyanurate which comprises at least 60% of biosourced carbons and diisocyanate allophanate which comprises at least 25% of biosourced carbons in a volume ratio of between 40:60 and 80:20, and the polyol phase is: either a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol in a volume ratio of between 30:70 and 45:55, or a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and castor oil in a volume ratio of between 40:60 and 50:50.the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid in a ratio of 70:30, and the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol in a volume ratio of 38:62. the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid in a ratio of 50:50, and the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and castor oil in a volume ratio of 45:55. the method 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.
[0017] The invention and its various applications will be better understood by reading the following description. 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 two polyisocyanates which each comprise at least 25% of biosourced carbons, and the polyol phase comprises at least one polyol which comprises at least 80% of biosourced carbons,
[0020] Alternatively, it may be provided that 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 polyisocyanate which comprises at least 25% bio-sourced carbons.
[0021] Under these assumptions, preferably, the polyisocyanate phase comprises at least one diisocyanate isocyanurate which comprises at least 60% biosourced carbons, and the polyol phase comprises at least one polyether polyol which comprises 100% biosourced 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 fulfills 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 a polyisocyanate and two polyols. In a second embodiment of the invention, the composition comprises two polyisocyanates and a polyol.
[0024] In a preferred embodiment of the invention, the composition is a mixture of at least two polyisocyanates, for the isocyanate phase, and at least two polyols, for the polyol phase. The polyisocyanates have at least 25% of biosourced carbons, preferably one of them has at least 50% of biosourced carbons, more preferably at least 60% of biosourced carbons, and the polyols each have at least 90% of biosourced carbons, preferably 100% of biosourced 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 biosourced compounds is low.
[0025] The presence of at least two polyisocyanates in the polyisocyanate phase and 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.
[0026] 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.
[0027] 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.
[0028] To do this, two polyisocyanates can be used in the polyisocyanate phase and two polyols in the polyol phase, which allows both the number of reactive functions in each to be modulated, while reasonably limiting the evaluations to be carried out to do so.
[0029] 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.
[0030] To do this, we work, according to the invention, in equivalent volume in reactive function.
[0031] 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)
[0032] 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.
[0033] 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.
[0034] 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
[0035] To do this, the equivalent volume in isocyanate function (IEVi, IEV2) of each of the two polyisocyanates of the polyisocyanate phase is evaluated, and the equivalent volume in alcohol function (HEV1, HEV2) of each of the two polyols of the polyol phase is evaluated in the same way. The respective volume percentage (%Vh, %Vl2) of each of the two polyisocyanates in the polyisocyanate phase is then adjusted, and the respective volume percentage (%VHi, %VH2) of each of the two polyols in the polyol phase in order to satisfy the above equation, it being understood that the equivalent volume in reactive site IEV of the polyisocyanate phase and the equivalent volume in reactive site HEV of the polyol phase satisfy the following formulas: I EV (poly iso cyanate phase) = (%VIi*IEVi)+(%Vl2*IEV2) Formula 4 Where IEVi is the isocyanate equivalent volume of the first polyisocyanate Where IEV2 is the isocyanate equivalent volume of the second polyisocyanate HEV (polyol phase) =(%VHI*HEVI) +(%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
[0036] 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 two polyisocyanates in the polyisocyanate phase and more than two polyols in the polyol phase.
[0037] In doming, it is commonly used that volumes V1 of polyisocyanate phase and V2 of polyol phase are identical. It is therefore a question of 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. It is thus a question of adjusting the respective volume percentage (%VI-i, %Vl2) of each of the two polyisocyanates in the polyisocyanate phase and the respective volume percentage (%VHI, %VH2) of each of the two polyols in the polyol phase to satisfy the following formula: (%V1I*1EVI) +(%V12*1EV2) = (%VHI*HEVI) + (%VH2*HEV2) Formula 6 This formula responds to the following more general formula: IEV (poly isocyanate phase) = HEV (polyol phase) Formula 3
[0038] In the case of the use of a single compound in the polyisocyanate phase or a single compound in the polyol phase, formulae 4, 5 and 6 are adapted accordingly, in accordance with what is indicated in examples 3 and 4.
[0039] 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).
[0040] 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.
[0041] The compounds used in each of the polyisocyanate and polyol phases are partially or totally bio-sourced.
[0042] For the polyisocyanate phase, a mixture of diisocyanate isocyanurate which comprises at least 60% biosourced carbons and diisocyanate allophanate which comprises at least 25% biosourced carbons is preferably used. More preferably, and more particularly when the volumes V1 of isocyanate phase and V2 of polyol phase are identical in the polyurethane resin composition of the invention, the diisocyanate isocyanurate and the diisocyanate allophanate are present in the isocyanate phase in a volume ratio of between 40:60 and 80:20. These isocyanate compounds also have low toxicity.
[0043] For the polyol phase, it is preferable to use either two polyether polyols of different molar masses, or a polyether polyol and castor oil, each polyol comprising 100% bio-sourced carbons.
[0044] In the case of the use of two polyether polyols, a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and a poly(1,3-propanediol) with a molar mass between 400 and 600g / mol is preferably used.
[0045] 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 either made of a mixture of poly(1,3-propanediol) with a molar mass of between 200 and 300g / mol and a poly(1,3-propanediol) with a molar mass of between 400 and 600g / mol in a volume ratio of between 30:70 and 45:55, or of a mixture of a mixture of poly(1,3-propanediol) with a molar mass of 250g / mol and castor oil in a volume ratio of between 40:60 and 50:50.
[0046] 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.
[0047] 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.
[0048] 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.
[0049] 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.
[0050] 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.
[0051] Example 1
[0052] The polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by Mitsui Chemicals (67% bio-sourced carbons according to the ASTM D6866 method) and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid marketed under the name Tolonate X Flo 100 by Vencorex (between 29 and 32% bio-sourced carbons according to the ASTM D6866 method).
[0053] The polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol marketed under the name Velvetol® H250 by the company Allessa (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).
[0054] The equivalent volumes in reactive function respectively of pentamethylene diisocyanate isocyanurate (IE Vi), pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid (IEV2), poly(1,3-propanediol) with a molar mass between 200 and 300g / mol (HEV1) and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (HEV2) are evaluated and reported in Table 1 below.
[0055] 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.
[0056] The respective volume percentages of pentamethylene diisocyanate isocyanurate (%Vh), polyethylene glycol and palmitic acid terminated pentamethylene diisocyanate allophanate (%Vh), poly(1,3-propanediol) with a molar mass between 200 and 300g / mol (%VHi) 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).
[0057] The respective volume percentages of each compound thus correspond to the following formula: (%V11*1EV1)+(%V12*1EV2) = (%VH1*HEV1) + (%VH2*HEV2) Formula 6
[0058] Table 1 shows 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 as well as the percentage of biosourced carbons per phase. Table 1: Equivalent volumes and volume percentage of each compound in the mixture
[0059] Table 2 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases. Table 2: Viscosity of each compound and resulting viscosity of each phase
[0060] To prepare the polyol phase, 38% by volume of Velvetol® H250 is mixed with 62% 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.
[0061] To prepare the polyisocyanate phase, 70% by volume of Stabio D376N is mixed with 30% by volume of Tolonate X Flo 100. The mixture is stirred for 30 seconds at 2500 rpm.
[0062] 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.
[0063] 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 the composition
[0064] This composition meets the criteria imposed in the field of doming.
[0065] Example 2
[0066] The polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by Mitsui Chemicals (67% bio-sourced carbons according to the ASTM D6866 method) and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid marketed under the name Tolonate X Flo 100 by Vencorex (between 29 and 32% bio-sourced carbons according to the ASTM D6866 method).
[0067] The polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol marketed under the name Velvetol H250 by the company Allessa (100% bio-sourced carbons according to the ASTM D6866 method) and castor oil marketed by the company Alberdingk Boley (100% bio-sourced carbons according to the ASTM D6866 method).
[0068] The equivalent volumes in reactive function respectively of pentamethylene diisocyanate isocyanurate (IE Vi), pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid (IEV2), poly(1,3-propanediol) with a molar mass between 200 and 300g / mol (HEV1) and castor oil (HEV2) are evaluated and reported in Table 4 below.
[0069] 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.
[0070] The respective volume percentages of pentamethylene diisocyanate isocyanurate (%Vh), polyethylene glycol and palmitic acid terminated pentamethylene diisocyanate allophanate (%Vl2>, poly(1,3-propanediol) with a molar mass between 200 and 300g / mol (%VHi) and castor oil (%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).
[0071] The respective volume percentages of each compound thus correspond to the following formula: (%V11*1EV1)+(%V12*1EV2) = (%VH1*HEV1) + (%VH2*HEV2) Formula 6
[0072] Table 4 shows 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 as well as the percentage of biosourced carbons per phase. Table 4: Equivalent volumes and volume percentage of each compound in the mixture
[0073] Table 5 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases. Table 5: Viscosity of each compound and resulting viscosity of each phase
[0074] To prepare the polyol phase, 45% by volume of Velvetol® H250 is mixed with 55% by volume of castor oil. 0.03% by mass of dibutyltin dilaurate is added to this polyol phase as a catalyst. The mixture is stirred for 30 seconds at 2500 rpm.
[0075] To prepare the isocyanate phase, 50% by volume of Stabio D-376-N is mixed with 50% by volume of Tolonate X Flo 100. The mixture is stirred for 30 seconds at 2500 rpm.
[0076] 50% by volume of polyol phase is then mixed with 50% by volume of isocyanate 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.
[0077] 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 the composition
[0078] This composition meets the criteria imposed in the field of doming.
[0079] Example 3
[0080] The polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by Mitsui Chemicals (67% bio-sourced carbons according to the ASTM D6866 method) and polyethylene glycol and acid-terminated pentamethylene diisocyanate allophanate palmitic marketed under the name Tolonate X Flo 100 by the company Vencorex (between 29 and 32% biosourced carbons according to the ASTM D6866 method).
[0081] The polyol phase consists of 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).
[0082] The equivalent volumes in reactive function respectively of pentamethylene diisocyanate isocyanurate (IE Vi), pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid (IEV2), and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (HEV1) are evaluated and reported in Table 7 below.
[0083] To comply with industrial constraints in terms of doming, the volume V1 of the isocyanate phase is equal to the volume V2 of the polyol phase.
[0084] The respective volume percentages of pentamethylene diisocyanate isocyanurate (%Vh), polyethylene glycol terminated pentamethylene diisocyanate allophanate and palmitic acid (%Vh) in the polyisocyanate phase are adjusted so that the isocyanate equivalent volume of the polyisocyanate phase (IEV) is equal to the alcohol equivalent volume of the polyol phase (HEV). The respective volume percentages of each compound thus correspond to the following formula: (%V7i * lEVi) + (%Vh * IEV2) = IEV (polyisocyanate phase) = HEV (polyo phase) Formula 7
[0085] Table 7 reports the reactive equivalent volume of each compound as well as the volume percentage of each compound in the polyisocyanate phase to satisfy the above formula. The reactive equivalent volume of each phase is also indicated as well as the percentage of biosourced carbons per phase. Table 7: Equivalent volumes and volume percentage of each compound in the mixture
[0086] Table 8 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases. Table 8: Viscosity of each compound and resulting viscosity of each phase
[0087] To prepare the polyol phase, 0.5% by mass of dibutyltin dilaurate is added to Velvetol® H500. The mixture is stirred for 30 seconds at 2500 rpm.
[0088] To prepare the isocyanate phase, 42.5% by volume of Stabio D-376-N is mixed with 57.5% by volume of Tolonate X Flo 100. The mixture is stirred for 30 seconds at 2500 rpm.
[0089] 50% by volume of polyol phase is then mixed with 50% by volume of isocyanate 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.
[0090] 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 the composition
[0091] This composition meets the criteria imposed in the field of doming.
[0092] Example 4
[0093] The isocyanate phase consists of pentamethylene diisocyanate isocyanurate marketed under the name Stabio D376N by Mitsui Chemicals (67% bio-sourced carbons according to the ASTM D6866 method).
[0094] The polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol marketed under the name Velvetol H250 by the company Allessa (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).
[0095] The equivalent volumes in reactive function respectively of pentamethylene diisocyanate isocyanurate (IEV), poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (HEVi) and poly(1,3-propanediol) with a molar mass between 200 and 300g / mol (HEV2) are evaluated and reported in Table 10 below.
[0096] To comply with industrial constraints in terms of doming, the volume V1 of the isocyanate phase is equal to the volume V2 of the polyol phase.
[0097] The respective volume percentages of poly(1,3-propanediol) with a molar mass between 400 and 600g / mol (HEVi) and poly(1,3-propanediol) with a molar mass between 200 and 300g / mol (HEV2) in the polyol phase are adjusted so that the isocyanate equivalent volume of the polyisocyanate phase (IEV) is equal to the isocyanate equivalent volume of the polyol phase (HEV). The respective volume percentages of each compound thus correspond to the following formula: (° / oVHi * HEVi) + (° / OVH2 * HEV2) = IEV (polyisocyanate phase) = HEV (polyol phase) Formula 8
[0098] Table 10 reports the reactive equivalent volume of each compound and the volume percentage of each compound in the polyol phase to satisfy the above formula. The reactive equivalent volume of each phase is also indicated as well as the percentage of biosourced carbons per phase. Table 10: Equivalent volumes and volume percentage of each compound in the mixture
[0099] Table 1 1 reports the respective viscosity of each compound as well as of each of the polyol and isocyanate phases. Table 11: Viscosity of each compound and resulting viscosity of each phase
[0100] To prepare the polyol phase, 78% by volume of Velvetol® H250 is mixed with 22% by volume of Velvetol® H500. 0.5% by mass of dibutyltin dilaurate is added to this polyol phase as a catalyst. The mixture is stirred for 30 seconds at 2500 rpm.
[0101] The polyisocyanate phase being made up of 100% by volume of Stabio D-376-N does not require any particular preparation.
[0102] 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.
[0103] 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 composition. Table 12: Physicochemical properties of the composition
[0104] This composition meets the criteria imposed in the field of doming.
Claims
DEMANDS
1. Bio-based 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, each containing at least 25% bio-based carbons, and the polyol phase comprises at least one polyol containing at least 80% bio-based carbons, - either the polyol phase comprises at least two polyols, each containing at least 80% bio-based carbons, and the polyisocyanate phase comprises at least one polyisocyanate containing at least 25% bio-based carbons.
2. Composition according to claim 1, characterized in that the number of isocyanate functions in the polyisocyanate phase is equal to the number of alcohol functions in the polyol phase.
3. Composition according to any one of claims 1 and 2, characterized in that the polyisocyanate phase comprises at least one diisocyanate isocyanurate which comprises at least 60% bio-based carbons, and in that the polyol phase comprises at least one polyether polyol which comprises 100% bio-based carbons.
4. Composition according to any one of claims 1 to 3, characterized in that it is obtained by mixing a volume V1 of polyisocyanate phase comprising at least two polyisocyanates each comprising at least 25% bio-based carbons, and a volume V2 of polyol phase comprising at least two polyols each comprising at least 80% bio-based carbons.
5. Composition according to claim 4, characterized in that it is obtained by mixing a polyisocyanate phase comprising at least two polyisocyanates, one of which comprises at least 50% bio-based carbons, and a polyol phase comprising at least two polyols, each of which comprises at least 90% bio-based carbons. Tl
6. Composition according to claim 5, characterized in that the polyisocyanate phase is made of a mixture of diisocyanate isocyanurate comprising at least 60% bio-based carbons and diisocyanate allophanate comprising at least 25% bio-based carbons.
7. Composition according to any one of claims 5 and 6, characterized in that the polyol phase is made of two different polyols which comprise 100% bio-based carbons.
8. Composition according to claim 7, characterized in that the polyol phase comprises either two polyether polyols, or one polyether polyol and castor oil.
9. Composition according to claim 8, characterized in that the polyol phase comprises a poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and a poly(1,3-propanediol) with a molar mass between 400 and 600g / mol.
10. Composition according to any one of claims 1 to 9, characterized in that it is obtained by mixing an equal 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 isocyanate phase is a mixture of diisocyanate isocyanurate comprising at least 60% bio-based carbons and diisocyanate allophanate comprising at least 25% bio-based carbons in a volume ratio of between 40:60 and 80:20, and in that the polyol phase is: - either a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and a poly(1,3-propanediol) with a molar mass between 400 and 600g / mol in a volume ratio between 30:70 and 45:55, - either a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and castor oil in a volume ratio between 40:60 and 50:
50.
12. Composition according to claim 11, characterized in that the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and acid palmitic in a ratio of 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol in a volume ratio of 38:
62.
13. Composition according to claim 1 1, characterized in that the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated polyethylene glycol and palmitic acid in a ratio of 50:50, and in that the polyol phase is a mixture of poly(1,3-propanediol) of molar mass between 200 and 300g / mol and castor oil in a volume ratio of 45:
55.
14. A method for 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, each containing at least 25% bio-based carbons, and the polyol phase comprises at least one polyol containing at least 80% bio-based carbons, o or the polyol phase comprises at least two polyols, each containing at least 80% bio-based carbons, and the polyisocyanate phase comprises at least one polyisocyanate containing at least 25% bio-based carbons, and - mixture of polyisocyanate and polyol phases.
15. A method according to claim 14, characterized in that it comprises at least the steps of: - supply or preparation of a polyisocyanate phase of volume V1 comprising at least two polyisocyanates, each containing at least 25% bio-based carbons, - supply or preparation of a polyol phase of volume V2 comprising at least two polyols, each containing at least 80% bio-based carbons, and - mixture of polyisocyanate and polyol phases.
16. A process according to claim 15, characterized in that the polyisocyanate phase comprises at least two polyisocyanates, one of which comprises at least 50% bio-based carbons, and in that the polyol phase comprises at least two polyols, each of which comprises at least 90% bio-based carbons.
17. A 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 as a function of isocyanate (IEV, IEVÜ >.... IEVi n ) of the polyisocyanate or of each of the at least two polyisocyanates of the polyisocyanate phase, - Evaluation of the equivalent volume as a function 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 (%Vh, %VIÜ,..., %Vh 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 polyols phase by responding to the following formula: VI * IEV = 72 * HEV where IEV is the isocyanate equivalent volume of the polyisocyanate phase and corresponds to the following formula: IEV = (%VIi * lEVi) + (%VIii * IEV H) + ••• + (%7 / in * IEVin) and where HEV is the alcohol equivalent volume of the polyol phase and corresponds to the following formula: HEV = (%VHh * HEVh) + %VHhh * HEVhh) + ••• + (%VHhn * HEVhn)
18. A manufacturing process according to claim 17, characterized in that the polyisocyanate phase is a mixture of two polyisocyanates, in that the polyol phase is a mixture of two polyols, and in that said process comprises the steps of: - evaluation of the isocyanate equivalent volume (IEVi, IEV2) of each of the two polyisocyanates in the polyisocyanate phase, - evaluation of the equivalent volume as an alcohol function (HEV1, HEV2) of each of the two polyols in the polyol phase, and - Adjustment of the respective volume percentage (%Vli, %Vl2) of each of the two polyisocyanates in the polyisocyanate phase, and of the respective volume percentage (%VHI, %VH2) of each of the two polyols in the polyols phase by responding to the following formula: VI * IEV = V2 * HEV where IEV is the isocyanate equivalent volume 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 = (%rai * HEV1) + (%VH2 * HEV2)
19. Manufacturing process 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 percentages (%V1, %V12) of the two polyisocyanates of the isocyanate phase and the respective volume percentages (%V1, %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 isocyanate equivalent volume of the polyisocyanate phase and corresponds to the following formula: I EV = (%VI1 * I EVI) + (%VI2 * IEV2) and where HEV is the alcohol-dependent volume equivalent of the polyol phase and corresponds to the following formula: HEV = (%rai * HEV1) + (%VH2 * HEV2)
20. A process according to claim 19, characterized in that the polyisocyanate phase is a mixture of diisocyanate isocyanurate comprising at least 60% bio-based carbons and diisocyanate allophanate comprising at least 25% bio-based carbons in a volume ratio of between 40:60 and 80:20, and in that the polyol phase is: - either a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol in a volume ratio between 30:70 and 45:55, - either a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and castor oil in a volume ratio between 40:60 and 50:
50.
21. A process according to claim 20, characterized in that the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid in a ratio of 70:30, and in that the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and poly(1,3-propanediol) with a molar mass between 400 and 600g / mol in a volume ratio of 38:
62.
22. A process according to claim 20, characterized in that the polyisocyanate phase is a mixture of pentamethylene diisocyanate isocyanurate and pentamethylene diisocyanate allophanate terminated with polyethylene glycol and palmitic acid in a ratio of 50:50, and in that the polyol phase is a mixture of poly(1,3-propanediol) with a molar mass between 200 and 300g / mol and castor oil in a volume ratio of 45:
55.
23. A manufacturing process according to any one of claims 14 to 22, characterized in that it further comprises a step of adding catalyst to the polyol phase before mixing the polyisocyanate and polyol phases.
24. Printed substrate 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.