FR3075801B1 - METHOD FOR MANUFACTURING A RESIN-BASED BINDER FOR COATING WITH PELLETS OF MATERIAL, BINDER OBTAINED AND COATING OBTAINED - Google Patents

Abstract

The present invention relates to a process for the production of a resin-based binder for granular material coating, said binder consisting of a single-component polyurethane resin comprising a single reaction component formed of an isocyanate part, a solvent and a catalyst. A non-flammable and non-toxic solvent consisting of a 2,5,7,10-TetraOxaUndecane (TOU) cleaning agent is especially used, the said solvent is added by mass in the said isocyanate portion, and the result is surprisingly and unexpectedly obtained. a non-toxic, transparent, one-component, non-toxic, one-component polyurethane resin with good behavior even under extreme use conditions of temperature up to 45 ° C and relative humidity up to 90% to bind granules of material between them and to a surface to cover and form a durable coating, resistant to mechanical stress and ultraviolet radiation, of good appearance and self-draining,

Description

METHOD FOR MANUFACTURING A RESIN-BASED BINDER FOR COATING WITH PELLETS OF MATERIAL, BINDER OBTAINED AND COATING OBTAINED

Technical area :

The present invention relates to a process for the production of a resin-based binder for granular material coating, said binder consisting of a single-component polyurethane resin comprising a single reaction component formed of an isocyanate part, a solvent and a catalyst.

The invention also relates to a resin-based binder obtained by said process, and a coating obtained by a mixture of granules of material with said mono-component polyurethane resin-based binder, said mixture being arranged to be applied to a surface and to form after polymerization of said binder a durable coating, resistant to mechanical stress and ultraviolet radiation, beautiful appearance and self-draining.

Prior art:

Material pellet coatings are widely used to cover floors, walls, stairs, curbs, beach areas bordering pools, walkways, balconies, terraces, play areas, etc. These examples application not being limiting. They can be applied to any type of surface, both indoors and outdoors, for both professional and domestic use. There are mainly two types of coating, namely so-called flexible coatings made from granules of rubber or the like of natural, synthetic or recycled origin, or plastic or similar granules of synthetic or recycled origin, and so-called coatings. made from granules of minerals or other hard materials. These latter coatings are commonly referred to as "stone carpets" or "stone carpets". They are generally made from natural stone granules based on marble, granite, quartz, or similar, and a mixture of stones to play with the colors, these stones can be derived for example from gravel pits or stones. careers. They can also be obtained from glass granules or any other hard material. They offer an alternative to conventional flooring and have the advantage of being particularly resistant to pedestrian traffic, of being non-slip and of being self-draining, thus avoiding the stagnation of surface water in the event of rain. The flexibility of this type of coating is a function of the characteristics of the granules, which are chosen according to the intended field of application. As a guide, preference is given to so-called flexible coatings based on more or less flexible rubber granules for sports and leisure applications, and so-called hard coatings for other applications.

The granules of material are agglomerated with each other and fixed to the surface to be covered by a binder, also called a binder resin, preferably transparent so as not to tarnish the color of the granules and to additionally provide gloss, this binder being particularly resistant to yellowing and to make a coating without joint or connection. The use of a bicomponent polyurethane resin binder comprising two reaction components, namely a polyol part and an isocyanate part, has been known for several years as a reliable, accessible and inexpensive technology. However, the technique of implementing this type of binder is restrictive since it requires two mixing operations before the coating can be applied. Indeed, it is necessary to proceed to a first mixture between the two reaction components of the binder in a precise predefined ratio, before adding the granules of material and to proceed to a second mixture to coat binder said granules of material. Once these two mixtures have been carried out, the granule-binder mixture obtained can be applied to a surface to be covered. This type of bicomponent binder has the advantage of polymerizing in air and at ambient temperature, which makes it possible to obtain, after polymerization, a compact coating, of good appearance, highly resistant to mechanical stresses, durable over time and insensitive to ultra-violet radiation. -violets, and self-draining.

To simplify the processing technique and avoid mixing errors, the binder formulas have evolved into single-component binders, i.e., a single reaction component. Thus, of the polyol portion and the isocyanate portion of the original two-component binder, there remains only the isocyanate portion. The two-component binders were obtained by reacting the polyol portion on the isocyanate portion to form a polyurethane resin. The single-component binders, composed solely of isocyanate, and optionally additives, form a polyurea resin through the reaction of the isocyanate with the moisture of the air, with or without the addition of catalyst. depending on the desired setting speed, and with or without a solvent to fluidify or not the binder.

The term "solvent" means a liquid agent that has the property of dissolving and diluting other substances (solid, liquid or gaseous), without chemically modifying the other substances and without itself modifying itself. The addition of a solvent has the advantage here of being able to control and modify the viscosity of the binder which conditions the use of the "granule-binder" mixture and its ease of being applied to a surface to be covered. It also has the advantage of being volatile, having the effect of dragging with it the gas generated during the polymerization reaction, and allowing both a faster drying and the absence of bubbles on the surface of the polymerization reaction. coating. The known solvents are mainly flammable solvents. This is why we sought first solutions of single-component binder without solvent to avoid this risk.

The choice of a solvent-free one-component binder therefore seemed to be the preferential mode because of the absence of solvent. Laboratory tests have yielded conclusive results. Nevertheless, real-life field tests have shown that the solvent-free one-component binder formula is unreliable at temperatures above ambient temperatures, that is, above 25 ° C. Indeed, under "extreme" temperature conditions (up to 45 ° C) with extreme relative humidity (RH up to 90%), the solvent-free one-component binder formula reacts quickly and foam. The reaction between the isocyanate and the water molecules in the air at these extreme conditions generates gas that has no time to escape and remains trapped in the binder. It has thus been found that the gas bubbles contained in the binder rise to the surface of the coating, remain on the surface and create a state of blistered surface. The coating thus obtained is therefore covered with bubbles, which is unacceptable. Following this failure, the choice of a single-component binder without solvent was abandoned.

Other solutions of single-component binder with solvent were then sought, but care was taken to select non-flammable solvents. Various formulation tests have been carried out with various known non-flammable solvents such as, for example, dimethylsulfoxide (DMSO), NOVEXPANS ™ N90 (solvent based on 1,2-trans-dichloroethylene), NOVEXPANS ™ N11B (solvent with dimethyl succinate base), etc. to replace the flammable solvent contained in the single-component binder but without acceptable results. Indeed, the main problem with non-flammable solvents lies in the fact that they are very little volatile. Their low volatility does not allow them to evacuate the gas generated during the polymerization reaction of the resin. Thus, the results obtained are disappointing, as well as a single-component binder without solvent as described above.

In the end, the choice of a single-component binder with flammable solvent proved to be the best solution. It has indeed been found that, thanks to the addition of a solvent, the mono-component binder obtained is more fluid, works better, does not foam and also gives superior results to traditional bicomponent binders and binder. mono-component without solvent. Real-life tests on site have verified these good results obtained in the laboratory, namely the obtaining of a high-quality flooring, both aesthetic and mechanical, by means of a single-component binder formula with solvent that has been used in severe temperature and relative humidity conditions: up to 45 ° C and up to 90% RH.

Thus, to date, many binders based on single-component resin with flammable solvent, marketed for applications in the field of flooring from granules of material. The solvents contained in these binders may be, for example, acetone, methyl ethyl ketone, xylene, n-butyl acetate, etc.

Although it has been proven that the single-component binder with solvent was an effective product for this type of application, the fact remains that it has a major defect related to the presence of flammable solvent. This solvent, essential for the implementation of the single-component binder and the good results obtained, has the major disadvantage of being flammable and to release a slight odore unpleasant. Consequently, its implementation entails health and safety risks for the operators, given the toxicity of the substances and the fire risk. These risks are aggravated if the application of the coating comprising this type of binder is performed inside a room in a closed environment in part or in whole.

Current solutions of single-component binder without solvent or with flammable or non-flammable solvent are therefore unsatisfactory.

Presentation of the invention

The present invention aims to overcome these disadvantages by proposing a binder based on single-component resin with solvent, without danger for operators even when the application is carried out in a closed environment, allowing easy implementation and application, in relatively severe temperature and humidity conditions: above 35 ° C and up to 45 ° C, with relative humidity up to 90%, without bubbling, or lack of appearance on the surface of said coating obtained, while guaranteeing better aesthetic and mechanical performance of the coating obtained than currently known solutions. The invention also aims to allow on the one hand to meet the new regulations in public health, and on the other hand to obtain a transparent resin, durable and resistant to ultraviolet radiation, without any defect of aspect, particularly suitable for applications in the field of granular material-based flooring, and whatever the nature of said granules.

For this purpose, the invention relates to a method for manufacturing a binder as defined in the preamble, characterized in that a non-flammable and non-toxic solvent consisting of a cleaning agent 2,5,7,10- is used. TetraOxaUndecane (TOU), in that said solvent is mixed by mass in said isocyanate portion to form said mono-component polyurethane resin, in that said mono-component polyurethane resin is conditioned, and in that a non-toxic, transparent, one-component, non-toxic, one-component polyurethane resin binder is obtained which has good behavior even under extreme use conditions of temperature up to 45 ° C and relative humidity of up to 90% for mixing said binder with granules of material in a predefined ratio, to apply said mixture to a surface to be covered both externally and internally, said binder being arranged to polymerize r at room temperature and air to bind said granules of material between them and said covered surface and to form, after polymerization, a durable coating, resistant to mechanical stresses and ultraviolet radiation, beautiful appearance and self- draining.

Said 2,5,7,10-TetraOxaUndecane (TOU) may be added up to at most 25% by weight and preferably at most 15% by mass with a minimum of 1% by weight of said resin.

It is also possible to advantageously use a non-toxic mercury-free catalyst designed to react the isocyanate functions of said single reaction component in the presence of water molecules contained in the ambient air. A conventional mercury-free metal-based catalyst selected from the group consisting of tin, lead, zinc, bismuth, cadmium, antimony, aluminum, zirconium, alone or in combination.

Preferably, a tin salt catalyst is selected from the dibutyltin compounds, and preferably from the group comprising dibutyltin diacetate, dibutyltin dilaurate, and said tin salt catalyst is added at least 200 ppm and at most 5000 ppm, and preferably at most 300 ppm of said resin.

Depending on the variant embodiments, at least one additive selected from an ultraviolet radiation absorber at a level of 0.1 to 4% by weight, a light stabilizer at a height of 0, may be added to the said mono-component polyurethane resin. 1 to 2% by weight. It is also possible to add in said mono-component polyurethane resin at least one additional additive chosen from a moisture absorber at a level of 0.1 to 3% by weight, an antioxidant at a level of 0.1 to 2% by weight.

In a preferred form of the invention, at least one aliphatic polyisocyanate having three isocyanate functions, representing at least 40% by weight and preferably at least 65% by weight with a maximum of 99% by mass, is selected for said isocyanate part. said resin selected from the group consisting of a trimer of hexamethylene diisocyanate (HDI), a trimer of IPDI, a trimer of PDI, alone or in combination.

Depending on the variant embodiments, at least one other aliphatic polyisocyanate having two or more isocyanate functional groups, representing at most 60% by weight and preferably at most 35% by weight of said resin selected from the group comprising, for example, a biuret of HDI, a polymer of HDI, alone or in combination.

It is also possible to choose in part or in full at least one biosourced aliphatic polyisocyanate to produce a binder with an ecological tendency.

The object of the invention is also achieved by a binder obtained according to the manufacturing method described above, by a surface coating advantageously obtained by mixing said binder and granules of material in a ratio of between 1/20 and 1 / 5.

Depending on the application, the granules of material may be chosen from flexible materials including natural, synthetic and recycled rubbers, plastics of synthetic and recycled origin, used alone or mixed. They can also be selected from hard materials including marble, granite, quartz, glass, used alone or mixed.

The resulting surface coating may optionally form a single, seamless liner applied directly to a surface to be coated, or a surface coating of plates arranged to be laid on a surface to be coated.

Description of the invention and its variants:

Quite coincidentally, single-component binder formulation tests were carried out with a cleaning agent, 2,5,7,10-TetraOxaUndecane, known under the name "TOU", used as a solvent for compositions. polyurethane dispersion. This product has the advantage of being nonflammable, so a priori not very volatile. H is known to have an extremely high dissolving power and a good toxicological and eco-toxicological profile. TOU is for example a replacement of NMP or N-methyl-pyrrolidone, which is a cyclic amide often used as an organic solvent. Publication WO 2016/144756 A1 discloses the use of TOU as a primer, and WO 2017/1088072 A1 discloses the use of TOU as a solvent for dispersed polyurethane compositions.

However, during these fortuitous tests, it was surprisingly and unexpectedly discovered that by replacing the TOU agent with the usual flammable solvent in bulk in a mono-component polyurethane resin, the binder obtained has a good behavior and produces the effects. expected techniques even for temperatures above ambient temperatures, that is, above 25 ° C. Indeed, under "extreme" temperature conditions (up to 45 ° C) with extreme relative humidity (RH up to 90%), the one-component binder formula with TOU as non-flammable solvent does not foam. It has indeed been found that the TOU is volatile enough to carry with it the gas generated during the polymerization reaction and thus avoid any bubble formation on the surface of the coating. In addition, the binder obtained is non-flammable, non-toxic, of homogeneous quality, transparent, of a viscosity adapted to the application of coating envisaged, easy to work at room temperature, in complete safety for the operators as well inside only outside.

The tests thus demonstrated that it was entirely possible to obtain a one-component binder with the TOU agent as a non-flammable solvent, and that the binder obtained made it possible to obtain results comparable to or even greater than those obtained under the same conditions. temperature and relative humidity as single-component binders with flammable solvent.

The invention therefore relates to a binder composed of a single-component resin called "poly-urea" arranged to create urea bonds by polymerizing, but hereinafter referred to as "polyurethane resin" which is the generic term commonly used, and a method of manufacturing said binder. The binder obtained after polymerization is transparent, durable and resistant to mechanical stress and ultraviolet radiation. The binder of the invention is crosslinked by the reaction of the moisture contained in the ambient air on the only isocyanate part which constitutes said single-component resin.

This mono-component polyurethane resin comprises one or more aliphatic isocyanates. It also includes a non-flammable solvent: the TOU. Finally, it preferably contains a catalyst to limit its setting time. It may further contain one or more additives, as explained later, to add properties to said binder.

The binder of the invention is mixed, according to a defined ratio, with granules of material chosen according to the type of coating to be produced, which may be granules of flexible material such as rubber or granules of hard material such as stone, as explained in detail in the state of the art. This defined ratio can be between 1/20 and 1/5, without this range being limiting. The resulting mixture can then be applied to a surface to be coated to provide a seamless, one-piece surface coating that will naturally polymerize in ambient air. The mixture obtained can also be poured into a mold to form surface coating plates that will be sufficient to pose with or without adhesive on a surface to be coated depending on the type of coating to be performed.

The single-component polyurethane resin of the present invention comprises a single reaction component consisting of its only isocyanate part which cross-links thanks to its isocyanate functions which will react with the water molecules contained in the ambient air. It comprises for this purpose one or more aliphatic isocyanates and preferably at least one aliphatic polyisocyanate. Polyisocyanates are components having two or more isocyanate functions. In the present invention, the resin is preferably composed of an aliphatic polyisocyanate having three isocyanate functions (f = 3), representing at least 40% by weight and preferably at least 65% by weight with a maximum of 99% by weight of said resin. The aliphatic polyisocyanate may be the only isocyanate compound, or it may be combined with other aliphatic polyisocyanates having two or more isocyanate functions (f> = 2), such as for example the IPDI trimer, the PDI trimer synthetic or biosourced biuret HDI, polymer HDI, etc. representing at most 60% by weight and preferably at most 35% by weight of said resin.

Preferably, the single-component polyurethane resin according to the invention requires a catalyst whose function is to accelerate the reaction of the isocyanate functions of the single reaction component with the water molecules present in the air to form urea bonds. . A catalyst, free of mercury in view of its toxicity, will be chosen, for example but not exclusively a metal catalyst selected from a group comprising tin, lead, zinc, bismuth, cadmium, antimony, aluminum , zirconium, taken alone or in combination, this list is not exhaustive. The choice of non-toxic catalyst can be extended to any other non-metallic catalyst known to those skilled in the art. A tin catalyst, especially dibutyltin compounds, and preferentially dibutyltin diacetate or dibutyltin dilaurate, is preferred. The catalyst is included at a level of at least 200 ppm and at most 5000 ppm of the resin and more preferably at most 300 ppm of said resin.

The single-component polyurethane resin contains a non-flammable solvent: 2,5,7,10-tetraoxaundecane (TOU). It is integrated at a maximum of 25% by weight and preferably at most 15% by weight with a minimum of 1% by weight of said resin.

Optionally, the single-component polyurethane resin according to the invention may include various additives. For example, UV absorbers (Ultra-Violet) can be used to improve the external exposure resistance of the binder. The UV absorbers generally recognized in the art are suitable for the invention, such as those sold under the trademark Tinuvin® 312, for example, without this example being limiting. The amount of UV absorber is preferably between 0.1 and 4% by weight of said resin.

It is also possible to use a light stabilizer called HALS (Hindered Amine Light Stabilizer) instead of or in combination with the UV absorber. H contributes to the photo stabilization of the mono-component polyurethane resin by trapping the alkoxy and hydroxy radicals that are produced by the dissociation of hydroperoxides. The HALS stabilizers generally recognized in the state of the art are suitable for the invention, such as those sold under the trademark Chisorb® 292, for example, without this example being limiting. The amount of HALS desired is preferably between 0.1 and 2% by weight of said resin.

In addition, other additives may optionally be incorporated in the mono-component polyurethane resin such as moisture absorbers and antioxidants etc. Conventional products of these product categories recognized in the state of the art may be suitable in the invention for improving the final properties of the binder. The moisture absorbers are preferably included between 0.1 and 3% by weight of said resin, and the antioxidants between 0.1 and 2% by weight of said resin.

The viscosity of the mono-component polyurethane resin obtained before mixing with the granules of material is maintained at a specific viscosity. The viscosity is measured on a Brookfield RVT viscometer with the mobile 2 at a speed of 10 revolutions per minute. Its viscosity is maintained in a range of 400 to 2000 mPa / s at 23 ° C. and preferably between 500 and 2000 mPa / s at 23 ° C.

The viscosity of the single-component polyurethane resin is important for the intended application: a too low viscosity will not allow sufficient coating of the granules of material, while a too high viscosity will cause a difficulty for the operator to spread correctly. its mixture on the surface to be covered.

The mono-component polyurethane resin as described thus constitutes the binder according to the invention. This binder is packaged in a container. The binder must remain transparent, ie it must not yellow with time under the effect of UV radiation. H is intended to be mixed on site with granules of material in a defined proportion, for example in a ratio of between 1/20 and 1/5, depending on the type of coating to be produced, without this range being limiting . The mixture obtained is then deposited and applied to a surface to be covered in one piece and without connection. The working time of the granulating mixture is estimated between 40 minutes and 1 hour. The binder polymerizes naturally at room temperature by agglomerating the granules of material together and fixing them solidarily to the surface covered by said mixture. It thus forms a uniform, hardened coating, with or without a certain flexibility depending on the type of material granules, very solid, resistant to mechanical stresses, weather and ultraviolet rays, and self-draining. The crosslinking is carried out correctly at temperatures between 5 ° C and 35 ° C, or even higher than 35 ° C and up to 45 ° C to work in summer, without encountering any difficulty, even under conditions extreme relative humidity up to 90% RH. The gelling level of the coating, ie a dust-free and carefully accessible coating, is approximately 12 hours after installation at ambient temperature, and the final curing time is 7 days after laying.

Basic formula

In order for the resin-based binder to last over time, it is common to incorporate additives, in particular to protect it against yellowing under the prolonged effect of ultraviolet radiation emitted by the sun.

Two variants of the formulation of the resin according to the invention are described below: a first variant of resin without additive and a second resin variant incorporating additives.

Formulation of resin without additives

91.91 g of trimer of hexamethylene diisocyanate (HDI), 8 g of 2, 5, 7, 10 tetraoxaundecane (TOU) and 0.09 g of dibutyltin dilaurate are introduced into the production reactor.

The temperature of the mixture is raised to 40 ° C.

The mixture is stirred for 2 hours under vacuum.

The product is then conditioned.

As stated, the mixture is heated to a temperature of 40 ° C to decrease its viscosity and to obtain a quality mixture after about 2 hours of stirring. However, the heating step is optional. Indeed, the formulation described above can do without the heating step but, in this case, the agitation step of the mixture will last a few more hours.

Formulation of the resin with additives

91.57 g of trimer of hexamethylene diisocyanate are introduced into the production reactor with the following additives: 0.37 g of Chisorb 1010 (pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) propionate)) and 0.28 g of Chisorb 1033 (2-ethyl-2'-ethoxyoxanilidine).

The temperature of the mixture is raised to 85 ° C.

The mixture is stirred for 4 hours under vacuum.

The heating went down to 50 ° C.

Then, 0.28 g of Chisorb 292 (0.232 g of bis (1,2,6,6-pentamethyl-4-piperidyl) sebacate and 0.058 g of methyl 1,2,6,6-pentamethyl-4-piperidyl sebacate), 0.09 g of dibutyltin dilaurate and 7.41 g of 2.5, 7, 10 tetraoxaundecane (TOU) are added to the mixture in the reactor at 50 ° C.

Stirring of the mixture continues for about 30 minutes before degassing for at least 30 minutes with stirring.

The product is conditioned.

There are variations in the choice of additives which will not be described and which are accessible to those skilled in the art. The formulations described below with the selected indicated additives are preferred formulations of the invention.

Tables of comparative tests carried out

Table 1 - Interest of the solvent in a binder according to the invention mixed with granules

Example 1 With solvent fireproof Example 2 Solvent free Example 3 With solvent flammable Example 4 Solvent free Example 5 With solvent fireproof Resin (composition per 100 grams) Tolonate HDT-LV 91.57 98.90 - - 98.90 Tolonate HDT-LV2 - - 90.90 98.90 - Desmodur eco N7300 - - - - - TOU 7.41 - - - - Additive OF - - 8.0 - - DMSO - - - - 8.0 Tinuvin 312 0.28 0.3 0.3 0.3 0.3 Irganox 1010 0.37 0.4 0.4 0.4 0.4 Chisorb 292 0.28 0.3 0.3 0.3 0.3 PC CATT-12 N 0.09 0.1 0.1 0.1 0.1 Clarity Transparent Transparent Transparent Transparent Transparent Bullage at 23 ° C No No No No No Bullage at 45 ° C Low Very important Low important Important

Example 1

This is a mono-component polyurethane resin according to the invention containing predominantly aliphatic polyisocyanates consisting of Tolonate ™ HDT-LV which is a trimer of hexamethylene diisocyanate (HDI) at 91.57 g, the solvent non-flammable TOU of the invention at a height of 7.41 g, a catalyst based on tin PC T-12 PC Dibutyltindilaurate at a level of 0.09 g and additives at a height of 0.93 g.

Example 2

H is the pendant of Example 1 but without the non-flammable solvent of the invention. Example 3

This is a mono-component polyurethane resin containing predominantly aliphatic polyisocyanates consisting of Tolonate ™ HDT-LV2 which is a trimer of hexamethylene diisocyanate (HDI) at 90.90 g, a conventional flammable solvent Additive OF at a level of 8 g, a PC T-12 Dibutyltindilaurate tin-based catalyst at a level of 0.1 g and additives at a level of 1 g. Example 4

H is the counterpart of Example 3 but without the conventional flammable solvent.

Example 5

This is a mono-component polyurethane resin comprising predominantly aliphatic polyisocyanates consisting of Tolonate ™ HDT-LV (as Examples 1 and 2) at 98.90 g, a conventional non-flammable solvent dimethylsulfoxide DMSO at 8g, a catalyst based on PC T-12 Dibutyltindilaurate tin at 0.1g and additives at 1g. Examples 6 and 7:

Each of these examples relates to a single-component polyurethane resin according to the invention comprising a part of aliphatic polyisocyanates consisting of Tolonate ™ HDT-LV which is a trimer of hexamethylene diisocyanate (HDI) at a height of 43.88 g and 81.91 g, and a part of biosourced polyisocyanates constituted by the Desmodur® eco N7300 at respectively 45 g and 10 g, the non-flammable solvent TOU of the invention at respectively

10.55 g and 8 g, a catalyst based on tin PC T-12 Dibutyltindilaurate PC at 0.09 g and additives respectively at 1 g.

Desmodur N 7300 is a biosourced pentamethylene diisocyanate (PDI), since its raw material is non-food corn starch. The addition of one part of biosourced isocyanates in the mono-component polyurethane resin according to the invention makes it possible to tend towards an ecological binder, which brings an additional advantage to the nontoxic binder of the invention.

Table 1 above illustrates the impact of the solvent on the final appearance of the single-component polyurethane resin after polymerization and thus on the final appearance of the coating obtained. With the examples 2 and 4 without solvent, there are significant bubbling problems. These Examples 2 and 4 thus demonstrate the utility of integrating a solvent into a single-component polyurethane resin for the intended application. Indeed, for high temperatures, especially in the summer, the addition of a solvent makes it possible to obtain a transparent non-bubble resin. Thus, the resins with solvent can be used outdoors regardless of the time of year.

Example 5 comprising as solvent DMSO shows that even with a nonflammable solvent base, mono-component polyurethane resin obtained is not guaranteed to be free of bubbling. Although having less bubbling than that observed with Examples 2 and 4, Example 5 does not guarantee the possibility of having an undblocked coating.

Examples 1 and 3 are very close to each other. Even in extreme conditions (temperature of 45 ° C with a relative humidity of 90%), the mono-component polyurethane resin obtained is only very slightly bubbled and has a good surface appearance. Example 1 has the advantage of containing a non-flammable solvent, unlike Example 3, which reduces the toxicity of the resin without losing quality on the finished coating.

Table 2 - Flexural strength of the coating obtained from the mixture "granules of marble and binder"

Example 1 Example 2 Example 3 Example 6 Example 7 Bending force in N (Norm NF- T51-001) 89 76 55 99 91

Examples 1, 2, 3, 6 and 7 are the same for Tables 1 and 2.

The mono-component polyurethane resin of Example 2 is logically that which gives the flooring the greatest flexural strength because of its absence of solvent. However, Examples 1, 6 and 7 containing the non-flammable solvent TOU according to the invention demonstrate just the opposite.

Example 3, which comprises a conventional flammable solvent in the same proportions as Example 1, has a flexural strength much lower than that of Example 2 without solvent.

These comparative tests make it possible to confirm the surprising technical effects brought about by the cleaning agent TOU used as non-flammable solvent in a single-component polyurethane resin intended to form a binder for a coating based on granules of material.

Table 3: Validation of a binder according to the invention mixed with rubber granules EPDM type

Example 1 Example 2 Example 3 Resin (composition per 100 grams) Tolonate HDT-LV 91.57 65.78 45.78 Tolonate X Flo 100 - 25.78 45.78 TOU 7.41 7.41 7.41 Irganox 1010 0.37 0.38 0.38 Tinuvin 312 0.28 0.28 0.28 Chisorb 292 0.28 0.28 0.28 PC CATT-12 N 0.09 0.09 0.09 Clarity Transparent Transparent Transparent Bullage at 23 ° C No No No Bullage at 45 ° C Low Low Low

Note: Example 1 of Table 1 and Example 1 of Table 3 are identical. This makes it possible to show that the same binder formula can be used for granules of hard material such as marble granules but also for granules of flexible material such as EPDM granules.

Examples 2 and 3 are other binder formulas according to the invention comprising one part of aliphatic polyisocyanates with three functionalities (f = 3), constituted by Tolonate ™ HDT-LV which is a trimer of hexamethylene diisocyanate (HDI ) respectively 65.78g and 45.78g, and one part aliphatic polyisocyanates with two or more functionalities (f> = 2), consisting of Tolonate ™ XElo 100 at 25.78g and 25.78g respectively. 45.78 g, the non-flammable solvent TOU of the invention at the level of 7.41, a catalyst based on tin PC T-12 Dibutyltindilaurate CAT at 0.09 g and additives respectively at 0.94 g. The addition of a complementary aliphatic polyisocyanate having a number of isocyanate functions other than three in particular makes it possible to modify the hardness of the resin as a function of the coating to be produced. These two examples demonstrate the versatility of the binder according to the invention.

Materials used

Designation Description Tolonate HDT-LV Low viscosity aliphatic polyisocyanate (f = 3) Tolonate HDT-LV2 Aliphatic polyisocyanate with very reliable viscosity (f = 3) Tolonate X FLO 100 Aliphatic polyisocyanate with very good viscosity (f> = 2) Desmodur eco N7300 Pentamethylene diisocyanate (PDI) biosourced (f = 3) TOU 2,5,7,10-T etraOxaUndecane Additive OF Solvent for polyurethane DMSO Organic polar solvent Tinuvin 312 Sun Creme Irganox 1010 Antioxidant Chisorb 292 HALS stabilizer PC CATT-12 N Dibutyltin dilaurate

Thus, it is clear from this description that the invention achieves the goals, namely a coating binder based on granules of material, non-flammable, non-toxic, transparent, insensitive to ultraviolet radiation, easy to put to mix and apply, maintaining a good behavior even in extreme conditions of use of temperature and relative humidity, and allowing the realization of coatings of high mechanical and aesthetic quality. The binder of the invention can thus constitute a so-called universal binder compatible with any type of granules of material that they are flexible or hard, which can be applied both outside and inside.

The present invention is not limited to the embodiments described but extends to any modification and variation obvious to a person skilled in the art.

Claims (28)

claims A process for producing a resin-based binder for granular coating of material, said binder consisting of a single-component polyurethane resin having a single reaction component consisting of an isocyanate moiety, a solvent and a catalyst, characterized in that a non-flammable and non-toxic solvent consisting of a 2,5,7,10-TetraOxaUndecane (TOU) cleaning agent is used, in that said solvent is mixed with said isocyanate portion for forming said single-component polyurethane resin, in that said single-component polyurethane resin is packaged, and in that a non-toxic, non-toxic, transparent one-component polyurethane resin binder is obtained , having good behavior even under extreme use conditions of temperature up to 45 ° C and relative humidity up to 90% for mixing said binder with granules of matter in a predefined ratio, to apply said mixture to a surface to be covered both externally and internally, said binder being arranged to polymerize in air and at room temperature to bind said granules of material to each other and to said surface covered and to form, after polymerization, a durable coating, resistant to mechanical stresses and ultra-violet radiation, beautiful appearance and self-draining. 2. Manufacturing process according to claim 1, characterized in that said 2,5,7,10-TetraOxaUndecane (TOU) is added up to at most 25% by weight and preferably at most 15% by weight. mass with a minimum of 1% by mass of said resin. 3. The manufacturing method according to claim 1, characterized in that a non-toxic mercury-free catalyst is used arranged to react the isocyanate functions of said single reaction component in the presence of water molecules contained in the ambient air. . 4. Process according to claim 3, characterized in that a conventional mercury-free catalyst based on a metal selected from the group comprising tin, lead, zinc, bismuth and cadmium is selected. antimony, aluminum, zirconium, taken alone or in combination. 5. Process according to claim 4, characterized in that a tin salt catalyst is selected from among the dibutyltin compounds, and preferably from the group comprising dibutyltin diacetate and dibutyltin dilaurate. 6. Process according to claim 5, characterized in that the tin salt catalyst is added at a level of at least 200 ppm and at most 5000 ppm, and preferably at most 300 ppm. of said resin. 7. Process according to claim 1, characterized in that at least one additive selected from an absorber of ultraviolet radiation at a level of 0.1 to 4% by weight, a stabilizer is added to said single-component polyurethane resin. 0.1 to 2% by weight of light. 8. Process according to claim 1, characterized in that at least one complementary additive selected from a moisture absorber of 0.1 to 3% by weight, an antioxidant at least one, is added to said mono-component polyurethane resin. height of 0.1 to 2% by weight. 9. Process according to claim 1, characterized in that at least one aliphatic polyisocyanate having three isocyanate functions, representing at least 40% by weight and preferably at least 65% by weight with a maximum, is selected for said isocyanate part. 99% by weight of said resin, selected from the group consisting of a trimer of hexamethylene diisocyanate (HDI), a trimer of IPDI, a trimer of PDI, alone or in combination. 10. Process according to Claim 9, characterized in that at least one other aliphatic polyisocyanate, having two or more isocyanate functional groups, representing at most 60% by weight and preferably at most 35% by mass, is added in the said isocyanate part. said resin, chosen from the group comprising, for example, a biuret of HDI, a polymer of HDI, alone or in combination. 11. Process according to any one of the preceding claims, characterized in that part or all of at least one biosourced aliphatic polyisocyanate is selected. 12. A binder based on a single-component polyurethane resin comprising a single reaction component formed of an isocyanate part, a solvent and a catalyst, said binder being arranged to bind granules of material together and form a coating on a surface to covering, characterized in that said binder is obtained by the method according to any one of the preceding claims, in that it comprises a non-flammable and non-toxic solvent consisting of a cleaning agent 2,5,7,10-TetraOxaUndecane ( TOU) mixed in mass with said isocyanate part, and in that said mono-component polyurethane resin thus obtained is non-flammable and nontoxic, transparent, and arranged to be used under extreme temperature conditions up to 45 ° C. and relative humidity up to 90%. 13. Binder according to claim 12, characterized in that said 2,5,7,10TetraOxaUndecane (TOU) represents at most 25% by weight and preferably at most 15% by weight with a minimum of 1% by weight of said resin. Binder according to claim 12, characterized in that said single-component polyurethane resin comprises a non-toxic mercury-free catalyst arranged to react the isocyanate functions of said single reaction component in the presence of water molecules contained in the air ambient. Binder according to Claim 14, characterized in that the said non-toxic mercury-free catalyst is a metal-based catalyst selected from the group consisting of tin, lead, zinc, bismuth and cadmium. antimony, aluminum, zirconium, taken alone or in combination. 16. Binder according to claim 15, characterized in that said tin salt catalyst is selected from dibutyltin compounds, and preferably from the group comprising dibutyltin diacetate, dibutyltin dilaurate. 17. Binder according to claim 16, characterized in that said tin salt catalyst represents at least 200 ppm and at most 5000 ppm, and preferably at most 300 ppm of said resin. 18. Binder according to claim 12, characterized in that said single-component polyurethane resin comprises at least one additive selected from an absorber of ultraviolet radiation at a level of 0.1 to 4% by weight, a light stabilizer at height. from 0.1 to 2% by weight of said resin. Binder according to claim 12, characterized in that said single-component polyurethane resin comprises at least one additional additive chosen from a moisture absorber at a level of 0.1 to 3% by weight of said resin, an antioxidant at a height of from 0.1 to 2% by weight of said resin. 20. Binder according to claim 12, characterized in that said isocyanate portion comprises at least one aliphatic polyisocyanate having three isocyanate functional groups, representing at least 40% by weight and preferably at least 65% by weight with a maximum of 99% by weight of said resin, selected from the group consisting of a trimer of hexamethylene diisocyanate (HDI), a trimer of IPDI, a trimer of PDI, alone or in combination 21. Binder according to claim 12, characterized in that said isocyanate portion comprises at least one other aliphatic polyisocyanate having two or more isocyanate functions, representing at most 60% by weight and preferably at most 35% by weight of said resin, selected in the group comprising, by way of example, a biuret of HDI, a polymer of HDI, alone or in combination. 22. Binder according to any one of claims 12 to 21, characterized in that said isocyanate portion comprises at least one biosourced aliphatic polyisocyanate. 23. Surface coating obtained by mixing granules of material and binder based on single-component polyurethane resin, said mixture being designed to be applied to a surface and to form after polymerization of said binder a durable coating, resistant to mechanical stresses and ultraviolet radiation, of good appearance and self-draining, characterized in that said binder consists of a single-component polyurethane resin according to any of claims 12 to 22, and in that said mono-component polyurethane resin obtained is non-flammable and non-toxic, transparent and arranged to have a good behavior allowing it to be applied both outdoors and indoors, even under extreme conditions of use of temperature up to 45 ° C and relative humidity up to 90%. 24. The coating of claim 23, characterized in that it is obtained by mixing the binder and granules of material in a ratio between 1/20 and 1/5. 25. The coating of claim 23, characterized in that the granules of material are selected from flexible materials including rubbers of natural, synthetic and recycled origin, plastics of synthetic and recycled origin, used alone or mixed. 26. The coating of claim 23, characterized in that the granules of material are selected from hard materials including marble, granite, quartz, glass, used alone or mixed. 27. A coating according to any one of claims 23 to 26, characterized in that it forms a surface coating in one piece and without connection to a surface to be covered. 28. Coating according to any one of claims 23 to 26, characterized in that it forms a surface coating plates arranged to be placed on a surface to be covered.