METHOD FOR PRODUCE A PRODUCT REINFORCED BY A REINFORCING ELEMENT

Description

[0001] The field of the present invention is that of products reinforced by at least one reinforcing element such as those used in the field of tires.

[0002] The present invention relates more particularly to a method for manufacturing a product reinforced with at least one reinforcing element comprising a step of manufacturing a composition comprising a mixture of two compounds, a step of embedding one or more reinforcing element(s) in this composition and a step of crosslinking by heating a resin based on the two compounds, a product reinforced with at least one reinforcing element obtained by this method, an elastomeric composite comprising this product reinforced with at least one reinforcing element, as well as a tire comprising this product reinforced with at least one reinforcing element or this composite.

[0003] A process for manufacturing a reinforced product comprising a matrix and reinforcing elements embedded within the matrix is ​​known from the prior art. This process includes a step of manufacturing a composition comprising a mixture of two compounds forming the basic constituents of a resin. In order to mix the two compounds and obtain a readily handleable liquid composition, particularly for embedding the reinforcing elements within this composition, a solvent is used in relatively large quantities to solubilize the two compounds. Examples of commonly used solvents, such as organic solvents, are methanol and ethylene glycol. Such a liquid composition exhibits a relatively satisfactory open time. It should be noted that, as is known to those skilled in the art, open time is the duration for which the composition is usable under normal conditions.

[0004] Next, the reinforcing elements are embedded in the liquid composition. Finally, the resin undergoes a crosslinking step by heating the composition to form the matrix in which the reinforcing elements are embedded.

[0005] The use of solvents to ensure the mixing of the two compounds and the handling of the composition necessitates one or more solvent removal steps. A significant portion of the solvents is thus removed by evaporation during the resin curing step by heating. However, such evaporation creates shrinkage within the matrix, that is, a geometric contraction of the matrix, and therefore a more or less predictable dimensional variation in the reinforced product.

[0006] Examples of reinforced materials and processes for their manufacture are described in documents WO 2016 / 116470 A1, WO 2016 / 116468 A1 and WO 2017 / 198967 A1.

[0007] The invention aims to obtain reinforced products by reducing as much as possible the amount of solvents used to mix the basic constituents of the resin, in particular to avoid shrinkage of the matrix.

[0008] In a first embodiment, the invention relates to a method for manufacturing a reinforced product (34) comprising a matrix (38) based on a composition and at least one reinforcing element (36), the reinforcing element(s) being embedded in the matrix (38), in which: A manufacturing step of the composition is carried out, comprising a mixture of at least one compound A1 having a melting point T1, and at least one compound A2 having a melting point T2. At least compound A1 and at least compound A2 are mixed at a temperature Tm such that T1 ≤ Tm < T2 so as to solubilize A2 in A1 and obtain the composition in the liquid state. The composition is free of any organic solvent or water. Then, the reinforcing element(s) (36) are dissolved in the composition in the liquid state. Next, compound A1 reacts with compound A2 to form the resin by heating from a temperature Tn. A crosslinking step is carried out on a resin based on at least compound A1 and at least compound A2 by heating the composition to at least the temperature Tn such that T1 ≤ Tm. <Tn de façon à former la matrice (38) in which is / are embedded the reinforcing element(s) (36) defined as a three-dimensional element enabling the mechanical reinforcement of a matrix in which this three-dimensional reinforcing element is intended to be embedded; in which at least one of the compounds A1, A2 is selected from: a compound A11 comprising at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, or a compound A12 selected from the group consisting of 1,2-benzene-dicarboxaldehyde, 1,3-benzene-dicarboxaldehyde, 1,4-benzene-dicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and mixtures of these compounds, or a mixture of a compound A11 and a compound A12.

[0009] The invention makes it possible to obtain reinforced products by eliminating the amount of solvents used to mix the basic components of the resin, particularly to prevent matrix shrinkage. Indeed, the process according to the invention allows, during the mixing step, the melting of compound A1 by selecting a temperature Tm higher than T1. The molten compound A1 then forms a liquid solvent, thus enabling the solubilization of the other compound A2 without the need for the addition of any solvent, unlike the prior art. Therefore, the resulting composition is easily handled due to its liquid state.

[0010] Choosing a melting temperature (Tm) between T1 and T2 allows A1 to melt, and choosing a Tm lower than Tn prevents the resin from crosslinking. Thus, the resulting composition has a relatively long open time, allowing the embedding step to be carried out without constraints related to potential premature resin crosslinking. It should be noted that the process according to the invention has the advantage of allowing the reinforcing elements to be embedded homogeneously in the matrix due to the liquid state of the composition during the embedding step, without the need for a solvent. Furthermore, the homogeneous dispersion of compounds A1 and A2 in the liquid composition ensures homogeneous mechanical properties within the matrix. Compounds A1 and A2 have chemical structures such that they react with each other at temperature Tn.

[0011] The composition is free of any organic solvents or water.

[0012] In a second embodiment, the invention relates to a method for manufacturing a reinforced product (34) comprising a matrix (38) based on a composition and at least one reinforcing element (36), the reinforcing element(s) being embedded in the matrix, in which: we carry out a manufacturing step of the composition comprising a mixture comprising: at least one compound A3 having a melting point T3, at least one compound A4 having a melting point T4, and at least one compound A5 having a melting point T5, by mixing at least the compounds A3, A4 and A5 at a temperature Tm such that: Tmin ≤ Tm < Tmax in which: Tmin is the lowest temperature among T3, T4 and T5, Tmax is the highest temperature among T3, T4 and T5, and Tint is the temperature among T3, T4 and T5 such that Tmin ≤ Tint ≤ Tmax, so as to solubilize at least one or two of the compounds A3, A5, A4 respectively in at least two others or another of the compounds A3, A5, A4 and obtain a composition in the liquid state, the composition being devoid of any organic solvent or water;then, the reinforcing element(s) (36) is embedded in the composition in the liquid state, then, the compounds A3, A4 and A5 reacting together to form the resin by heating from a temperature Tn, a crosslinking step is carried out of a resin based on at least the compounds A3, A4 and A5 by heating the composition to at least the temperature Tn such that Tmin ≤ Tm < Tn so as to form the matrix (38) in which the reinforcing element(s) (36) is / are embedded, defined as a three-dimensional element allowing the mechanical reinforcement of a matrix in which this three-dimensional reinforcing element is intended to be embedded;in which at least one of the compounds A3, A4, A5 is chosen from: a compound A11 comprising at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, or a compound A12 comprising at least one aldehyde function or a mixture of a compound A11 and a compound A12. ;

[0013] The process according to the second embodiment of the invention allows, during the mixing step, the melting of one or two of the compounds A3, A4, or A5 by selecting a temperature Tm higher than Tmin. The melted compound(s) then form a liquid solvent, thus enabling the solubilization of the other compound(s) without the need to add any solvent, unlike the prior art.

[0014] Compounds A3, A4 and A5 have chemical structures such that at temperature Tn, they react together.

[0015] In a third embodiment, the invention relates to a method for manufacturing a reinforced product (34) comprising a matrix (38) based on a composition and at least one reinforcing element (36), the reinforcing element(s) being embedded in the matrix (38), in which: We carry out a manufacturing step of the composition comprising a mixture including: at least one compound A3 having a melting point T3, at least one compound A4 having a melting point T4, at least one compound A5 having a melting point T5, at least one compound A6 having a melting point T6, by mixing at least compounds A3, A4, A5 and A6 at a temperature Tm such that Tmin ≤ Tm < Tmax in which: Tmin is the lowest temperature among T3, T4, T5 and T6, and Tmax is the highest temperature among T3, T4, T5 and T6; Tint1 is the temperature among T3, T4, T5 and T6, and Tint2 is the temperature among T3, T4, T5 and T6 such that: Tmin ≤ Tint1 ≤ Tint2 ≤ Tmax, so as to solubilize one, two or three of compounds A3, A4, A5, A6 in respectively three, two or another of compounds A3, A4, A5, A6 and obtain a composition in the liquid state, the composition being devoid of any organic solvent or water;then, the reinforcing element(s) (36) is / are embedded in the composition in the liquid state, then, the compounds A3, A4, A5 and A6 reacting together to form the resin by heating from a temperature Tn, a crosslinking step is carried out of a resin based on at least the compounds A3, A4, A5 and A6 by heating the composition to at least the temperature Tn such that Tmin ≤ Tm < Tn so as to form the matrix (38) in which the reinforcing element(s) (36) is / are embedded, defined as a three-dimensional element allowing the mechanical reinforcement of a matrix in which this three-dimensional reinforcing element is intended to be embedded;in which at least one of the compounds A3, A4, A5, A6 is chosen from: a compound A11 comprising at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, or a compound A12 comprising at least one aldehyde function, or a mixture of a compound A11 and a compound A12.

[0016] The process according to the third embodiment of the invention allows, during the mixing step, the melting of one or two of the compounds A3, A4, A5, or A6 by selecting a temperature Tm higher than Tmin. The melted compound(s) then form a liquid solvent, thus enabling the solubilization of the other compound(s) without the need to add any solvent, unlike the prior art.

[0017] Compounds A3, A4, A5 and A6 have chemical structures such that at temperature Tn, they react together.

[0018] Advantageously, using a mixture of three or four compounds allows, on the one hand, for the solubilization of all the compounds using the compound with the lowest melting point and, on the other hand, for the utilization of the mechanical properties conferred by the other compounds with melting points higher than Tm. Furthermore, as in the first embodiment, it should be noted that the process according to the invention has the advantage of allowing the reinforcing elements to be homogeneously embedded in the matrix due to the liquid state of the composition during the embedding step, without the need for a solvent.

[0019] Preferably, in the three embodiments described above, the mixing step and the crosslinking step are carried out at the same pressure, preferably atmospheric pressure. More preferably, the mixing step, the drowning step, and the crosslinking step are carried out at the same pressure, preferably atmospheric pressure.

[0020] Naturally, in each of the three embodiments described above, the relevant temperature for a step is that measured at the pressure to which that step is carried out. For example, the relevant melting temperatures for the mixing step are those measured at the pressure to which the mixing step is carried out, and the relevant melting temperatures for the crosslinking step are those measured at the pressure to which the crosslinking step is carried out, regardless of whether the pressure of the mixing step is the same as or different from that of the crosslinking step.

[0021] A reinforced product comprising a matrix and at least one reinforcing element, the reinforcing element(s) being embedded in the matrix, capable of being obtained by the process as defined above, is also described.

[0022] In a preferred embodiment, the reinforced product has a general shape of a sheet, strip, band, or ribbon extending along a principal direction. The width L of the reinforced product, measured along a direction perpendicular to the principal direction, and the thickness E of the reinforced product are such that L > E, preferably L > 10 x E.

[0023] An elastomer composite comprising an elastomer matrix in which is embedded at least one reinforced product as defined above, is also described.

[0024] A tire comprising at least one reinforced product as defined above or an elastomer composite as defined above, is also described.

[0025] By pce, we mean parts by weight per hundred parts of elastomer.

[0026] On the other hand, any interval of values ​​designated by the expression "between a and b" represents the domain of values ​​going from more than a to less than b (that is, bounds a and b excluded) while any interval of values ​​designated by the expression "from a to b" means the domain of values ​​going from a to b (that is, including the strict bounds a and b).

[0027] Within the scope of the invention, the carbon products mentioned in the description may be of fossil origin or bio-based. In the latter case, they may be partially or totally derived from biomass or obtained from renewable raw materials derived from biomass.

[0028] The invention and its advantages will be readily understood in light of the description and implementation examples that follow.

[0029] In this description, unless expressly stated otherwise, all percentages (%) indicated are % by mass.

[0030] A composition in the liquid state is understood to be neither solid nor gaseous. The liquid composition may be viscous or non-viscous.

[0031] The ambient temperature of a step refers to the temperature of the environment in which the step is carried out, i.e., the temperature of the surrounding rooms where the step is implemented. For example, the ambient temperature is between 20 and 30°C.

[0032] An elastomer composition is understood to be a composition comprising at least one elastomer (or indistinctly rubber) and at least one other constituent.

[0033] A "diene" elastomer (or, indiscriminately, rubber) is defined as an elastomer derived at least in part (i.e., a homopolymer or copolymer) from diene monomer(s) (i.e., bearing two carbon-carbon double bonds, conjugated or not). An "isoprene" elastomer is defined as a homopolymer or copolymer of isoprene; in other words, a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), various isoprene copolymers, and mixtures of these elastomers.

[0034] An elastomeric matrix is ​​understood to be a matrix with elastomeric behavior.

[0035] By "meta position relative to each other", we mean that the hydroxyl functions are carried by carbons of the aromatic ring separated from each other by a single other carbon of the aromatic ring.

[0036] By "in ortho position of a function", we mean the position occupied by the carbon of the aromatic ring immediately adjacent to the carbon of the aromatic ring bearing the function.

[0037] By "member" of a nucleus, we mean an atom that makes up the nucleus's skeleton. For example, a benzene ring has six members, each member being a carbon atom. In another example, a furanine ring has five members, four of which are carbon atoms and the remaining member an oxygen atom.

[0038] “CHO” represents the aldehyde function.

[0039] “CH2OH” represents the hydroxymethyl function.

[0040] By "aromatic polyphenol" we mean an aromatic compound comprising at least one benzene ring bearing more than one hydroxyl function.

[0041] The expression "composition based on" means a composition comprising the mixture and / or the in situ reaction product of the different constituents used, some of these constituents being able to react and / or being intended to react with each other, at least partially, during the different phases of manufacturing the composition; the composition can thus be in a totally or partially crosslinked state or in a non-crosslinked state.

[0042] The term "resin-based" refers to a resin comprising the mixture and / or the reaction product between the various basic constituents used for the final condensation of that resin, preferably only the reaction product between the various basic constituents used for that resin. Some of these constituents may be intended to react, or are likely to react, with each other or with their immediate chemical environment, at least partially, during the various phases of the manufacturing process of the composition, composites, or tire, particularly during a curing step. Thus, the basic constituents are the reactants intended to react together during the final condensation of the resin and are not reactants intended to react together to form these basic constituents.

[0043] A reinforcing element is defined as a three-dimensional element that provides mechanical reinforcement to a matrix in which this three-dimensional reinforcing element is intended to be embedded. METHOD ACCORDING TO THE INVENTION

[0044] Advantageously, T1 ≤ 110°C, preferably T1 ≤ 100°C and more preferably T1 ≤ 90°C. Thus, as little energy as possible is supplied to melt compound A1.

[0045] Advantageously, T1 ≥ 40°C and preferably T1 ≥ 50°C.

[0046] Advantageously, Tm-T1 ≥ 1°C, preferably Tm-T1 ≥ 2°C and more preferably Tm-T1 ≥ 5°C.

[0047] Advantageously, Tm-T1 ≤ 30°C, preferably Tm-T1 ≤ 10°C and more preferably Tm-T1 ≤ 5°C.

[0048] Advantageously, T2-T1 ≥ 30°C, preferably T2-T1 ≥ 40°C and more preferably T2-T1 ≥ 50°C.

[0049] Advantageously, T2-T1 ≤ 200°C, preferably T2-T1 ≤ 190°C and more preferably T2-T1 ≤ 170°C.

[0050] The difference between the melting temperatures T1 and T2 of compounds A1 and A2 is preferably large enough to ensure a sufficiently wide range for the melting temperatures Tm and Tn. This reduces, on the one hand, the risk of incomplete melting of compound T1 and therefore poor solubilization of compounds A1 and A2, which would result from an insufficient difference between T1 or T2 and Tm. On the other hand, it reduces the risk of premature crosslinking of the resin, which would be due to poor control of Tn.

[0051] In the first embodiment, we preferably have T2 ≥ Tn.

[0052] In the second embodiment of the invention, we preferably have Tint ≤ Tn ≤ Tmax.

[0053] In the second embodiment of the invention, we more preferably have Tn ≤ Tint ≤ Tmax.

[0054] In the third embodiment of the invention, we preferably have Tint1 ≤ Tint2 ≤ Tn ≤ Tmax.

[0055] In the third embodiment of the invention, we more preferably have Tint1 ≤ Tn ≤ Tint2 ≤ Tmax.

[0056] In the third embodiment of the invention, we have even more preferably Tn ≤ Tint1 ≤ Tint2 ≤ Tmax.

[0057] Advantageously, in the second and third embodiments, at least one compound A3, A5, A4, or A6 has a melting point greater than or equal to Tn. Thus, the process can be carried out with compounds having relatively high melting points, provided that these compounds are mixed with a compound having a sufficiently low melting point and in sufficient quantity to solubilize the mixture.

[0058] Advantageously, Tm-Tmin ≥ 1°C, preferably Tm-Tmin ≥ 2°C and more preferably Tm-Tmin ≥ 5°C.

[0059] Advantageously, Tm-Tmin ≤ 30°C, preferably Tm-Tmin ≤ 10°C and more preferably Tm-Tmin ≤ 5°C.

[0060] Advantageously, Tmax-Tmin ≥ 30°C, preferably Tmax-Tmin ≥ 40°C and more preferably Tmax-Tmin ≥ 50°C.

[0061] Advantageously, Tmax-Tmin ≤ 200°C, preferably Tmax-Tmin ≤ 190°C and more preferably Tmax-Tmin ≤ 170°C.

[0062] In a first variant, the process is such that, during the manufacturing stage of the composition, all the compounds are in a solid state at room temperature, the composition is heated to a temperature Tm strictly higher than room temperature.

[0063] In this first variant, for all embodiments, heating is done only as much as necessary to solubilize the compounds. Thus, the resulting composition is in a liquid state at Tm and has a relatively long open time, allowing the drowning step to be carried out without any constraint related to potential premature crosslinking of the resin.

[0064] In this second variant, the process is such that, during the manufacturing step of the composition, at least one compound is in a liquid state at room temperature and at least one compound is in a solid state at room temperature, the compound in the solid state is solubilized in the compound in the liquid state at room temperature.

[0065] Advantageously, in this second variant, for the first embodiment, it is not necessary to heat compound A2 to dissolve compound A1 because compound A1 is already liquid at room temperature. Thus, the resulting composition is liquid at room temperature and has a relatively long open time, allowing the drowning step to be carried out without any constraint related to premature crosslinking of the resin.

[0066] Advantageously, in this second variant, for the second and third embodiments, from the moment one of the compounds is liquid at room temperature, the other compounds which have higher melting points will dissolve in the composition, making it possible to obtain a composition that is easily handled due to its liquid state.

[0067] Preferably, Tm ≤ 110°C, preferably Tm ≤ 100°C and more preferably Tm ≤ 80°C.

[0068] Preferably, Tn ≤ 140°C, preferably Tn ≤ 130°C and more preferably Tn ≤ 120°C.

[0069] Advantageously, Tn-Tm ≥ 5°C and more preferably Tn-Tm ≥ 10°C.

[0070] Advantageously, Tn-Tm ≤ 100°C and more preferably Tn-Tm ≤ 60°C.

[0071] The difference between temperatures Tm and Tn is preferably large enough to reduce the risk of early crosslinking of the resin.

[0072] Advantageously, the process is such that, subsequent to the resin crosslinking step, a final resin crosslinking step is carried out by heating to a temperature Tp with Tn < Tp.

[0073] Advantageously, the pressure at which the final crosslinking step is carried out is less than or equal to 1.50 bar, preferably less than or equal to 1.20 bar and more preferably less than or equal to 1.10 bar.

[0074] Advantageously, the pressure at which the final crosslinking step is carried out is strictly greater than 1.00 bar, preferably greater than or equal to 1.01 bar and more preferably greater than or equal to 1.03 bar.

[0075] Thus, a slight overpressure is applied in order to precisely control the dimensions of the reinforced product.

[0076] Advantageously, Tp ≤ 200°C.

[0077] The process according to the invention allows the resin crosslinking step to be carried out at a relatively low temperature, thus preventing the degradation of the compounds. Consequently, the final resin crosslinking step requires less energy input, resulting in a less expensive process. Resin

[0078] In the first embodiment of the invention, the resin is obtained by the reaction of at least compound A1 and at least compound A2 which are described below.

[0079] According to this first embodiment, the basic constituents of the resin therefore comprise at least compound A1 and at least compound A2. Alternatively, the basic constituents may comprise other additional constituents other than compound A1 and compound A2. In another alternative, the basic constituents consist of at least compound A1 and at least compound A2.

[0080] In the second embodiment of the invention, the resin is obtained by the reaction of at least three compounds A3, A4 and A5 as described below.

[0081] According to this second embodiment, the basic constituents of the resin therefore comprise at least the three compounds A3, A4, and A5. Alternatively, the basic constituents may comprise other additional constituents other than compounds A3, A4, and A5. In another alternative, the basic constituents consist of at least the three compounds A3, A4, and A5.

[0082] In the third embodiment of the invention, the resin is obtained by the reaction of four compounds A3, A4, A5 and A6 as described below.

[0083] According to this third embodiment, the basic constituents of the resin therefore comprise at least the four compounds A3, A4, A5 and A6. Alternatively, the basic constituents may comprise other additional constituents other than compounds A3, A5, A4 and A6. In another alternative, the basic constituents consist of at least the four compounds A3, A4, A5 and A6.

[0084] Preferably, in the three embodiments described above, a person skilled in the art will choose the proportions of the different basic constituents of the resin so as to obtain the desired mechanical properties.

[0085] Preferably, in the embodiment where the basic constituents include other additional constituents, these other additional constituents are formaldehyde-free and / or free of a methylene donor selected from the group consisting of hexamethylenetetramine (HMT), hexamethoxymethylmelamine (H3M), hexaethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, trioxane formaldehyde hexamethoxymethylmelamine polymers, hexakis(methoxymethyl)melamine, N,N',N"-trimethyl / -N,N',N"-trimethylolmelamine, hexamethylolmelamine, N-methylolmelamine, N,N'-dimethylolmelamine, N,N',N"-tris(methoxymethyl)melamine, N,N',N"-tributyl-N,N',N"-trimethylolmelamine. More advantageously, these other additional constituents are formaldehyde-free and free of the methylene donors described in this paragraph.

[0086] More preferably, in the embodiment where the basic constituents include other additional constituents, these other additional constituents are formaldehyde-free and / or free of a methylene donor selected from the group consisting of hexamethylenetetramine, hexaethoxymethylmelamine, hexamethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, trioxane hexamethoxymethylmelamine and N-substituted oxymethylmelamines corresponding to the general formula: in which Q represents an alkyl group containing from 1 to 8 carbon atoms; G1, G2, G3, G4, and G5 are chosen independently from among the group consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms, the -CH2OQ group, and their condensation products. More advantageously, these additional constituents are formaldehyde-free and free of the methylene donors described in this paragraph.

[0087] Even more preferably, in the embodiment where the basic constituents include other additional constituents, these other additional constituents are formaldehyde-free and / or methylene-donor-free. More advantageously, these other additional constituents are formaldehyde-free and methylene-donor-free.

[0088] By formaldehyde-free or methylene donor-free, we mean that the total mass percentage of formaldehyde or of the methylene donor(s) belonging to the groups described above by total weight of the compound(s) in the basic constituents is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

[0089] Formaldehyde-free and methylene donor-free means that the total mass percentage of formaldehyde and of the methylene donor(s) belonging to the groups described above in total weight of the compound(s) in the basic constituents is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

[0090] Thus, the resins described above are based on compounds that comply with regulations aimed at excluding certain compounds such as formaldehyde. Furthermore, formaldehyde is a petroleum-derived compound that is being phased out as much as possible due to its increasing scarcity. Drying agent

[0091] Advantageously, the process is such that, during the manufacturing stage of the composition, a drying agent is added.

[0092] Preferably, the drying agent is chosen from kaolin, montmorillonite, mica, magnesium sulfate, magnesium chloride and mixtures of these drying agents.

[0093] In the event that water is released during the reaction between the compounds, a drying agent is introduced with the aim of capturing this water.

[0094] The addition of this drying agent can, in particular, allow for the modulation of the resin's mechanical properties. Additives

[0095] The composition of the process of the invention may of course include all or part of the usual additives for compositions such as those used to form products reinforced by reinforcing elements; examples include fillers, colorants, antioxidants or other stabilizers.

[0096] Advantageously, the filler is chosen from carbon black and silica. Compounds A1, A2, A3, A4, A5 or A6

[0097] At least one basic constituent of the resin is a compound A1, A2, A3, A4, A5 or A6, this compound A1, A2, A3, A4, A5 or A6 being chosen from: a compound A11 comprising at least one aromatic ring bearing at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function or a compound A12 comprising at least one aromatic ring bearing at least one aldehyde function or a mixture of a compound A11 and a compound A12. In the case where the basic constituent of the resin is compound A1 or A2, compound A12 is chosen from the group consisting of 1,2-benzene-dicarboxaldehyde, 1,3-benzene-dicarboxaldehyde, 1,4-benzene-dicarboxaldehyde, 2-hydroxybenzene-1,3-5-tricarbaldehyde and mixtures of these compounds.

[0098] In a first embodiment, where the basic constituent of the resin is compound A3, A4, A5 or A6, compound A12 comprises at least one aromatic ring bearing at least one aldehyde function.

[0099] More preferably, compound A12 carries at least two aldehyde functions.

[0100] Even more preferentially, the aromatic nucleus of compound A12 carries two aldehyde functions.

[0101] In one embodiment, where the basic constituent of the resin is compound A3, A4, A5 or A6, the aromatic ring of compound A12 is chosen from the group consisting of a benzene ring and a furanine ring, preferably the aromatic ring of the aromatic aldehyde is a benzene ring.

[0102] Preferably, in the case where the basic constituent of the resin is compound A3, A4, A5 or A6, compound A12 is chosen from the group consisting of 1,2-benzene-dicarboxaldehyde, 1,3-benzene-dicarboxaldehyde, 1,4-benzene-dicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and mixtures of these compounds.

[0103] In the first embodiment, where the basic constituent of the resin is compound A3, A4, A5 or A6, compound A12 is, in a variant, of general formula (A): in which: X includes N, S or OR represents -H or -CHO.

[0104] Preferably, compound A12 has the general formula (A'):

[0105] Even more preferentially, R represents -CHO.

[0106] According to a preferred embodiment, X represents O.

[0107] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, a variant of compound A12 has the general formula (A), in which X represents O and R represents H. The compound A12 used then has the formula (Ba):

[0108] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, a variant of compound A12 has the general formula (A'), where X represents O and R represents -H. The compound A12 used is then furfuraldehyde and has the formula (B'a):

[0109] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, another variant of compound A12 has the general formula (A), where X represents O and R represents -CHO. The compound A12 used then has the formula (Bb):

[0110] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, another variant of compound A12 has the general formula (A'), in which X represents O and R represents -CHO. The compound A12 used is then 2,5-furanedicarboxaldehyde and has the formula (B'b):

[0111] In another embodiment, X includes N.

[0112] Preferably, compound A12 is chosen from the group consisting of furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these compounds.

[0113] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, a variant of compound A12 has the general formula (A), where X represents NH. The compound A12 used has the formula (Ca):

[0114] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, a variant of compound A12 has the general formula (A') , where X represents NH. The compound A12 used has the formula (That) :

[0115] Preferably, R represents -CHO in the variant of compound A12 with formula (That) and the compound A12 obtained is then 2,5-1H-pyrroledicarboxaldehyde.

[0116] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, another variant of compound A12 has the general formula (A), in which X represents NT1 with T1 representing an alkyl, aryl, arylalkyl, alkylaryl, or cycloalkyl group. The compound A12 used has the formula (Cb):

[0117] In another embodiment, X includes S.

[0118] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, a variant of compound A12 has the general formula (A), X represents S. The compound A12 used has the formula (Da):

[0119] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, a variant of compound A12 has the general formula (A'), in which X represents S. The compound A12 used has the formula (D'a):

[0120] Preferably, R represents -CHO in the variant of compound A12 with formula (IV'a) and is then 2,5-thiophenedicarboxaldehyde.

[0121] In cases where the basic constituent of the resin is compound A3, A4, A5, or A6, another variant of compound A12 has the general formula (A), in which X represents ST2 with T2 representing an alkyl, aryl, arylalkyl, alkylaryl, or cycloalkyl group. The compound A12 used has the formula (dB):

[0122] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, yet another variant of compound A12 has the general formula (A), in which X represents T3-ST2, with T2 and T3 each independently representing an alkyl, aryl, arylalkyl, alkylaryl, or cycloalkyl group. The compound A12 used has the formula (Dc):

[0123] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, yet another variant of compound A12 has the general formula (A), in which X represents S=O. The compound A12 used has the formula (Dd)

[0124] In the case where the basic constituent of the resin is compound A3, A4, A5 or A6, yet another variant of compound A12 has the general formula (A), in which X represents O=S=O. The compound A12 used has the formula (Of)

[0125] Among the various embodiments described above, preference is given to those embodiments and variants in which X represents NH, S, or O. In these embodiments and variants, R may represent -H or -CHO, and preferably R represents -CHO. In these embodiments and variants, R is preferably located at position 5 and the -CHO group at position 2 on the aromatic ring (general formula). (A') ).

[0126] In a second embodiment, compound A11 is an aromatic compound comprising at least one aromatic ring bearing at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function.

[0127] Thus, in this second embodiment, it is the aromatic ring that bears the hydroxymethyl and aldehyde functions. Compound A11 therefore corresponds, in this second embodiment, to the general formula (I): HO-CH2-Ar-B (I) where Ar represents an aromatic ring and B represents CHO or CH2OH.

[0128] The aromatic ring is advantageously a 5- or 6-membered ring, comprising, as members, carbon atoms and optionally one or more heteroatoms, in particular nitrogen, oxygen, or sulfur atoms, possibly oxidized as N-oxide or S-oxide. In a variant, the aromatic ring comprises 0, 1, or 2 heteroatoms. The remainder of the aromatic ring may or may not be substituted.

[0129] The aromatic ring may bear 0, 1 or 2 aldehyde functions, advantageously 0 or 1 aldehyde function, provided that the compound A11 comprises at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function.

[0130] The aromatic ring may bear 1, 2 or 3 hydroxymethyl functions, advantageously 1 or 2 hydroxymethyl functions, provided that the compound A11 comprises at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function.

[0131] In addition, the aromatic ring can also carry 0, 1 or 2 other function(s), in particular hydroxyl.

[0132] In the embodiment in which the aromatic ring is a 6-membered ring, the B and hydroxymethyl functions are advantageously in meta or para positions relative to each other.

[0133] In the embodiment in which the aromatic ring is a 5-membered ring, the ring may comprise one or more heteroatoms, in particular nitrogen, oxygen, and sulfur atoms, optionally oxidized as N-oxide or S-oxide. Advantageously, the aromatic ring comprises one or two heteroatoms, preferably one heteroatom.

[0134] In this embodiment in which the aromatic ring is a 5-membered ring, at least one of the following three conditions is met, provided that compound A11 comprises at least two functional groups, one of these functional groups being a hydroxymethyl group, the other being an aldehyde group or a hydroxymethyl group: the aromatic ring comprises 0 or only one aldehyde function; the aromatic ring comprises one or two hydroxymethyl functions; apart from the aldehyde and hydroxymethyl functions, the rest of the aromatic ring is unsubstituted.

[0135] Advantageously, these three conditions are met.

[0136] In the first case, the aromatic core comprises a single aldehyde function; a single hydroxymethyl function; apart from the aldehyde and hydroxymethyl functions, the rest of the aromatic ring is not substituted.

[0137] In a second case, the aromatic core comprises 0 aldehyde functions; two hydroxymethyl functions; apart from the hydroxymethyl functions, the rest of the aromatic ring is unsubstituted.

[0138] Advantageously, compound A11 corresponds to the general formula (II): where B represents CHO or CH2OH, Y represents O, NR1, NO, S, SO, SO2, SR2, R3, R4 represents a hydrogen, an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group, R2, R3 each represent, independently of each other, a hydrogen, an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group.

[0139] Advantageously, compound A11 has the general formula (II'): in which Y, B are as defined previously.

[0140] In a particularly advantageous embodiment, B represents CHO. In another embodiment, B represents CH2OH.

[0141] According to a preferred embodiment, Y represents O.

[0142] In one variant, compound A11 has the formula (IIa): B being as defined previously.

[0143] More specifically, compound A11 corresponds to the general formula (II'a1) or (II'a2):

[0144] 5-(Hydroxymethyl)-Furfural (II'a1) is a particularly suitable A11 compound, given that this organic compound can easily be derived from renewable resources. Indeed, it is produced notably from the dehydration of certain sugars such as fructose, glucose, sucrose, cellulose, and insulin.

[0145] In another embodiment, Y represents NR1 or NO, advantageously NR1. R1 represents a hydrogen, an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group.

[0146] In one variant, the compound has the formula (Ilb): B being as defined previously and more particularly of formula (II'b1) or (II'b2): in which R1 is as defined previously. Advantageously R1 represents a hydrogen or an alkyl group in C1-C6.

[0147] In another embodiment, Y represents S, SO, SO 2 or SR 2 R 3 with R 2 and R 3 as defined previously.

[0148] In one variant, the compound has the formula (Ilc): B being such as defined previously with Y representing S, SR2 R3, SO, SO2, R2, R3 each represent, independently of each other, a hydrogen, an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group, B, R2 and R3 being such as defined previously; and more particularly of formula (II'c1) or (II'c2): in which Y represents S, SR2 R3, SO, SO2, R2, R3 each represent, independently of each other, a hydrogen, an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group.

[0149] The compound can therefore be:

[0150] Advantageously R2, R3 each represent, independently of each other, a C1-C6 alkyl radical.

[0151] The compound advantageously has the formula (lI'c3) or (II'c4).

[0152] In another variant, the aromatic ring is a 6-membered ring, which may include 0, 1, or more heteroatoms, particularly nitrogen, possibly oxidized as an N-oxide. In a further variant, the aromatic ring comprises 0, 1, or 2 heteroatoms.

[0153] The B and hydroxymethyl functions are advantageously in meta or para positions relative to each other.

[0154] The aromatic ring can bear 0, 1 or 2 aldehyde functions, advantageously 0 or 1 aldehyde function.

[0155] The aromatic ring can bear 1, 2 or 3 hydroxymethyl functions, advantageously 1 or 2 hydroxymethyl functions.

[0156] In addition, the aromatic ring can also carry 0, 1 or 2 other function(s), in particular hydroxyl.

[0157] Advantageously, compound A11 has the general formula (III): where Y represents C or NR1, n is 0, 1 or 2, m is 0 or 1, p is 1, 2 or 3. R1 represents a hydrogen, an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group. Thus, p+n>1 with p>0.

[0158] Advantageously R1 represents a hydrogen or an alkyl group in C1-C6.

[0159] In one variant, n equals 1, m equals 0 and p equals 1.

[0160] In another variant, n equals 1, m equals 1 and p equals 1.

[0161] In another variant, n equals 2, m equals 1 and p equals 1.

[0162] In another variant, n equals 1, m equals 1 and p equals 2.

[0163] In another variant, n equals 0, m equals 0 and p equals 2.

[0164] In another variant, n equals 0, m equals 1 and p equals 2.

[0165] In another variant, n equals 1, m equals 1 and p equals 2.

[0166] In another variant, n equals 0, m equals 1 and p equals 3.

[0167] Preferably the aromatic ring of compound A11 is a benzene ring. More preferably, this aldehyde is chosen from the group consisting of 2-hydroxymethylbenzene-1-carboxaldehyde, 3-hydroxymethylbenzene-1-carboxaldehyde, 4-hydroxymethylbenzene-1-carboxaldehyde, 3-hydroxymethyl-6-hydroxybenzene-1-carboxaldehyde, 3-hydroxymethyl-4-hydroxybenzene-1-carboxaldehyde, 3-hydroxymethyl-2-hydroxybenzene-1-carboxaldehyde, 3-hydroxymethyl-2-hydroxybenzene-1,5-dicarboxaldehyde, 5-hydroxymethyl-2-hydroxybenzene-1,3-dicarboxaldehyde, 3,5-hydroxymethyl-4-hydroxybenzene-1-carboxaldehyde, 3,5-hydroxymethyl-2-hydroxybenzene-1-carboxaldehyde, 1,2-hydroxymethylbenzene, 1,3-hydroxymethylbenzene, the 1,4-hydroxymethylbenzene, 1,3-hydroxymethyl-6-hydroxybenzene, 1,3-hydroxymethyl-4-hydroxybenzene, 1,3-hydroxymethyl-2-hydroxybenzene, 1,3,5-hydroxymethyl-2-hydroxybenzene, 1,3-hydroxymethyl-6-hydroxybenzene, 1,3,5-Hydroxymethyl-4-hydroxybenzene, 1,3,2-Hydroxymethyl-2-hydroxybenzene and mixtures of these compounds.

[0168] Even more preferably, the compound A11 used is 1-hydroxymethyl-benzene-4-carboxaldehyde of formula (IIIa) or 1,4-hydroxymethyl-benzene of formula (IIIb):

[0169] Among the other advantages of using A11 and / or A12 compounds, it should be noted that the composition can be formaldehyde-free. It is desirable to reduce, or even eventually eliminate, the use of formaldehyde in adhesive compositions due to recent changes in European regulations concerning this type of compound. Furthermore, formaldehyde is a petroleum-derived compound that is being phased out as much as possible due to its increasing scarcity. Compound A1, A2, A3, A4, A5 or A6

[0170] At least one basic constituent of the resin is a compound A1, A2, A3, A4, A5 or A6.

[0171] Advantageously, this compound A1, A2, A3, A4, A5 or A6 is a phenol.

[0172] Advantageously, phenol is chosen from among: • an aromatic polyphenol A21 comprising at least one aromatic ring bearing at least two hydroxyl functions in meta positions relative to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted • an aromatic monophenol A22 comprising at least one six-membered aromatic ring bearing a single hydroxyl function, the two ortho positions of the hydroxyl function being unsubstituted or at least one ortho position and the para position of the hydroxyl function being unsubstituted • a mixture of A21 and A22.

[0173] In one embodiment, the phenol is an aromatic polyphenol A21 comprising one or more aromatic ring(s). The aromatic polyphenol comprises at least one aromatic ring bearing at least two hydroxyl groups in meta positions relative to each other, the two ortho positions of at least one of the hydroxyl groups being unsubstituted.

[0174] In another embodiment, phenol is an aromatic monophenol A22 comprising at least one six-membered aromatic ring bearing a single hydroxyl group. In this aromatic monophenol, both ortho positions of the hydroxyl group are unsubstituted, or at least one ortho position and the para position of the hydroxyl group are unsubstituted.

[0175] In yet another embodiment, phenol is a mixture of aromatic polyphenol A21 and aromatic monophenol A22 as described above.

[0176] According to the invention, aromatic polyphenol A21 can be, in one embodiment, a simple aromatic polyphenol molecule comprising one or more aromatic rings, at least one of these aromatic rings, or even each aromatic ring, bearing at least two hydroxyl functions in meta positions relative to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted.

[0177] Similarly, aromatic monophenol A22 may, in one embodiment, be a simple aromatic monophenol molecule comprising one or more six-membered aromatic rings, at least one of these six-membered aromatic rings, or even each six-membered aromatic ring, bearing a single hydroxyl function, the two ortho positions of the hydroxyl function being unsubstituted, or at least one ortho position and the para position of the hydroxyl function being unsubstituted.

[0178] Such simple molecules do not include a repeating pattern.

[0179] According to the invention, aromatic polyphenol A21 can, in another embodiment, be a pre-condensed resin based on: of at least one aromatic polyphenol, comprising at least one aromatic ring bearing at least two hydroxyl functions in meta positions relative to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted; and of at least one compound comprising at least one aldehyde function and / or at least one compound comprising at least two hydroxymethyl functions borne by an aromatic ring.

[0180] Such a pre-condensed resin based on aromatic polyphenol conforms to the invention and, unlike the simple molecule described above, comprises a repeating motif. In this case, the repeating motif comprises at least one aromatic ring bearing at least two hydroxyl groups in meta positions relative to each other.

[0181] Similarly and in accordance with the invention, aromatic monophenol A22 can, in another embodiment, be a pre-condensed resin based on: of at least one aromatic monophenol comprising at least one six-membered aromatic ring bearing a single hydroxyl function: ∘ both ortho positions of the hydroxyl function are unsubstituted, or ∘ at least one ortho position and the para position of the hydroxyl function are unsubstituted; of at least one compound comprising at least one aldehyde function and / or at least one compound comprising at least two hydroxymethyl functions borne by an aromatic ring.

[0182] Such a pre-condensed resin based on aromatic monophenol conforms to the invention and, unlike the simple molecule described above, comprises a repeating motif. In this case, the repeating motif comprises at least one six-membered aromatic ring bearing a single hydroxyl group.

[0183] In another embodiment, phenol is a mixture of an aromatic polyphenol forming a simple molecule and a pre-condensed resin based on aromatic polyphenol.

[0184] In yet another embodiment, phenol is a mixture of an aromatic monophenol forming a simple molecule and a pre-condensed resin based on aromatic monophenol.

[0185] In the specific embodiments that follow, the aromatic ring(s) of the aromatic polyphenol and / or aromatic monophenol are described. For clarity, the "aromatic polyphenol" and / or "aromatic monophenol" are described in their simple molecular form. This aromatic polyphenol and / or aromatic monophenol can then be condensed and will partially define the repeating motif. The characteristics of the pre-condensed resin are described in more detail later. Aromatic polyphenol A21

[0186] In a preferred embodiment, the aromatic core of the aromatic polyphenol bears three hydroxyl functions in meta positions relative to each other.

[0187] Preferably, the two ortho positions of each hydroxyl function are unsubstituted. This means that the two carbon atoms located on either side (in ortho position) of the hydroxylated carbon atom (i.e., bearing the hydroxyl function) each have a single hydrogen atom attached.

[0188] Even more preferentially, the remainder of the aromatic ring of the aromatic polyphenol is unsubstituted. This means that the other carbon atoms of the remainder of the aromatic ring (those other than the carbon atoms bearing the hydroxyl groups) are bonded to a single hydrogen atom.

[0189] In one embodiment, the aromatic polyphenol comprises several aromatic rings, at least two of them each bearing at least two hydroxyl functions in meta positions relative to each other, the two ortho positions of at least one of the hydroxyl functions of at least one aromatic ring being unsubstituted.

[0190] In a preferred embodiment, at least one of the aromatic rings of the aromatic polyphenol bears three hydroxyl functions in meta positions relative to each other.

[0191] Preferably, the two ortho positions of each hydroxyl function of at least one aromatic ring are unsubstituted.

[0192] Even more preferentially, the two ortho positions of each hydroxyl function of each aromatic ring are unsubstituted.

[0193] Advantageously, the aromatic ring or rings of the aromatic polyphenol are benzene rings.

[0194] As an example of an aromatic polyphenol containing a single aromatic ring, we can cite in particular resorcinol and phloroglucinol, for a reminder of their respective developed formulas (IV) and (V):

[0195] For example, in cases where the aromatic polyphenol has several aromatic rings, at least two of these aromatic rings, identical or different, are chosen from those with general formulas: in which the symbols Z 1 , Z 2, identical or different if there are several on the same aromatic nucleus, represent an atom (for example carbon, sulfur or oxygen) or a bonding group by definition at least divalent, which links at least these two aromatic nuclei to the rest of the aromatic polyphenol.

[0196] Another example of an aromatic polyphenol is 2,2',4,4'-tetrahydroxydiphenyl sulfide with the following structural formula (VII):

[0197] Another example of an aromatic polyphenol is 2,2',4,4'-tetrahydroxydiphenyl benzophenone with the following structural formula (VIII):

[0198] It is noted that each compound VII and VIII is an aromatic polyphenol comprising two aromatic rings (of formula VI-c) each of which carries at least two (in this case two) hydroxyl functions in meta position relative to each other.

[0199] Note that in the case of an aromatic polyphenol with at least one aromatic ring conforming to formula VI-b, the two ortho positions of each hydroxyl group of at least one aromatic ring are unsubstituted. In the case of an aromatic polyphenol with several aromatic rings conforming to formula VI-b, the two ortho positions of each hydroxyl group of each aromatic ring are unsubstituted.

[0200] According to one embodiment of the invention, the aromatic polyphenol is selected from the group consisting of resorcinol (IV), phloroglucinol (V), 2,2',4,4'-tetrahydroxydiphenyl sulfide (VII), 2,2',4,4'-tetrahydroxybenzophenone (VIII), and mixtures of these compounds. In a particularly advantageous embodiment, the aromatic polyphenol is phloroglucinol.

[0201] In one embodiment, the aromatic polyphenol A21 comprises a pre-condensed resin based on the aromatic polyphenol as described in any one of these embodiments.

[0202] This pre-condensed resin is advantageously based on: of at least one aromatic polyphenol as defined above, and preferably chosen from the group consisting of resorcinol, phloroglucinol, 2,2',4,4'-tetrahydroxydiphenyl sulfide, 2,2',4,4'-tetrahydroxybenzophenone, and mixtures thereof; and of at least one compound capable of reacting with the aromatic polyphenol comprising at least one aldehyde function and / or at least one compound capable of reacting with the aromatic polyphenol comprising at least two hydroxymethyl functions, and preferably an aromatic aldehyde comprising at least one aromatic ring bearing at least one aldehyde function.

[0203] The compound capable of reacting with the aromatic polyphenol may be an A1, A3 or A5 compound as defined above or any other aldehyde. Advantageously, said compound is chosen from the group consisting of an aromatic compound comprising an aromatic ring bearing at least two functional groups, one of these functional groups being a hydroxymethyl group, the other being an aldehyde or a hydroxymethyl group, formaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,2-benzenedicarboxaldehyde and mixtures of these compounds.Most advantageously, when the compound likely to react with the aromatic polyphenol is an aromatic compound comprising an aromatic ring bearing at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, this compound is chosen from the group consisting of 5-(hydroxymethyl)-furfural, 2,5-di(hydroxymethyl)furan and mixtures of these compounds.

[0204] Thus, in the pre-condensed aromatic polyphenol-based resin, the repeating motif meets the characteristics of aromatic polyphenol defined previously, except that at least one of the carbon atoms of the aromatic ring, which was unsubstituted, is linked to another motif.

[0205] Regardless of the compound other than the aromatic polyphenol used as the basis for the pre-condensed resin, this pre-condensed resin is free of free formaldehyde. Indeed, even if the pre-condensed resin is based on an aromatic polyphenol as described above and formaldehyde, the formaldehyde having already reacted with the aromatic polyphenol, the pre-condensed resin is free of free formaldehyde that could react with a compound A1 according to the invention in a subsequent step.

[0206] Aromatic polyphenol A21 may also comprise a mixture of a free aromatic polyphenol molecule and a pre-condensed aromatic polyphenol resin, as described previously. In particular, aromatic polyphenol A21 may also comprise a mixture of phloroglucinol and a pre-condensed phloroglucinol resin. Aromatic monophenol A22

[0207] The aromatic monophenol A22 can conform to two variants. In one variant, both ortho positions of the hydroxyl group are unsubstituted. In another variant, at least one ortho position and the para position of the hydroxyl group are unsubstituted.

[0208] Advantageously, in the variant in which at least one ortho position and the para position of the hydroxyl function are unsubstituted, a single ortho position is unsubstituted and the para position of the hydroxyl function is unsubstituted.

[0209] Preferably, regardless of the variant, the two ortho positions of the hydroxyl group are unsubstituted. This means that the two carbon atoms located on either side (in ortho positions) of the hydroxylated carbon atom (i.e., bearing the hydroxyl group) each have a single hydrogen atom attached.

[0210] Even more preferentially, the rest of the aromatic ring is unsubstituted. This means that the other carbon atoms of the rest of the aromatic ring (those other than the carbon atoms bearing the hydroxyl groups) are bonded with a single hydrogen atom.

[0211] In one embodiment, the aromatic monophenol comprises several six-membered aromatic rings, at least two of them each bearing a single hydroxyl function and, for at least one of the hydroxyl functions, both ortho positions of the hydroxyl function are unsubstituted, or at least one ortho position and the para position of the hydroxyl function are unsubstituted.

[0212] Preferably, the two ortho positions of each hydroxyl function of at least one six-membered aromatic ring are unsubstituted.

[0213] Even more preferentially, the two ortho positions of each hydroxyl function of each six-membered aromatic ring are unsubstituted.

[0214] Even more preferably, the remainder of each aromatic ring is unsubstituted. This means that the other carbon atoms of the remainder of each aromatic ring (those other than the carbon atoms bearing the hydroxyl functions or bearing the group linking the aromatic rings together) bear a single hydrogen atom.

[0215] Advantageously, the aromatic ring or rings of the aromatic monophenol are benzene rings.

[0216] Preferably, the aromatic monophenol is chosen from the group consisting of phenol, orthocresol, metacresol, paracresol, orthochlorophenol, metachlorophenol, parachlorophenol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-vinylphenol, 4-ethylphenol, 4-isopropylphenol, 4-isobutylphenol, paracoumaric acid and mixtures of these compounds.

[0217] In one embodiment, aromatic monophenol A22 comprises a pre-condensed resin based on aromatic monophenol as described in any one of these embodiments.

[0218] This pre-condensed resin is advantageously based on: of at least one aromatic monophenol as defined above, and preferably chosen from the group consisting of phenol, orthocresol, metacresol, paracresol, orthochlorophenol, metachlorophenol, parachlorophenol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-vinylphenol, 4-ethylphenol, 4-isopropylphenol, 4-isobutylphenol, paracoumaric acid and mixtures of these compounds; and of at least one compound capable of reacting with the aromatic monophenol comprising at least one aldehyde function and / or at least one compound capable of reacting with the aromatic monophenol comprising at least two hydroxymethyl functions and preferably an aromatic aldehyde comprising at least one aromatic ring bearing at least one aldehyde function.

[0219] The compound capable of reacting with the aromatic monophenol may be an A1, A3 or A5 compound as defined above or any other aldehyde. Advantageously, said compound capable of reacting with the aromatic monophenol is chosen from the group consisting of an aromatic compound comprising an aromatic ring bearing at least two functional groups, one of these functional groups being a hydroxymethyl group, the other being an aldehyde or a hydroxymethyl group, formaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,2-benzenedicarboxaldehyde and mixtures of these compounds.Most advantageously, when the compound is an aromatic compound comprising an aromatic ring bearing at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, this compound is chosen from the group consisting of 5-(hydroxymethyl)-furfural, 2,5-di(hydroxymethyl)furan and mixtures of these compounds.

[0220] Thus, in the pre-condensed aromatic monophenol-based resin, the repeating motif meets the characteristics of aromatic monophenol defined previously, except that at least one of the carbon atoms of the six-membered aromatic ring, which was unsubstituted, is linked to another motif.

[0221] Regardless of the compound other than the aromatic monophenol used as the basis for the pre-condensed resin, this pre-condensed resin is free of free formaldehyde. Indeed, even if the pre-condensed resin is based on an aromatic monophenol as described above and formaldehyde, since the formaldehyde has already reacted with the aromatic monophenol, the pre-condensed resin is free of free formaldehyde that could react with a compound A1, A3, or A5 according to the invention in a subsequent step.

[0222] Aromatic monophenol A22 may also comprise a mixture of a free molecule of aromatic monophenol and a pre-condensed aromatic monophenol resin, as described previously. In particular, aromatic monophenol A22 may also comprise a mixture of phenol and a pre-condensed phenol resin. Mixture of aromatic polyphenol A21 and aromatic monophenol A22

[0223] Phenol may also comprise a mixture of an aromatic polyphenol A21 and an aromatic monophenol A22, as described previously.

[0224] Preferably, the phenol comprises a mixture of aromatic polyphenol and a pre-condensed resin based on aromatic polyphenol. REINFORCED PRODUCT OBTAINED BY THE PROCESS ACCORDING TO THE INVENTION

[0225] A product reinforced by at least one reinforcing element that can be obtained by the process as defined above is also described.

[0226] Advantageously, the reinforced product comprises one or more reinforcing elements embedded in the matrix of the composition, and in the case of several reinforcing elements, the reinforcing elements are arranged side by side along a principal direction. Each reinforcing element comprises at least one wire element and may, in certain embodiments, comprise several wire elements.

[0227] In one embodiment, the reinforcing element may comprise a wire element and optionally a sheath covering the wire element individually or several wire elements collectively. The sheath may comprise one or more layers, each layer being based on a polymer composition, for example as described in WO2010 / 136389, WO2010 / 105975, WO2011 / 012521, WO2011 / 051204, WO2012 / 016757, WO2012 / 038340, WO2012 / 038341, WO2012 / 069346, WO2012 / 104279, WO2012 / 104280 and WO2012 / 104281.

[0228] A wire element is defined as an element whose length is at least 10 times greater than the longest dimension of its cross-section, regardless of the cross-section's shape: circular, elliptical, oblong, polygonal, including rectangular, square, or oval. In the case of a rectangular cross-section, the wire element takes the form of a strip.

[0229] In another embodiment, the reinforcing element can be a knit or a fabric.

[0230] A knitted fabric is an assembly of yarn elements as defined above, comprising stitches formed by one or more of these yarn elements. Each stitch consists of a loop interlaced with another loop. Examples include stockinette stitch or English rib knits, and charmeuse or atlas knits, which are knitted with yarn overs.

[0231] A fabric is an assembly of two sets of threads: a first set of warp threads, which are substantially parallel to each other, and a second set of weft threads, which are also substantially parallel to each other. Preferably, the warp threads are substantially perpendicular to the weft threads.

[0232] The wire element can be metallic or textile.

[0233] A metallic wire element can be a basic metallic monofilament. Such a basic metallic monofilament comprises a steel core, optionally coated with one or more layers of a coating that may be metallic and / or based on a non-metallic adhesive composition.

[0234] The metallic cladding comprises a metal selected from zinc, copper, tin, cobalt, and alloys of these metals. Examples of alloys of these metals include brass and bronze. The core steel is a carbon steel containing between 0.1% and 1.2% carbon by mass, a maximum of 11% chromium by mass, and less than 1% by mass of each of the following elements: manganese, silicon, aluminum, boron, cobalt, copper, molybdenum, nickel, niobium, titanium, tungsten, vanadium, zirconium, phosphorus, sulfur, and nitrogen. The remainder consists of iron and unavoidable impurities resulting from the manufacturing process. The steel may exhibit a pearlitic, ferritic, austenitic, bainitic, or martensitic microstructure, or a microstructure resulting from a mixture of these microstructures.

[0235] The elementary metallic monofilament exhibits a mechanical strength ranging from 1000 MPa to 5000 MPa. Such mechanical strengths correspond to the steel grades commonly encountered in the tire industry, namely NT (Normal Tensile), HT (High Tensile), ST (Super Tensile), SHT (Super High Tensile), UT (Ultra Tensile), UHT (Ultra High Tensile), and MT (Mega Tensile). The use of high mechanical strengths potentially allows for improved reinforcement of the matrix in which the reinforcing element is intended to be embedded, and a reduction in the weight of the reinforced matrix.

[0236] In the case where the elementary metallic monofilament has a circular cross-section, the diameter of these elementary metallic monofilaments preferentially ranges from 0.05 mm to 0.50 mm.

[0237] A metallic wire element can be an assembly of several elementary metallic monofilaments as described above, assembled together in a helix, for example by cabling or twisting the elementary metallic monofilaments to form, for example, layered cables comprising several concentric layers of elementary metallic monofilaments or stranded cables, each strand comprising several concentric layers of elementary metallic monofilaments. Optionally, and as described in WO2005071157, such a metallic wire element includes a layer based on a polymer composition, preferably a composition comprising an elastomer, this layer being disposed between two layers of elementary metallic monofilaments of the layered cable or of a strand of the stranded cable.

[0238] A textile fiber element can be a basic textile monofilament, optionally coated with one or more layers of a non-metallic adhesive composition. This basic textile monofilament is obtained, for example, by melt spinning, solution spinning, or gel spinning. Each basic textile monofilament is made from an organic material, particularly a polymer, or an inorganic material, such as glass or carbon. Polymeric materials can be thermoplastic, such as aliphatic polyamides, particularly polyamide 6-6, and polyesters, particularly polyethylene terephthalate. Polymeric materials can be non-thermoplastic, such as aromatic polyamides, particularly aramid, and cellulose, both natural and synthetic, particularly rayon.Each elementary textile monofilament has a substantially circular cross-section with a diameter ranging, for example, from 2 µm to 100 µm.

[0239] A textile yarn element can be an assembly of several elementary textile monofilaments as defined above, also called a strand. A strand preferably comprises more than 10 elementary textile monofilaments, preferably more than 100 elementary textile monofilaments, and more preferably more than 500 elementary textile monofilaments.

[0240] A textile yarn element can also be an assembly of several strands as defined above. In one variation, the materials from which the elementary textile monofilaments of each strand are made are identical. In another variation, the materials from which the elementary textile monofilaments of each strand are made are different; the textile yarn element is then commonly called a hybrid textile yarn element.

[0241] Whether in the case of a metallic or textile filament, the layer based on a non-metallic adhesive composition is, in one embodiment, formed by a layer of an adhesion primer that improves the adhesion of the filament, for example, to an elastomeric matrix. Such adhesion primers are those commonly used by those skilled in the art for pre-gluing certain textile fibers (particularly polyester fibers, for example PET, aramid, and aramid / nylon). For example, an epoxy-based primer, particularly one based on polyglycerol polyglycidyl ether, may be used. A blocked isocyanate-based primer may also be used.

[0242] Whether in the case of a metallic or textile wire element, the layer based on a non-metallic adhesive composition is, in another embodiment, formed by a layer based on a resin and an elastomer latex. Examples include RFL (Resorcinol-Formaldehyde-Latex) type adhesive compositions, as well as adhesive compositions as described in WO2015118041.

[0243] Whether in the case of a metallic or textile wire element, in yet another embodiment, there may be a layer of an adhesion primer coating the wire element, this layer of adhesion primer itself being coated with a layer based on a resin and an elastomer latex(s). COMPOSITE REINFORCED BY A REINFORCED PRODUCT OBTAINED BY THE PROCESS ACCORDING TO THE INVENTION

[0244] A composite elastomer reinforced with at least one product reinforced by at least one reinforcing element as defined above is also described. The elastomer matrix is ​​based on an elastomer composition comprising at least one elastomer and another constituent.

[0245] This elastomer composite can be prepared using a process comprising at least the following steps: in a first step, combine at least one reinforced product with an elastomer composition to form a reinforced elastomer composite of the reinforced product; then, in a second step, crosslink by baking, for example by vulcanization, preferably under pressure, the composite thus formed.

[0246] Preferably, the elastomer composition includes a diene elastomer. By elastomer or rubber (the two terms being synonymous) of the "diene" type, we generally mean an elastomer derived at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or not).

[0247] Elastomer compositions may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer(s) being able to be used in association with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.

[0248] In a first embodiment preferably intended for pneumatic use, the elastomer composition comprises a diene elastomer selected from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), various butadiene copolymers, various isoprene copolymers, and mixtures of these elastomers.

[0249] Such copolymers are most preferentially chosen from the group consisting of butadiene-styrene copolymers (SBR), whether the latter are prepared by emulsion polymerization (ESBR) or solution polymerization (SSBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-butadiene-styrene copolymers (SBIR).

[0250] Advantageously, the ethylene alpha olefin type elastomer is chosen from the group consisting of ethylene-propylene copolymers (EPM), ethylene-propylene-diene copolymers (EPDM) and mixtures of these copolymers.

[0251] Preferably, the elastomer composition includes a reinforcing filler.

[0252] When a reinforcing filler is used, any type of reinforcing filler known for its ability to reinforce an elastomer composition usable for the manufacture of tires can be used, for example an organic filler such as carbon black, an inorganic reinforcing filler such as silica, or a blend of these two types of filler, in particular a blend of carbon black and silica.

[0253] All carbon blacks conventionally used in tires (so-called tire-grade blacks) are suitable. For example, reinforcing carbon blacks from the 100, 200, or 300 series (ASTM grades) are particularly suitable.

[0254] In the case of using carbon blacks with an isoprene elastomer, the carbon blacks could, for example, already be incorporated into the isoprene elastomer in the form of a masterbatch (see, for example, applications WO 97 / 36724 or WO 99 / 16600).

[0255] Examples of organic fillers other than carbon blacks include functionalized polyvinylaromatic organic fillers as described in applications WO-A-2006 / 069792 and WO-A-2006 / 069793.

[0256] In this application, the term "reinforcing inorganic filler" is defined as any inorganic or mineral filler (regardless of its color or origin, whether natural or synthetic), also called "white" filler, "light" filler, or even "non-black filler" (as opposed to carbon black), capable of reinforcing an elastomeric composition on its own, without the need for an intermediate coupling agent; in other words, capable of replacing conventional, pneumatic-grade carbon black in its reinforcing function. Such a filler is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface.

[0257] The physical state of the reinforcing inorganic filler is irrelevant, whether it be in the form of powder, micro-beads, granules, spheres, or any other suitable densified form. Of course, the term "reinforcing inorganic filler" also includes mixtures of different reinforcing inorganic fillers, particularly highly dispersible siliceous and / or aluminous fillers as described below.

[0258] Suitable inorganic reinforcing fillers include mineral fillers of the siliceous type, particularly silica (SiO2), or of the aluminous type, particularly alumina (Al2O3). The silica used may be any reinforcing silica known to those skilled in the art, including any precipitated or pyrogenated silica with a BET surface area and a CTAB specific surface area both less than 450 m² / g, preferably from 30 to 400 m² / g. Examples of highly dispersible precipitated silicas (known as "HDS") include "Ultrasil" 7000 and "Ultrasil" 7005 from Evonik, "Zeosil" 1165MP, 1135MP and 1115MP from Rhodia, "Hi-Sil" EZ150G from PPG, "Zeopol" 8715, 8745 and 8755 from Huber, and high specific surface area silicas as described in application WO 03 / 16837.

[0259] Finally, a person skilled in the art will understand that, as an equivalent charge to the reinforcing inorganic charge described in this paragraph, a reinforcing charge of another nature, in particular organic, could be used, provided that this reinforcing charge is covered with an inorganic layer such as silica, or has functional sites on its surface, in particular hydroxyl, requiring the use of a coupling agent to establish the bond between the charge and the elastomer.

[0260] Preferably, the total reinforcing charge (carbon black and / or inorganic reinforcing charge such as silica) is in the range of 5 to 120 pc, more preferably 5 to 100 pc and even more preferably 5 to 90 pc.

[0261] Carbon black can advantageously be used as the sole reinforcing filler or as the predominant reinforcing filler. Of course, a single carbon black or a blend of several carbon blacks of different ASTM grades can be used. Carbon black can also be used in blends with other reinforcing fillers, particularly inorganic reinforcing fillers as described previously, and especially silica.

[0262] When an inorganic filler (for example silica) is used in the composition of rubber, alone or in blending with carbon black, its rate is in the range of 0 to 70 pc, preferably 0 to 50 pc, particularly also 5 to 70 pc, and even more preferably this proportion ranges from 5 to 50 pc, particularly 5 to 40 pc.

[0263] Preferably, the elastomer composition includes various additives.

[0264] Rubber compositions may also include all or part of the usual additives commonly used in elastomer compositions for the manufacture of tires, such as plasticizers or extension oils, whether aromatic or non-aromatic, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents or adhesion promoters.

[0265] Preferably, the elastomer composition includes a crosslinking system, more preferably a vulcanizing system.

[0266] In the embodiment preferably intended for pneumatic use, the elastomer composition includes a vulcanization system.

[0267] The vulcanization system includes a sulfur-donating agent, for example sulfur.

[0268] Preferably, the vulcanization system includes vulcanization activators such as zinc oxide and stearic acid.

[0269] Preferably, the vulcanization system includes a vulcanization accelerator and / or a vulcanization retarder.

[0270] Advantageously, the composite is such that the elastomer matrix is ​​based on an elastomer composition comprising a crosslinking system with a molecular sulfur content ranging from 1 to 10 parts per cubic centimeter. Molecular sulfur is defined as sulfur derived from a Sn compound with n > 2.

[0271] The sulfur content is measured by elemental analysis using the Thermo Scientific Flash 2000 microanalyzer. The analysis includes a sample combustion step followed by a separation step of the resulting compounds. Approximately 1 mg of sample is introduced into the microanalyzer, where it undergoes flash combustion at 1000°C under oxygen. The gases formed are then oxidized by excess oxygen and a tungstic anhydride catalyst. A reduction step using copper then traps excess oxygen and reduces nitrogen oxides to N₂ and sulfites to sulfur dioxide (SO₂). Water is trapped, and the resulting N₂, CO₂, and SO₂ compounds are separated on a chromatographic column and then detected by a heat halide meter. Total sulfur is quantified by measuring the area of ​​the SO₂ peak after calibration with standards.

[0272] All vulcanization accelerators, retarders, and activators are used at a preferential rate within a range of 0.5 to 15 parts per million (ppm). The vulcanization activator(s) is / are used at a preferential rate within a range of 0.5 to 12 ppm.

[0273] The crosslinking system itself is preferably sulfur-based and includes a primary vulcanization accelerator, particularly a sulfenamide-type accelerator. Various known secondary accelerators or vulcanization activators, such as zinc oxide, stearic acid, and guanidine derivatives (especially diphenylguanidine), are added to this vulcanization system.

[0274] Any compound capable of acting as a vulcanization accelerator of diene elastomers in the presence of sulfur can be used as an accelerator (primary or secondary), including thiazole-type accelerators and their derivatives, thiuram-type accelerators, and zinc dithiocarbamate-type accelerators. These accelerators are most preferably chosen from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N,N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated "DCBS"), N-ter-butyl-2-benzothiazyl sulfenamide (abbreviated "TBBS"), N-ter-butyl-2-benzothiazyl sulfenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate (abbreviated "ZBEC"), and mixtures of these compounds. Preferably, a sulfenamide-type primary accelerator is used. PNEUMATIC

[0275] A tire is also described. The reinforced product of the invention or the elastomer composite described above are advantageously usable for reinforcing tires of all types of vehicles, in particular passenger vehicles or industrial vehicles such as heavy goods vehicles.

[0276] The invention will be better understood upon reading the following description, given solely by way of non-limiting example and made with reference to the drawings in which: there figure 1 is a diagram of a tire; the figure 2 is a cross-sectional view of a composite forming a working layer of the tire of the figure 1 ; and the figure 3 is a diagram illustrating the different stages of a manufacturing process for a reinforced product according to the invention.

[0277] There figure 1The attached figure represents, in a very schematic way (without respecting a specific scale), a radial cross-section of a tire for a passenger vehicle.

[0278] This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3, and two bead 4, each bead 4 being reinforced with a strand 5. The crown 2 is surmounted by a tread not shown in this schematic figure. A carcass reinforcement 7 is wound around the two strands 5 in each bead 4, the folded edge 8 of this reinforcement 7 being, for example, oriented towards the outside of the tire 1, which is shown here mounted on its rim 9.The carcass reinforcement 7 is known in itself to consist of at least one layer reinforced by so-called "radial" cables, for example textile, that is to say that these cables are arranged practically parallel to each other and extend from one bead to the other so as to form an angle between 80° and 90° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located halfway between the two beads 4 and passes through the middle of the apex reinforcement 6).

[0279] This tire 1 of the invention has, for example, as its essential characteristic that at least one apex reinforcement 6 comprises a conductive element, here a coated conductive wire element or an elastomer composite according to the invention. According to another embodiment, the rods themselves could, for example, be made, in whole or in part, of a conductive element, here a coated conductive wire element.

[0280] Of course, the invention relates to the objects previously described, namely the elastomer composite such as the tire comprising it, both in the raw state (before crosslinking) and in the cured state (after crosslinking).

[0281] We have represented on the figure 2 a cross-sectional view of a composite, designated by the general reference 30, forming a working layer of the tire. figure 1 The composite 30 comprises at least one product reinforced 34 by reinforcing elements 36, in this case metallic monofilaments, embedded in the elastomeric matrix 32.

[0282] On the figure 2 The elastomeric matrix 32, the reinforced product 34, and the reinforcing elements 36 are represented in an X, Y, Z coordinate system in which the Y direction is the radial direction and the X and Z directions are the axial and circumferential directions. figure 2The composite 30 comprises three reinforced products 34 arranged side by side along the principal direction X. Each reinforced product 34 comprises a matrix 38 based on the compounds described above and three reinforcing wire elements 36 arranged side by side along the principal direction X and extending parallel to each other within the reinforced product 34 and collectively embedded in the matrix 38. Each reinforcing wire element 36 comprises, here, a metallic monofilament 40. Alternatively, each reinforcing wire element 36 could be an assembly of several metallic monofilaments.

[0283] In another variant, each reinforced product 34 comprises a single reinforcing wire element 36 individually embedded in the matrix 38. Several reinforced products 34 conforming to this other variant are then embedded in the elastomeric matrix 32. The reinforcing wire element 36 can be a metallic monofilament or an assembly of several metallic monofilaments.

[0284] We will now describe an example of a manufacturing process for a reinforced product 34 with reference to the figure 3 .

[0285] In a first embodiment, the composition comprises a compound A1 and a compound A2.

[0286] During the process, the components of the composition are mixed in step 42. To do this, 30.43 g of compound A1 are mixed with 19.07 g of compound A2 at a temperature Tm. In the example described, compound A1 is 1,2-benzenedicarboxaldehyde, which has a melting point of 57°C at atmospheric pressure, and compound A2 is phloroglucinol, which has a melting point of 218°C at atmospheric pressure. The mixture is prepared at a temperature of 60°C at atmospheric pressure.

[0287] In step 44, additives are added, which can be fillers or drying agents. Here, 0.25 g of magnesium sulfate and 0.25 g of N326 carbon black are added.

[0288] In step 46, the reinforcement elements 36 are then embedded in the composition.

[0289] Then, in step 48, the resin based on 1,2-benzenedicarboxaldehyde and phloroglucinol is crosslinked by heating to at least 110°C under atmospheric pressure and here 110°C at atmospheric pressure.

[0290] Finally, a final crosslinking step 50 of the resin is carried out by heating to a temperature of 180°C at 1.03 bar.

[0291] In the embodiment described here, the reinforced product 36 is obtained which will then be embedded in an elastomeric composition to form the elastomeric composite 30 as described previously which will be used in the tire.

[0292] In another embodiment of the invention not described here, the reinforced product 36 is obtained which will be used directly in the tire.

[0293] The invention is not limited to the embodiments described above.

[0294] Examples of compositions implementing or not the process according to the first embodiment of the invention are gathered in Table 1 below.

[0295] In example T1, which uses 1,4-benzenedicarboxaldehyde and phloroglucinol, the mixture is heated to 120°C at atmospheric pressure to melt the compound with the lowest melting point, in this case 1,4-benzenedicarboxaldehyde (which melts at 115°C at atmospheric pressure). This temperature of 120°C is greater than or equal to the crosslinking temperature of the resin based on 1,4-benzenedicarboxaldehyde and phloroglucinol. This results in premature crosslinking of the resin, which prevents further manipulation of the composition, particularly any step involving the embedding of reinforcing elements. Premature crosslinking of the resin in example T2 is also observed for the same reasons.

[0296] In the other processes according to the invention implementing compositions E1 to E5, the liquid dissolution temperature is adjusted to just the necessary level to solubilize compound A2 in compound A1 without the resin crosslinking step starting, i.e. the composition remains liquid for a sufficient opening time to embed the reinforcing element(s) in the matrix based on this composition and thus form a reinforced product according to the invention.

[0297] In the example process implementing composition E1 according to the first embodiment of the invention, the temperatures satisfy, at atmospheric pressure, the following conditions: T1= 57°C ≤ Tm= 60°C ≤ Tn = 110°C and T2 = 218°C ≥ Tn = 110°C with T1 < T2, 10°C ≤ Tn-Tm= 50°C ≤ 60°C, and Tp= 180°C > Tn =110°C with Tn ≤ 120°C and Tm ≤ 80°C.

[0298] Other examples of compositions implemented in processes conforming to the second embodiment (composition F1 to F4) and the third embodiment (F5) of the invention are gathered in Tables 2 and 3 below.

[0299] In the processes according to the second embodiment of the invention implementing compositions F1 to F4, the liquid dissolution temperature is adjusted to just the necessary extent to allow two of the compounds A3, A4, A5 to be solubilized in the one of the compounds A3, A4, A5 having the lowest melting temperature without the resin crosslinking step beginning.

[0300] In the example process implementing composition F1 according to the second embodiment of the invention, the temperatures satisfy, at atmospheric pressure, the following conditions: Tmin= 57°C ≤ Tm= 60°C ≤ Tn = 110°C and Tint = 115°C and Tmax = 218°C are greater than or equal to Tn = 110°C, 10°C ≤ Tn-Tm= 50°C ≤60°C, and Tp= 180°C> Tn = 110°C, with Tn ≤ 120°C and Tm ≤ 80°C.

[0301] Thus, it is possible to implement the second embodiment of the process of the invention for the composition comprising 1,4-benzenedicarboxaldehyde and phloroglucinol (example T1 above) by adding 1,2-benzenedicarboxaldehyde (example composition F1 according to the invention). The reactivity of the resin is thereby controlled by regulating the solubilization temperature of the various components, and in particular that of 1,4-benzenedicarboxaldehyde.

[0302] In the process according to the third embodiment of the invention implementing composition F5, it is observed that it is indeed the compound with the lowest melting temperature that will control the solubilization temperature.

[0303] In the example process implementing composition F5 according to the invention, the temperatures satisfy, at atmospheric pressure, the following conditions: Tmin= 88°C ≤ Tm= 100°C ≤ Tn = 110°C and Tint1 = 115°C, Tint2 = 175°C and Tmax = 218°C are greater than or equal to Tn = 110°C, 10°C ≤ Tn-Tm= 10°C ≤ 60°C, and Tp= 180°C> Tn =110°C with Tn ≤ 120°C and Tm ≤ 100°C.

[0304] In this F5 composition, only one component has a melting point below 100°C at atmospheric pressure, while the other three have melting points at atmospheric pressure well above 110°C. Thus, the resin's reactivity is controlled by adjusting the solubilization temperature of the different components by selecting the one with the lowest melting point.

[0305] It will also be possible to combine the characteristics of the different embodiments described or envisaged above, provided that they are compatible with each other. Table 1 Compositions T1 T2 E1 E2 E3 E4 E5 A1 1,4-benzenedicarboxyl (3) 1,4-benzenedicarboxyl (3) 1,2-benzenedicarboxyl (1) 1,3-benzenedicarboxyl (2) 1,2-benzenedicarboxyl (1) 1,3-benzenedicarboxyl (2) 5-(hydroxymethyl)-furfural (4) T1 115°C 115°C 57°C 88°C 57°C 88°C 31°C A2 phloroglucinol(5) Resorcinol sulfide (6) phloroglucinol(5) phloroglucinol(5) Resorcinol sulfide (6) Resorcinol sulfide (6) phloroglucinol(5) T2 218°C 175°C 218°C 218°C 175°C 175°C 218°C T2-T1 103°C 60°C 161°C 130°C 118°C 87°C 187°C Temperatures of the process stages Tm 120°C 120°C 60°C 90°C 60°C 90°C 60°C Tm-T1 5°C 5°C 3°C 2°C 3°C 2°C 29°C Tn 120°C 120°C 110°C 110°C 110°C 110°C 110°C Tn-Tm 0°C 0°C 50°C 20°C 50°C 20°C 50°C Tp 180°C 180°C 180°C 180°C 180°C 180°C 180°C Method according to the invention No No Yes, 1st mode Yes, 1st mode Yes, 1st mode Yes, 1st mode Yes, 1st mode (1) 1,2-benzenedicarboxaldehyde (from Sigma Aldrich; 99% purity); (2) 1,3-benzenedicarboxaldehyde (from Sigma Aldrich; 99% purity); (3) 1,4-benzenedicarboxaldehyde (from Sigma Aldrich; 99% purity); (4) 5-(hydroxymethyl)-furfural (from Aldrich; 99% purity); (5) Phloroglucinol (from Sigma Aldrich; 99% purity); (6) Resorcinol sulfide (from Sigma Aldrich; 99% purity). Table 2 Compositions F1 F2 F3 F4 F5 A3 1,2-benzenedicarboxaldehyde (1) 1,3-benzenedicarboxaldehyde (2) 1,2-benzenedicarboxaldehyde (1) 1,3-benzenedicarboxaldehyde (2) 1,3-benzenedicarboxaldehyde (2) A4 1,4-benzenedicarboxaldehyde of (3) 1,4-benzenedicarboxaldehyde (3) 1,4-benzenedicarboxaldehyde (3) 1,4-benzenedicarboxaldehyde (3) 1,4-benzenedicarboxaldehyde (3) T3 57°C 88°C 57°C 88°C 88°C T4 115°C 115°C 115°C 115°C 115°C A5 Phloroglucinol (5) Phloroglucinol (5) Resorcinol sulfide (6) Resorcinol sulfide (6) Phloroglucinol (5) A6 - - - - Resorcinol sulfide (6) T5 218°C 218°C 175°C 175°C 218°C T6 - - - - 175°C Tmin 57°C 88°C 57°C 88°C 88°C Tmax 218°C 218°C 175°C 175°C 218°C Tint 115°C 115°C 115°C 115°C - Tint1 - - - - 115°C Tint2 - - - - 175°C Tmax - Tmin 161°C 130°C 118°C 87°C 130°C Table 3 Compositions F1 F2 F3 F4 F5 Temperatures of the process stages Tm 60°C 90°C 60°C 90°C 100°C Tm - Tmin 3°C 2°C 3°C 2°C 12°C Tn 110°C 120°C 110°C 120°C 110°C Tn-Tm 50°C 30°C 50°C 30°C 10°C Tp 180°C 180°C 180°C 180°C 180°C Method according to the invention Yes, 2nd mode Yes, 2nd mode Yes, 2nd mode Yes, 2nd mode Yes, 3rd mode

Claims

1. Process for the manufacture of a reinforced product (34) comprising a matrix (38) based on a composition and at least one reinforcing element (36), the reinforcing element(s) being embedded in the matrix (38), characterized in that: • a stage of manufacture of the composition comprising a mixture comprising: - at least one compound A1 exhibiting a melting point T1, and - at least one compound A2 exhibiting a melting point T2, is carried out by mixing at least the compound A1 and at least the compound A2 at a temperature Tm such that: - T1 ≤ Tm < T2, so as to dissolve A2 in A1 and to obtain the composition in the liquid state, the composition is devoid of any organic solvent or of water; • then the reinforcing element(s) (36) is / are drowned in the composition in the liquid state, • then, as the compound A1 reacts with the compound A2 to form the resin by heating from a temperature Tn, a stage of crosslinking a resin based on at least the compound A1 and on at least the compound A2 is carried out by heating the composition to at least the temperature Tn such that T1 ≤ Tm < Tn so as to form the matrix (38) in which the reinforcing element(s) (36) is / are embedded defined as a three-dimensional element which makes possible the mechanical reinforcement of a matrix in which this three-dimensional reinforcing element is intended to be embedded; wherein one base constituent of the resin A1, A2, being chosen from: • a compound A11 comprising at least one aromatic nucleus bearing at least two functional groups, one of these functional groups being a hydroxymethyl functional group and the other being an aldehyde functional group or a hydroxymethyl functional group, or • a compound A12 is selected from 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and the mixtures of these compounds, or • a mixture of a compound A11 and of a compound A12.

2. Process for the manufacture of a reinforced product (34) comprising a matrix (38) based on a composition and at least one reinforcing element (36), the reinforcing element(s) being embedded in the matrix (38), characterized in that: • a stage of manufacture of the composition comprising a mixture comprising: - at least one compound A3 exhibiting a melting point T3, - at least one compound A4 exhibiting a melting point T4, and - at least one compound A5 exhibiting a melting point T5, is carried out by mixing at least the compounds A3, A4 and A5 at a temperature Tm such that Tmin ≤ Tm < Tmax, in which: - Tmin is the lowest temperature among T3, T4 and T5, - Tmax is the highest temperature among T3, T4 and T5, and - Tint is the temperature among T3, T4 and T5 such that Tmin ≤ Tint ≤ Tmax, so as to dissolve at least one or two of the compounds A3, A5, A4 respectively in at least two others or another of the compounds A3, A5, A4 and to obtain the composition in the liquid state, the composition is devoid of any organic solvent or of water; • then the reinforcing element(s) (36) is / are drowned in the composition in the liquid state, • then, as the compounds A3, A4 and A5 react together to form the resin by heating from a temperature Tn, a stage of crosslinking a resin based on at least the compounds A3, A4 and A5 is carried out by heating the composition to at least the temperature Tn such that Tmin ≤ Tm < Tn so as to form the matrix (38) in which the reinforcing element(s) (36) is / are embedded, defined as a three-dimensional element which makes possible the mechanical reinforcement of a matrix in which this three-dimensional reinforcing element is intended to be embedded; wherein one base constituent of the resin A3, A4, A5 being chosen from: • a compound A11 comprising at least one aromatic nucleus bearing at least two functional groups, one of these functional groups being a hydroxymethyl functional group and the other being an aldehyde functional group or a hydroxymethyl functional group, or • a compound A12 is selected from 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and the mixtures of these compounds, or • a mixture of a compound A11 and of a compound A12.

3. Process for the manufacture of a reinforced product (34) comprising a matrix (38) based on a composition and at least one reinforcing element (36), the reinforcing element(s) being embedded in the matrix (38), characterized in that: • a stage of manufacture of the composition comprising a mixture comprising: - at least one compound A3 exhibiting a melting point T3, - at least one compound A4 exhibiting a melting point T4, - at least one compound A5 exhibiting a melting point T5, - at least one compound A6 exhibiting a melting point T6, is carried out by mixing at least the compounds A3, A4, A5 and A6 at a temperature Tm such that Tmin ≤ Tm < Tmax, in which: - Tmin is the lowest temperature among T3, T4, T5 and T6, and - Tmax is the highest temperature among T3, T4, T5 and T6, - Tint1 is the temperature among T3, T4, T5 and T6, and - Tint2 is the temperature among T3, T4, T5 and T6 such that: Tmin ≤ Tint1 ≤ Tint2 ≤ Tmax, so as to dissolve one, two or three of the compounds A3, A4, A5, A6 in respectively three, two or another of the compounds A3, A4, A5, A6 and to obtain the composition in the liquid state; the composition is devoid of any organic solvent or of water; • then the reinforcing element(s) (36) is / are drowned in the composition in the liquid state, • then, as the compounds A3, A4, A5 and A6 react together to form the resin by heating from a temperature Tn, a stage of crosslinking a resin based on at least the compounds A3, A4, A5 and A6 is carried out by heating the composition to at least the temperature Tn such that Tmin ≤ Tm < Tn so as to form the matrix (38) in which the reinforcing element(s) (36) is / are embedded, defined as a three-dimensional element which makes possible the mechanical reinforcement of a matrix in which this three-dimensional reinforcing element is intended to be embedded; wherein one base constituent of the resin A3, A4, A5, A6 being chosen from: • a compound A11 comprising at least one aromatic nucleus bearing at least two functional groups, one of these functional groups being a hydroxymethyl functional group and the other being an aldehyde functional group or a hydroxymethyl functional group, or • a compound A12 is selected from 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and the mixtures of these compounds, or • a mixture of a compound A11 and of a compound A12.

4. Process according to any one of the preceding claims, in which Tn-Tm ≥ 5°C and more preferentially Tn-Tm ≥ 10°C.

5. Process according to any one of the preceding claims, in which Tn-Tm ≤ 100°C and more preferentially Tn-Tm ≤ 60°C.

6. Process according to any one of the preceding claims, in which, subsequent to the stage of crosslinking of the resin, a stage of final crosslinking of the resin is carried out by heating to a temperature Tp with Tn < Tp.

7. Process according to the preceding claim, in which the temperature Tp ≤ 200°C.

8. Process according to any one of the claims 2 to 7, in which the compound A12 is selected from the group consisting of 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and the mixtures of these compounds.

9. Process according to any one of the claims 2 to 7, in which the compound A12 is selected from the group consisting of furfuraldehyde, 2,5-furandicarboxaldehyde and the mixtures of these compounds.

10. Process according to any one of the preceding claims, in which the compound A11 corresponds to the general formula (II): where B represents CHO or CH2OH, Y represents O, NR1, NO, S, SO, SO2 or SR2R3, R1 represents a hydrogen or an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group and R2 and R3 each represent, independently of each other, a hydrogen or an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group.

11. Process according to any one of the preceding claims, in which the compound A11 corresponds to the general formula (II'a1) or (II'a2):

12. Process according to any one of the preceding claims, in which at least one of the compounds A1, A2, A3, A4, A5, A6 is a phenol chosen from: ∘ an aromatic polyphenol A21 comprising at least one aromatic nucleus bearing at least two hydroxyl functional groups in the meta position with respect to each other, the two positions ortho to at least one of the hydroxyl functional groups being unsubstituted, ∘ an aromatic monophenol A22 comprising at least one six-membered aromatic nucleus bearing a single hydroxyl functional group, - the two positions ortho to the hydroxyl functional group being unsubstituted, or - at least one position ortho to and the position para to the hydroxyl functional group being unsubstituted, ∘ a mixture of A21 and A22.