FR3119844A1 - Fire-resistant glazing comprising a sheet of glass coated with an intumescent coating - Google Patents

Abstract

The present invention relates to a process for manufacturing an intumescent coating on a sheet of glass, as well as a fire-resistant glazing thus obtained, said process comprising:- the preparation of a solution of precursors comprising 20 to 80% by weight of dry matter and having a pH of less than 7; said solution comprising, on a total dry matter weight basis, 10 to 40% of a phosphorus agent and 50 to 90% of hydrolysable silanes; said hydrolyzable silanes comprising 50 to 100% by weight of at least one silane chosen from the silanes of formula I and the silanes of formula II:(I) (R1O)4Si(II) R2k(R1O)4-kSi- the pre -condensation and curing of the precursor solution for 10 to 150h comprising heating the precursor solution for 1 to 50h at a temperature of 30 to 100°C, to obtain an intumescent coating composition;- depositing the composition intumescent coating on the glass sheet; and- drying the intumescent coating composition to form an intumescent coating.

Description

Fire-resistant glazing comprising a sheet of glass coated with an intumescent coating

The present invention relates to the field of fire-resistant glazing. It relates in particular to a method of manufacturing an intumescent coating on a sheet of glass, as well as a glazing comprising a sheet of glass coated with an intumescent coating capable of being obtained by this process.

Fire-resistant glazing is conventionally formed from a very viscous aqueous solution based on hydrated alkali silicates sealed between two sheets of glass (EP 3023245, WO 2007/118886, WO 2007/053248, EP 2072247, EP 2282889, 053248). Other fire-resistant glazing is formed from a layer of solid hydrogel between two sheets of glass, obtained by crosslinking a solution of water-soluble monomers (US 2016/2000077, EP 2330174). In the first case, protection against fire is ensured by the opaque mineral foam formed by the expansion of the layer of silicates due to the evaporation of the water it contains under the effect of heat. For the hydrogel layer, the spread of fire is retarded by the evaporation of water and the inorganic additives contained in the hydrogel layer. These solutions, although effective, implement manufacturing processes that can be complex due to the constraints associated with injecting a solution between two sheets of glass. The glazing thus obtained cannot be cut after assembly and must therefore be custom made to the desired dimensions.

There are intumescent organic coatings, such as paints or varnishes, developed to improve the fire resistance of building materials. Such coatings comprise a polymer binder and an intumescent system generally formed from an acid source such as phosphoric acid or an ammonium polyphosphate, a carbonaceous compound such as a polyol, and an expansion agent such as urea or melamine. When exposed to fire, these coatings foam and produce a protective carbonaceous residue. The carbonaceous residue acts as a barrier physically and thermally protecting the coated material. In most cases, the coating also plays an aesthetic role by modifying the appearance of the surfaces of the coated materials. There are also so-called transparent intumescent varnishes, intended for application on wooden or plastic surfaces, allowing the aesthetic appearance of the covered surfaces to be maintained.

This type of intumescent coating is of interest for improving the fire resistance of glazing. However, the so-called transparent intumescent varnishes known to date do not provide complete satisfaction for these applications: applied in a thick layer on glass, they have a milky appearance which is not acceptable from an aesthetic point of view. It would indeed seem that these coatings actually need to be applied to a sufficiently porous or rough surface to be perceived as transparent after application.

More recently, the Applicant has developed an intumescent organic coating suitable for application to a sheet of glass. However, there is a continuous need to improve intumescent coating solutions compatible with fire-resistant glazing applications.

The object of the present invention is to provide a solid intumescent coating, preferably mainly inorganic, which does not affect the optical properties thereof and exhibits good intumescence.

Thus, one aspect of the present invention relates to a method of manufacturing an intumescent coating on a sheet of glass comprising:
- the preparation of a solution of precursors comprising 20 to 80% by weight of dry matter and having a pH of less than 7; said composition comprising, based on the total weight of dry matter, 10 to 40%, preferably 20 to 35%, of a phosphorus agent and 50 to 90%, preferably 60 to 80%, of hydrolysable silanes; said hydrolysable silanes comprising 50 to 100% by weight of at least one silane chosen from the silanes of formula I and the silanes of formula II:
(I) (R1O) ₄ If
(II) R2 _k (R1O) _4-k Si
in which
each R1 is independently selected from C1-C4 alkyl;
k is an integer between 1 and 3; and
each R2 is independently selected from C1-C12 alkyls, optionally substituted by one or more substituents, preferably one substituent, independently selected from the group consisting of aryl, –[NH(CH ₂ ) _n ] _m NR ₂ , –[ O(CH ₂ ) _n ] _m OR, –C(O)OR, –[O(CH ₂ ) _n ] _m OC(O)R, –OC(O)NHR, glycidyl, –Si(OR') _{3- p} R' _p , where m is an integer between 0 and 3, n is an integer between 1 and 6, each R is independently selected from H, C1-C4 alkyl, aryl, C2-C4 alkenyl, glycidyl, – (CH ₂ ) _q Si(OR') _3-p R' _p , p is an integer between 0 and 2, q is an integer between 1 and 6, and each R' is independently chosen from C1-C4 alkyl;
- the pre-condensation and the ripening of the solution of precursors for 10 to 150 h comprising the heating of the solution of precursors for 1 to 50 h at a temperature of 30 to 100° C., to obtain an intumescent coating composition;
- depositing the intumescent coating composition on the glass sheet; and
- drying the intumescent coating composition to form an intumescent coating.

The present invention also relates to a fire-resistant glazing capable of being obtained by the above process. The Applicant has in fact demonstrated that the process according to the invention makes it possible to obtain a mainly inorganic coating in an easy manner and which, after drying, has optical properties compatible with use in glazing. The coating has after drying a solid structure facilitating the manufacture, handling and integration of the glazing according to the invention. In particular, the use of a solid coating associated with sheets of non-tempered glass allows the production of large glazing that can be cut to the desired dimensions without the need for sealing the edges with any gasket or adhesive.

The precursor solution comprises, on the basis of the total dry matter, from 50 to 90%, preferably from 55 to 80%, even 60 to 75%, by weight of dry matter of hydrolysable silanes, that is to say say of silanes comprising at least one hydrolysable group. Hydrolyzable silanes are typically silicon alkoxides. They can nevertheless comprise other hydrolysable silanes such as chlorosilanes.

The hydrolyzable silanes comprise at least 50%, preferably at least 70%, or even 90 to 100% by weight relative to the total quantity of hydrolyzable silanes, of at least one silane chosen from the silanes of formula I and the silanes of formula II. They may in particular comprise 0, or even 10%, to 60%, or even 50%, by weight of at least one silane chosen from the silanes of formula I and 40, or even 50% to 100%, or even 90%, by weight of at least one silane chosen from the silanes of formula II, relative to the total amount of hydrolysable silanes. The hydrolysable silanes preferably comprise only silanes chosen from the silanes of formula I or of formula II. More preferentially, the hydrolysable silanes comprise only silanes chosen from the silanes of formula II. In certain embodiments, the hydrolyzable silanes comprise at least one silane chosen from the silanes of formula IIa, corresponding to the silanes of formula II in which at least one R2 group comprises an amine, carboxylic acid, ester, epoxy, ether, acrylate , urethane or alcohol, or comprises a carbon chain (linear, cyclic or branched) of 8 or more carbons, in particular an aryl. In other embodiments, the hydrolyzable silanes comprise at least one silane chosen from the silanes of formula IIb, corresponding to the silanes of formula II in which no R2 group comprises an amine, carboxylic acid, ester, epoxy, ether, acrylate, urethane, alcohol, or with a carbon chain (linear, cyclic or branched) of 8 or more carbons. The hydrolysable silanes can also comprise at least one silane chosen from the silanes of formula IIa and at least one silane chosen from the silanes of formula IIb.

Without wishing to be bound by any theory, it is assumed that the presence of silanes of formula II, comprising at least one non-hydrolyzable group, makes it possible to provide a certain flexibility to the network forming the intumescent layer, having the effect of reducing the risk appearance of defects, such as fissures or cracks, during the formation and aging of the latter. The intumescent layer thus has a better resistance to aging.

It is also assumed that the intumescence properties of the layer according to the invention come on the one hand from the formation of an organophosphorus network resulting from the reaction of the phosphorus agent and the organic residues, and on the other hand from the release of large quantities of gas at relatively low temperatures. The gases are assumed to come from both the evaporation of the residual water (free water trapped during gelation or water bound to the network) and the decomposition of the non-hydrolyzable R2 group of the silanes of formula II. In this regard, it has been observed that the silanes of formula IIa provide improved intumescent properties. This effect is attributed to the generation of a greater quantity of gas during their decompositions and/or the formation of a greater quantity of carbonaceous residue. The organophosphorus network, more flexible than the silica network, allows foaming of the intumescent coating at low temperature, thus quickly forming a protective carbonaceous residue when the intumescent coating is exposed to fire. The silica network, very predominantly inorganic, is intimately intertwined with the organophosphorus network at the molecular level due to the sol-gel process. It thus allows the carbonaceous residue to withstand high temperatures, in particular above 500°C.

Thus, in a first embodiment, the hydrolyzable silanes may comprise 10 to 50%, preferably 20 to 40%, of at least one silane chosen from the silanes of formula I, 40 to 80%, preferably 50 to 70 %, of at least one silane chosen from the silanes of formula IIa and 0 to 20%, preferably 0 to 10%, of at least one silane chosen from the silanes of formula IIb. In a second embodiment, they comprise 0 to 20%, preferably 0 to 10%, of at least one silane chosen from the silanes of formula I, 40 to 90, preferably 50 to 80%, of at least a silane chosen from the silanes of formula IIa and 10 to 50%, preferably 20 to 40%, of at least one silane chosen from the silanes of formula IIb. In a third embodiment, they comprise 10 to 60%, preferably 20 to 50%, of at least one silane chosen from the silanes of formula I, 0 to 30%, preferably 0 to 20%, of at least at least one silane chosen from the silanes of formula IIa and 10 to 60%, preferably 20 to 50%, of at least one silane chosen from the silanes of formula IIb. In a fourth embodiment, they comprise 50 to 100%, preferably 60 to 100%, of at least one silane chosen from the silanes of formula IIa, 0 to 50%, preferably 0 to 40%, of at least one silane chosen from the silanes of formula IIb, and preferably no silane of formula I.

By the expression “Ci-Cj alkyl” within the meaning of the present invention, is meant any alkyl group, linear, branched or cyclic, of i to j carbon atoms. Examples of C1-C4 alkyl include methyl, ethyl, n -propyl, isopropyl isobutyl groups. Examples of C1-C12 alkyl groups include methyl, ethyl, n -propyl, isopropyl, prop-2-yl, n -butyl, isobutyl, n -pentyl, n -hexyl, n -heptyl, n -octyl, n -nonyl, n -decyl, n -undecyl, n -dodecyl, as well as C3-C10 cycloalkyls, in particular cyclopropyl, cyclopentyl, cyclohexyl, cyclopropyl(C1-C4 alkyl), cyclopentyl(C1-C4 alkyl) ) and cyclohexyl(C1-C4 alkyl).

By the expression “aryl” within the meaning of the present invention, is meant any aromatic group, in particular the phenyl, tolyl, xylyl and naphthyl groups.

By the expression “C2-C4 alkenyl” within the meaning of the present invention, is meant any alkenyl group, linear or branched, of 2 to 4 carbon atoms, comprising a double bond, in particular vinyl and propenyl groups, in particular propen-2-yl.

In formula II, each R2 is preferably independently selected from
C1-C12, preferably C1-C4, alkyls,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by an aryl group,
C1-12 alkyls substituted by an –NR ₂ group in which each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') _3-p R' _p in which q is an integer between 1 and 6, p is an integer between 0 and 2 and each R' is independently selected from C1-C4 alkyls,
C1-C12 alkyls substituted by a group –[NH(CH ₂ ) _n ] _m NR ₂ in which m is an integer between 1 and 2, n is an integer between 2 and 6 and each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') _3-p R' _p in which q is an integer between 1 and 6, p is an integer between 0 and 2 and each R' is independently chosen from C1-C4 alkyls,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by a glycidyl group,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by an –OR group in which R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C12, preferably C1-C4, alkyls, substituted by a group –[O(CH ₂ ) _n ] _m OR in which m is an integer between 1 and 2, n is an integer between 2 and 6 and R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C12, preferably C1-C4, alkyls, substituted by a –C(O)OR group in which R is chosen from H and C1-C4 alkyls,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by a –[O(CH ₂ ) _n ] _m OC(O)R group in which m is an integer between 0 and 2, n is an integer between 2 and 6 and R is selected from H, C1-C4 alkyls and C2-C4 alkenyls,
C1-C12, preferably C1-C4, alkyls substituted by an –OC(O)NHR group in which R is chosen from H, C1-C4 alkyls, and
C1-C12 alkyls substituted by a group –(CH ₂ ) _q Si(OR') _3-p R' _p in which q is an integer between 1 and 6, p is an integer between 0 and 2 and each R' is independently selected from C1-C4 alkyl.

More preferably, each R2 is independently chosen from
C1-C4 alkyls,
C1-12 alkyls substituted by an –NR ₂ group in which each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') ₃ in which q is an integer between 2 and 4, p is an integer between 0 and 2 and R' is chosen from C1-C4 alkyls,
C1-C12 alkyls substituted by a group –[NH(CH ₂ ) _n ] _m NR ₂ in which m is an integer between 1 and 2, n is an integer between 2 and 6 and each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') ₃ in which q is an integer between 2 and 4, p is an integer between 0 and 2 and R' is chosen from C1-C4 alkyls ,
C1-C4 alkyls substituted by an –OR group in which R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C4 alkyls substituted by an –OC(O)R group in which R is chosen from H, C1-C4 alkyls and C2-C4 alkenyls, and
C1-C12 alkyls substituted by a group –(CH ₂ ) _q Si(OR′) ₃ in which q is an integer between 1 and 6 and R′ is chosen from C1-C4 alkyls.

In formula II, k is preferably 1 or 2. When k is 2, at least one R2 is typically C1-C12 alkyl, preferably C1-C4 alkyl.

The silanes of formula IIa preferably comprise at least one R2 is chosen from
C8-C12 alkyls,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by an aryl group,
C1-12 alkyls substituted by an –NR ₂ group in which each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') _3-p R' _p in which q is an integer between 1 and 6, p is an integer between 0 and 2 and each R' is independently selected from C1-C4 alkyls,
C1-C12 alkyls substituted by a group –[NH(CH ₂ ) _n ] _m NR ₂ in which m is an integer between 1 and 2, n is an integer between 2 and 6 and each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') _3-p R' _p in which q is an integer between 1 and 6, p is an integer between 0 and 2 and each R' is independently chosen from C1-C4 alkyls,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by a glycidyl group,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by an –OR group in which R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C12, preferably C1-C4, alkyls, substituted by a group –[O(CH ₂ ) _n ] _m OR in which m is an integer between 1 and 2, n is an integer between 2 and 6 and R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C12, preferably C1-C4, alkyls, substituted by a –C(O)OR group in which R is chosen from H and C1-C4 alkyls,
C1-C12 alkyls, preferably C1-C4 alkyls, substituted by a –[O(CH ₂ ) _n ] _m OC(O)R group in which m is an integer between 0 and 2, n is an integer between 2 and 6 and R is selected from H, C1-C4 alkyls and C2-C4 alkenyls,
C1-C12, preferably C1-C4, alkyls substituted by an –OC(O)NHR group in which R is chosen from H, C1-C4 alkyls, and
C7-C12 alkyls substituted by a group –(CH ₂ ) _q Si(OR') _3-p R' _p in which q is an integer between 1 and 6, p is an integer between 0 and 2 and each R' is independently selected from C1-C4 alkyl.

More preferably, each R2 is independently chosen from
C1-12 alkyls substituted by an –NR ₂ group in which each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') ₃ in which q is an integer between 2 and 4, p is an integer between 0 and 2 and R' is chosen from C1-C4 alkyls,
C1-C12 alkyls substituted by a group –[NH(CH ₂ ) _n ] _m NR ₂ in which m is an integer between 1 and 2, n is an integer between 2 and 6 and each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') ₃ in which q is an integer between 2 and 4, p is an integer between 0 and 2 and R' is chosen from C1-C4 alkyls ,
C1-C4 alkyls substituted by an –OR group in which R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C4 alkyls substituted by an –OC(O)R group in which R is chosen from H, C1-C4 alkyls and C2-C4 alkenyls, and
C7-C12 alkyls substituted by a –(CH ₂ ) _q Si(OR′) ₃ group in which q is an integer between 1 and 6 and R′ is chosen from C1-C4 alkyls.

In the silanes of formula IIb, each R2 is preferably independently chosen from C1-C7 alkyls, preferably C1-C4 alkyls, and C1-C7 alkyls substituted by a group –Si(OR') _3-p R ' _p wherein p is an integer between 0 and 2 and each R' is independently selected from C1-C4 alkyl.

In a particularly preferred embodiment, the silanes of formula II are silanes wherein k is 1 or 2, each R2 is independently selected from
C1-C4 alkyls,
C1-12 alkyls substituted by an –NR ₂ group in which each R is independently chosen from H, C1-C4 alkyls and –(CH ₂ ) _q Si(OR') ₃ in which q is an integer between 2 and 4, p is an integer between 0 and 2 and R' is chosen from C1-C4 alkyls,
C1-C12 alkyls substituted by a group –[NH(CH ₂ ) _n ] _m NR ₂ in which m is an integer between 1 and 2, n is an integer between 2 and 6 and each R is independently chosen from H and C1-C4 alkyls,
C1-C4 alkyls, substituted by an –OR group in which R is chosen from H, C1-C4 alkyls and glycidyl,
C1-C4 alkyls substituted by an –OC(O)R group in which R is chosen from H, C1-C4 alkyls and C2-C4 alkenyls, and
C1-C12 alkyls substituted by a -(CH ₂ ) _q Si(OR') ₃ group in which q is an integer between 1 and 6 and R' is chosen from C1-C4 alkyls,
and when k is 2 at least one R2 is selected from C1-C4 alkyl.

The silanes of formula I are preferably chosen from tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane.

The silanes of formula II are preferably chosen from methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 11-aminoundecyltriethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane , N-butylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, (N,N-diethyl-3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane , N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, N-(6-aminohexyl)aminomethyltriethoxysilane, 3-trimethoxysilylpropyl)diethylenetriamine, 1,2-bis(triethoxysilyl)ethane, 1,6-bis(trimethoxysilly )hexane, 1,8-bis(triethoxysilyl)octane, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-N-methylamine, N,N'-bis[(3-trimethoxysilyl)propyl] ethylenediamine, tris(triethoxysilylpropyl)amine, 3-glycido xypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylethoxysilane, acryloxypropyltrimethoxysilane, and methacryloxypropyltrimethoxysilane.

The silanes of formula IIa are preferably chosen from 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 11-aminoundecyltriethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, N-butylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane , (N,N-diethyl-3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)- 11-aminoundecyltrimethoxysilane, N-(6-aminohexyl)aminomethyltriethoxysilane, 3-trimethoxysilylpropyl)diethylenetriamine, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(triethoxysilyl)octane, bis(3-triethoxysilylpropyl) amine, bis(3-trimethoxysilylpropyl)-N-methylamine, N,N'-bis[(3-trimethoxysilyl)propyl]ethylenediamine, tris(triethoxysilylpropyl)amine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -glycidoxypropylmethyldiethoxysilane, the 3 -glycidoxypropyldimethylethoxysilane, acryloxypropyltrimethoxysilane, and methacryloxypropyltrimethoxysilane.

The silanes of formula IIb are preferably chosen from methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane.

The solution of precursors can also comprise other sol-gel precursors, other than hydrolysable silanes, such as metal alkoxides, in particular titanium or aluminum.

The precursor solution comprises 10 to 40%, preferably 20 to 35%, of a phosphorus agent.

The phosphorus agent is generally chosen from compounds capable of forming hydrogen bonds in order to limit the appearance of blurring. It is typically chosen from phosphorus acids and organophosphorus compounds, in particular phosphonates, phosphates, phosphites and polyphosphates. Phosphorus acids include phosphoric acid, phosphorous acid, metaphosphoric acid and pyrophosphoric acid. Examples of phosphonates include dialkyl alkyl phosphonates, such as diethyl ethyl phosphonate or diethyl methyl phosphonate. Examples of phosphates include alkyl phosphates, alkyl alkenyl phosphates such as diethylallyl phosphate, aryl phosphates such as tricresyl phosphate, and melanin phosphate. Examples of phosphites include alkyl phosphites such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite or trimethyl phosphite, and aryl phosphites such as diphenyl phosphite or dibenzyl phosphite. Examples of polyphosphates include triphosphoric acid and melanin pyrophosphate. The phosphorus agent is preferably chosen from phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, dimethyl methylphosphonate, dimethyl ethylphosphonate, diethylallylphosphate, diethylphosphite, dimethylphosphite, dipropylphosphite, dibutylphosphite, trimethylphosphite, diphenylphosphite and dibenzylphosphite. More preferentially, the phosphorus agent is preferably phosphoric acid or diethylphosphte.

The solution of precursors has a pH of less than 7, preferably less than 6, more preferably from 1 to 5. The pH of the solution is measured at room temperature, typically 22°C. The pH of the solution can be adjusted if necessary by adding an acid catalyst. Thus, in some embodiments, the precursor solution comprises an acid catalyst, typically 2-20%, preferably 5-9%, by weight acid catalyst based on total dry matter weight. The acid catalyst can be chosen from mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid or acid boric acid, and organic acids, preferably of low molecular mass, for example less than 250 g/mol, or even less than 200 g/mol, such as citric acid or acetic acid.

The solution of precursors can also comprise fillers, in particular inorganic, such as silica particles (in particular colloidal silica), silicates or glass fibers. The fillers are advantageously chosen so as not to affect the optical properties of the coating. It can comprise from 0.5%, even 1% to 60%, even 50%, 40%, 20%, or even 15% by weight of fillers. Contents of less than 5%, or even 2% by dry weight are however preferable to limit the appearance of blurring. Preferably, the coating composition does not include fillers.

The precursor solution has a dry matter content of 20%, even 30%, or even 40% to 80%, even 70%, or even 60% by weight. It therefore comprises less than 80%, preferably less than 70%, even less than 60%, or even less than 50%, by weight of a solvent. The solvent is generally based on water or a water/alcohol mixture, for example in a water:alcohol mass ratio of 2:1 to 20:1, preferably 3:1 to 15:1. Alcohol is typically ethanol. In some embodiments, the solvent does not include ethanol.

The precursor solution is typically prepared by successive addition of the hydrolysable silanes, the phosphorus agent, and any fillers or additives in a solvent. When the nature of the constituents, in particular the silanes, does not make it possible to obtain a solution at acid pH, an acid catalyst can be added to it. In this case the acid catalyst is preferably added to the solvent before the introduction of the silanes and the other constituents.

Before being applied to the glass sheet, the precursor solution undergoes a pre-condensation/curing step for 10 to 150 hours to obtain an intumescent coating composition. This pre-condensation/ripening step comprising heating the solution of precursors, in particular heating under reflux, for 1 to 50 h at a temperature of 30 to 100° C., preferably 30 to 80° C., or even 30 at 70°C. The pre-condensation of the silicate network is ensured by this heating step. The ripening of the solution, typically lasting 20 to 100 hours, can meanwhile be at room temperature or with continued heating. The pre-condensation and ripening step can thus include heating the precursor solution for 1 to 50 hours at a temperature of 30 to 100°C, preferably 30 to 80°C, or even 30 to 70°C, and maintaining the precursor solution for 20 to 100 h at a temperature of 10 to 100°C, or even 10 to 70°C, and preferably at room temperature, typically 10 to 30°C. It has indeed been noticed that this pre-condensation and curing step was necessary, especially when implementing large volumes, to obtain an intumescent coating composition allowing the deposition of a coating of satisfactory quality. It is indeed assumed that the high dry matter content of the precursor solution affects the kinetics of condensation favoring the appearance of defects during drying and/or aging of the coating.

The intumescent coating composition obtained after the pre-condensation/curing step has a dry matter content greater than 20%, preferably greater than 30%, or even greater than 50%, and typically less than 90%, preferably less at 80%. The method according to the invention can also comprise a step of concentrating the intumescent coating composition, for example by distillation. This step makes it possible, if necessary, to eliminate part of the solvent in order to maintain or increase the dry matter content, in particular due to the release of water and volatile alcohols such as ethanol during the hydrolysis and condensation.

The intumescent coating composition is then deposited on the glass sheet and dried to form an intumescent coating. The coating composition can be applied to the surface of the glass sheet by any technique known to those skilled in the art, such as for example wet deposition techniques such as by spraying ( spray coating ), by curtain application ( curtain coating ), by spraying ( flow coating ), by application by roller ( roller coating ), by blade ( blade coating ) or by casting or by inkjet ( inkjet ). It is in particular appreciable that the coating composition according to the invention is in particular suitable for deposition methods of the application type by spraying, by casting, by roller or by curtain, which are economical and easily industrializable methods.

After application, the deposit is dried, typically at temperatures of 20 to 100° C. for 1 minute to 24 hours, preferably for 1 to 20 minutes, to obtain an intumescent coating.

The intumescent coating obtained after deposition and drying typically has a thickness of 30 to 700 μm, preferably 50 to 500 μm. The coating composition according to the invention in fact makes it possible to obtain, due to the relatively high quantity of dry matter, an unusually thick coating for a layer obtained by a sol-gel process. The deposition and drying steps can nevertheless be repeated several times, in particular two or three times to obtain the desired final coating thickness.

The glass sheet can have a thickness which varies from 1 to 8 mm, preferably 2 to 6 mm. The glass can be a silico-sodo-lime glass obtained by floating on a tin bath (according to the “ float ” process), a borosilicate glass, a transparent vitroceramic or any other type of transparent glass. It can be clear or colored glass depending on the desired aesthetic result. In a first alternative, the glass sheet is an untempered glass sheet. In a second alternative, it is a tempered glass sheet.

Another aspect of the present invention relates to glazing comprising a sheet of glass coated with an intumescent coating, in particular capable of being obtained by the process according to the above process, characterized in that the intumescent coating is based on a sol-gel material obtained from a solution of precursors comprising, based on the total weight of dry matter, 10 to 40%, preferably 20 to 35%, of a phosphorus agent and 50 to 90%, preferably from 60 to 80% of hydrolysable silanes; said hydrolysable silanes comprising 50 to 100% by weight of at least one silane chosen from the silanes of formula I and the silanes of formula II.

The characteristics of the precursor solution described above concerning the nature of the components and their quantities also apply to the intumescent coating.

The intumescent coating according to the invention is preferably a mainly inorganic coating, that is to say comprising at most 50% by weight of carbon based on the total by weight of the elements excluding hydrogen and oxygen. It typically comprises 10 to 40%, preferably 20 to 35%, by weight of silicon, 10 to 60%, preferably 15 to 50%, or even 25 to 40%, by weight of carbon and 5 to 40%, of preferably 10 to 25%, by weight of phosphorus based on the total by weight of the elements excluding hydrogen and oxygen. It comprises The Si/C mass ratio is preferably from 0.5 to 1.5, more preferably from 0.8 to 1.5. The P/Si mass ratio is preferably from 0.2 to 1.0, more preferably from 0.4 to 0.8. The composition of the coating can be measured by microprobe.

The intumescent coating typically has a thickness of 30 to 700 μm, preferably 50 to 500 μm. It typically has a total light transmission greater than 85%, preferably greater than 87%, and a haze of less than 15%, preferably less than 10%, or even less than 5%, measured with a Hazemeter according to standard ASTM D1003-00 with illuminant C.

The intumescent coating may be in direct contact with the glass sheet. Within the meaning of the present invention, an element A "in direct contact" with an element B means that no other element is placed between said elements A and B. On the contrary, an element A "in contact" with an element B does not exclude the presence of another element between said elements A and B. Alternatively, a bonding layer, in particular based on silanes, can be placed between the intumescent coating and the glass sheet in order to improve its adhesion to the sheet of glass.

The intumescent coating has the property of foaming under the effect of temperature, typically at temperatures above 100° C., or even above 180° C., for example between 200 and 400° C., to reach at least eight times, preferably at least 10 times their initial thickness.

The glazing can be single glazing, multiple glazing (for example double or triple) or laminated glazing. It may comprise several intumescent coatings according to the invention. In the case of single glazing, for example, the glass sheet can be coated with an intumescent coating on each of its faces. In the case of laminated glazing, a single sheet of glass or each sheet of glass may be coated on at least one of their faces with an intumescent coating. In the case of multiple glazing, several sheets of glass, or even each sheet of glass, can be coated on at least one of their faces with an intumescent coating. The glazing can also comprise functional coatings, in particular for solar control, low-e, photocatalytic, etc. In a particular embodiment, the glazing according to the invention is a fire-resistant glazing comprising a first sheet of glass coated on a of its faces with a first intumescent coating according to the invention and a second glass sheet coated on one of its faces with a second intumescent coating according to the invention, said first and second glass sheets being assembled together, by their respective faces coated with intumescent coatings, using an interlayer. In this case, the first and second intumescent coatings are preferably in direct contact respectively with the first and second sheets of glass. The interlayer may be a lamination interlayer, for example based on poly(vinyl butyral) (PVB). This fire-resistant glazing can also be integrated into multiple glazing possibly comprising functional coatings.

The invention is illustrated with the aid of the following non-limiting examples.

EXAMPLE

According to example 1 according to the invention, an intumescent coating composition is prepared as follows: 46.3 g of an aqueous solution of hydrochloric acid at 2.36 mol/L is mixed with 3.6 g of ethanol; the various silanes (22.4 g of aminopropyltriethoxysilane, 11.4 g of tetraethoxysilane, 2.72 g of methyltriethoxysilane) and 14.6 g of diethylphosphite are successively added to this solution. The solution of precursors obtained is subjected to pre-condensation/ripening by heating under reflux at 60° C. for 24 h.

The intumescent coating composition thus obtained is deposited on a sheet of glass using a bar applicator. The coating obtained after drying for 8 minutes at 70°C has a thickness, measured using a mechanical profilometer (Dektak 8 Veeco), of 70 µm. The deposition operation is repeated to obtain a layer with a thickness of about 200 μm.

Examples 2 to 4, according to the invention, and comparative examples 5 and 8 are carried out in an identical manner to example 1 with different compositions, examples 7 and 8 having moreover not undergone a pre-preparation step. condensation/ripening.

A fire test according to standard EN1363-1: 2020 is carried out on the samples of examples 1 to 5 consisting of single glazing coated with the intumescent coating.

The characteristics of the coating obtained (thickness, appearance of deposit and haze), as well as the results of the fire test are summarized in Table 1. The appearance of the deposit is noted as follows:
(--) composition unsuitable for thick layer deposition
(-) discontinuous deposit
(+) continuous deposit
The resistance to the fire test is rated as follows:
(-) absence of intumescence of the coating
(+) intumescence of the coating and preservation of the integrity in the fire test for more than 30 min

Ex1 Ex2 Ex3 Ex4 Ex5 Ex6 Ex7 Ex8 TEOS (g) 11.6 11.6 0 0 0 0 11.6 11.6 MTEOS (g) 2.7 2.7 14.7 10 14.7 14.7 2.7 2.7 APTEOS (g) 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 GLYMO (g) 0 0 0 4.73 0 0 0 0 DEP (g) 14.6 14.6 14.6 14.6 0 14.6 14.6 14.6 HCI (g) 3.8 3.7 3.8 3.8 3.8 0 3.8 - Water (g) 42.5 107.9 42.5 42.5 42.5 42.5 42.5 378 Ethanol (g) 3.6 14.6 3.6 3.6 3.6 3.6 3.6 14.6 MS (%) 54 31 54 55 43 54 54 11.6 pH <5 <5 <5 <5 <5 >7 <5 >7 Aspect (+) (+) (+) (+) (+) (+) (-) (--) Vague (%) <5 <5 <5 <5 <5 >20 n.m. >20 Fire test (+) (+) (+) (+) (-) n.m. n.m. n.m. TEOS: tetraethoxysilane
MTEOS: methyltriethoxysilane
APTEOS: aminopropyltriethoxysilane
GLYMO: 3-glycidoxypropyltrimethoxysilane
DEP: diethylphosphite
MS: dry matter of the precursor solution
nm: not measured

Examples 1 to 4 according to the invention all have a continuous coating, without cracks, transparent and with low haze. These coatings also have good intumescent properties allowing the integrity of the sample to be maintained beyond 35min during the fire test.

The composition of the coatings of examples 3 and 4 was analyzed with an SX Five microprobe (tungsten source), at 10kV in delocalized beam mode 120c 80μm, by studying C-Kα, O-Kα, P-Kα at 80nA and Si -Kα at 10nA, with a PGT grid C as standard for carbon, amorphous SiO ₂ for oxygen and silicon and PGT grid GaP for phosphorus. The results, measured on the basis of the total by weight of the elements excluding hydrogen and oxygen, are presented in Table 2.

Composition (wt%) Whether VS P NOT Cl Si/C P/If Ex3 30 32 17 8 12 1.0 0.6 Ex4 27 36 15 7 14 0.8 0.6

Example 5 presents a coating with a satisfactory appearance but no intumescent properties. This coating does not generate foam of carbonaceous residue loaded with silica unlike the examples according to the invention, but only a thin layer of silica without mechanical resistance which disintegrates when it is exposed to weak mechanical stresses. This layer does not provide effective fire protection.

The coating of example 6 is not transparent and has a whitish appearance, with a very significant haze, even opaque. It is not suitable for the glazing applications covered by the present invention.

Example 7, which did not undergo pre-condensation/curing, exhibits a discontinuous deposit due to the dewetting of the coating composition during its application/drying.

The coating composition of Example 8 is not suitable for depositing a thick layer, even in several passes, due to its low dry matter content. The coating obtained also has a whitish appearance, with a very significant haze.

A fire-resistant glazing according to the invention was prepared from two sheets of annealed, non-tempered glass, 3 mm thick. An intumescent coating about 200 μm thick is produced on each of the glass sheets by depositing intumescent coating compositions similar to examples 1 to 4. The two glass sheets thus coated are arranged parallel to each other, the intumescent coatings face to face, and assembled using a 380 µm thick PVB interlayer at 100°C under 10 bar.

Claims (11)

A method of making an intumescent coating on a sheet of glass comprising:
- the preparation of a solution of precursors comprising 20 to 80% by weight of dry matter and having a pH of less than 7; said solution comprising, based on the total weight of dry matter, 10 to 40% of a phosphorus agent and 50 to 90% of hydrolysable silanes; said hydrolysable silanes comprising 50 to 100% by weight of at least one silane chosen from the silanes of formula I and the silanes of formula II:
(I) (R1O) ₄ If
(II) R2 _k (R1O) _4-k Si
in which
each R1 is independently selected from C1-C4 alkyl;
k is an integer between 1 and 3; and
each R2 is independently selected from C1-C12 alkyls, optionally substituted by one or more substituents, preferably one substituent, independently selected from the group consisting of aryl, –[NH(CH ₂ ) _n ] _m NR ₂ , –[ O(CH ₂ ) _n ] _m OR, –C(O)OR, –[O(CH ₂ ) _n ] _m OC(O)R, –OC(O)NHR, glycidyl, –Si(OR') _{3- p} R' _p , where m is an integer between 0 and 3, n is an integer between 1 and 6, each R is independently selected from H, C1-C4 alkyl, aryl, C2-C4 alkenyl, glycidyl, – (CH ₂ ) _q Si(OR') _3-p R' _p , p is an integer between 0 and 2, q is an integer between 1 and 6, and each R' is independently chosen from C1-C4 alkyl;
- the pre-condensation and the ripening of the solution of precursors for 10 to 150 h comprising the heating of the solution of precursors for 1 to 50 h at a temperature of 30 to 100° C., to obtain an intumescent coating composition;
- depositing the intumescent coating composition on the glass sheet; and
- drying the intumescent coating composition to form an intumescent coating. Process according to Claim 1, characterized in that the hydrolysable silanes comprise 0 to 60% by weight of at least one silane chosen from the silanes of formula I and 40 to 100% by weight of at least one silane chosen from the silanes of formula II relative to the total amount of hydrolysable silanes. Process according to one of Claims 1 or 2, characterized in that the hydrolysable silanes comprise:
10 to 50% of at least one silane chosen from silanes of formula I, 40 to 80% of at least one silane chosen from silanes of formula IIa and 0 to 20% of at least one silane chosen from silanes of formula IIb
0 to 20% of at least one silane chosen from the silanes of formula I, 40 to 90 of at least one silane chosen from the silanes of formula IIa and 10 to 50% of at least one silane chosen from the silanes of formula IIb
10 to 60% of at least one silane chosen from the silanes of formula I, 0 to 30% of at least one silane chosen from the silanes of formula IIa and 10 to 60% of at least one silane chosen from the silanes of formula IIb;
50 to 100% of at least one silane chosen from the silanes of formula IIa and 0 to 50% of at least one silane chosen from the silanes of formula IIb;
in which the silanes of formula IIa correspond to silanes of formula II in which at least one R2 group comprises an amine, carboxylic acid, ester, epoxy, ether, acrylate, urethane or alcohol function, or a carbon chain of 8 carbons or more , and the silanes of formula IIb correspond to silanes of formula II in which no R2 group comprises an amine, carboxylic acid, ester, epoxy, ether, acrylate, urethane, alcohol function, or a carbon chain of 8 or more carbons. Process according to one of Claims 1 to 3, characterized in that the silanes of formula I are chosen from tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane. Process according to one of Claims 1 to 4, characterized in that the silanes of formula II are chosen from methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 11 -aminoundecyltriethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, N-butylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, (N,N-diethyl-3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane , N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, N-(6-aminohexyl)aminomethyltriethoxysilane, 3-trimethoxysilylpropyl)diethylenetriamine, 1,2-bis (triethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(triethoxysilyl)octane, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-N-methylamine, N ,N'-bis[(3-trimethoxysilyl)propyl]ethylenedia mine, tris(triethoxysilylpropyl)amine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylethoxysilane, acryloxypropyltrimethoxysilane and methacryloxypropyltrimethoxysilane. Process according to one of Claims 1 to 5, characterized in that the phosphorus agent is chosen from phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, dimethyl methyl phosphonate, ethyl phosphonate dimethyl, diethylallylphosphate, diethylphosphite, dimethylphosphite, dipropylphosphite, dibutylphosphite, trimethylphosphite, diphenylphosphite and dibenzylphosphite. Process according to one of Claims 1 to 6, characterized in that the solution of precursors comprises an acid catalyst preferably chosen from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid , metaphosphoric acid, pyrophosphoric acid, boric acid, citric acid and acetic acid. Fire-resistant glazing comprising a sheet of glass and an intumescent coating on at least one of these faces, obtained by the method defined in one of Claims 1 to 7, characterized in that the intumescent coating is based on a material sol-gel obtained from a solution of precursors comprising, based on the total weight of dry matter, 10 to 40% of a phosphorus agent and 50 to 90% of hydrolysable silanes; said hydrolysable silanes comprising 50 to 100% by weight of at least one silane chosen from the silanes of formula I and the silanes of formula II:
(I) (R1O) ₄ If
(II) R2 _k (R1O) _4-k Si
in which
each R1 is independently selected from C1-C4 alkyl;
k is an integer between 1 and 3; and
each R2 is independently selected from C1-C12 alkyls, optionally substituted by one or more substituents, preferably one substituent, independently selected from the group consisting of aryl, –[NH(CH ₂ ) _n ] _m NR ₂ , –[ O(CH ₂ ) _n ] _m OR, –C(O)OR, –[O(CH ₂ ) _n ] _m OC(O)R, –OC(O)NHR, glycidyl, –Si(OR') _{3- p} R' _p , where m is an integer between 0 and 3, n is an integer between 1 and 6, each R is independently selected from H, C1-C4 alkyl, aryl, C2-C4 alkenyl, glycidyl, – (CH ₂ ) _q Si(OR') _3-p R' _p , p is an integer between 0 and 2, q is an integer between 1 and 6, and each R' is independently chosen from C1-C4 alkyl; Glazing according to Claim 8, characterized in that the intumescent coating comprises 10 to 40% by weight of silicon and 10 to 60% by weight of carbon and 5 to 40% by weight of phosphorus on the basis of the total by weight of the elements excluding hydrogen and oxygen. Pane according to one of Claims 8 or 9, characterized in that the intumescent coating has a thickness of 30 to 700 µm, preferably 50 to 500 µm. Glazing according to one of Claims 8 to 10, characterized in that the glazing comprises a first sheet of glass coated on one of its faces with the said intumescent coating and a second sheet of glass coated on one of its faces with the said intumescent coating, the said first and second sheets of glass being assembled together, by their respective faces coated with said intumescent coating, using an interlayer.