EP1692238A2

EP1692238A2 - Adhesion promoting agent for a thermal insulation surface

Info

Publication number: EP1692238A2
Application number: EP04805604A
Authority: EP
Inventors: Catherine Hedouin; Daniel Joubert; Roland Reeb
Original assignee: Hexion Specialty Chemicals Inc
Current assignee: Hexion Research Belgium SA
Priority date: 2003-12-01
Filing date: 2004-12-01
Publication date: 2006-08-23
Also published as: EA200601073A1; US20100028692A1; FR2862978B1; US20070256600A1; CA2547403C; WO2005054391A2; BRPI0417062A; UA90851C2; EA008650B1; FR2862978A1; CN1890338A; CN1890338B; US8044124B2; WO2005054391A3; CA2547403A1

Abstract

The invention relates to a novel agent that promotes adhesion to a thermal insulation surface and, in particular, to a polystyrene surface, such as in the wet state or owing to a significant variation in temperature. The invention also relates to the use of said agent in a water-insoluble film-forming polymer composition or in a mineral binder composition for applications in the field of construction and, more specifically, in external thermal insulation systems.

Description

New adhesion promoting agent on a thermal insulating surface and in particular on a polystyrene surface, and its use in the field of construction and more particularly in exterior thermal insulation systems

The present invention relates to a new adhesion promoting agent on a thermal insulating surface and in particular on a polystyrene surface, in particular in the wet state or under the effect of a significant variation in temperature. The invention also relates to its use in a film-forming polymer composition insoluble in water or in a mineral binder composition for applications in the construction field and more particularly in exterior thermal insulation systems.

In general, in the construction of new buildings, there is an increasing incorporation, especially in Europe, of polystyrene-based materials.

For example, insulating coating elements such as polystyrene such as extruded or expanded polystyrene or polyurethane constitute a support material for laying ceramic tiles in a thin bed process.

In addition, building elements made of polystyrene materials are suitable for interrupting thermal bridges, as they appear, for example, where concrete or masonry meet.

The application of plates of polystyrene-based materials is also used on building facades, for the purpose of thermal insulation.

A common method consists in the case of thermal insulation to be fixed on the facade (for example in masonry, concrete, mineral plaster, etc.) the back of the insulating plates of polystyrene or another mineral wool insulator by means mortar or cement. On the front side of polystyrene or other mineral wool insulation plates, a mortar is also applied as that coating says reinforcement. This is used in particular for the inclusion of fiber reinforcements (for example reinforcements based on glass fibers, polyester, polypropylene), which are used to reinforce the mechanical properties of the external thermal insulation system. Then a reinforcing coating is usually applied to the fiberglass mesh again, for the complete inclusion of the mesh, the surface is leveled and, after drying, a finishing coating is applied, for example a mineral coating or a coating based on synthetic resin, such as plaster, or paint.

In general, according to the above, there is an increasing problem of obtaining a permanent adhesive bond between materials based on insulators and in particular based on polystyrene and mineral building materials. In particular, this adhesion must be satisfactory even under the effect of humidity or a significant variation in temperature.

The disadvantage of known mineral building materials is that their adhesion to thermal insulating materials and in particular to polystyrene-based materials, after consolidation, is not satisfactory.

It has been described in document EP 0698586 the possibility of using an additive based on aromatic polyether to improve the adhesion of mineral building materials to materials based on polystyrene. However, these compounds have the drawback in particular of not sufficiently improving the adhesion in the wet state and of not sufficiently reducing the uptake of water by capillarity.

One of the aims of the present invention is to provide mineral building materials which, after their consolidation, have increased adhesion, in the wet state or under the effect of a significant variation in temperature, to thermal insulating materials and in particular to materials based on polystyrene. This object and others are achieved by the present invention which relates to a new adhesion promoting agent on a surface of thermal insulator and in particular on a polystyrene surface, in particular in the wet state or under the effect a significant variation in temperature, based on a mono, di or tri phosphate ester or their mixture.

The invention also relates to a film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester or a mixture thereof.

The subject of the invention is also the use of a film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester - or their mixture as an adhesion primer on a thermal insulating support and in particular to polystyrene base.

The invention also relates to a mineral binder composition comprising a mono, di or tri phosphate ester or a mixture thereof.

Another subject of the invention is the use of the mineral binder composition to increase the adhesion of a thermal insulator and in particular of polystyrene to a support material.

The invention also relates to a method for increasing the adhesion properties on a support by thermal insulation and in particular in polystyrene, in particular in the wet state or under the effect of a significant variation in temperature, after consolidation. , of a composition of hydraulic mineral binders characterized in that a sufficient amount of at least one mono, di or tri phosphate ester or their mixture is added to said composition. The invention therefore firstly relates to a new adhesion promoting agent on a thermal insulating surface and in particular polystyrene, in particular to wet or under the effect of a significant change in temperature, based on a mono, di or tri phosphate ester or their mixture.

By thermal insulating material or support is meant in particular polystyrene, polyurethane, mineral wools such as glass wool or rock wool.

Polystyrene is preferred.

The phosphate mono, di or tri esters of the invention may in particular be compounds corresponding to the following formula (I): O = P (OR1) (OR2) (OR3) (I)

in which,

R1, R2 and R3, which are identical or different, represent: a hydrogen atom, or - a saturated or unsaturated, linear or branched or cyclic alkyl radical, having from 1 to 22 carbon atoms, preferably from 2 to 12 atoms carbon, and even more preferably from 2 to 8 carbon atoms, optionally substituted by halogen atoms, such as fluorine or chlorine, hydroxyl groups, ether groups having between 1 and 12 carbon atoms and preferably between 1 and 6 carbon atoms, thioether groups, ester groups, amide groups, carboxy groups, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups, or an aryl radical, having from 6 to 22 carbon atoms, preferably from 6 to 8 carbon atoms, optionally substituted by halogen atoms, such as fluorine or chlorine, hydroxyl groups, ether groups having between 1 and 12 carbon atoms and preferably between 1 and 6 carbon atoms, thioether groups, ester groups, amide groups, carboxy groups, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups, it being understood that at least one of the substituents R1, R2 or R3 is different from a hydrogen atom.

Mention may be made, among mono, di or tri phosphate phosphate compounds of formula (I), of the following compounds: tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate, di (2-ethylhexyl) phosphate, mono (2-ethylhexyl) phosphate, - tris (2-isooctyl) phosphate, tricresylphosphate, cresyldiphenylphosphate, trixylilphosphate,. .. triphenylphosphate, - tributyl phosphate, triethyl phosphate, tri (2chloroethyl) phosphate, or a mixture thereof.

The mono, di or tri phosphate ester of the agent according to the invention can be incorporated in liquid form or in the form of solid powder in a film-forming polymer composition insoluble in water or in a mineral binder composition. If the mono, di or tri phosphate ester of the invention is in liquid form at room temperature, as is the case of the particular compounds listed above with the exception of triphenylphosphate which is solid at room temperature, it it is possible to adsorb them on an inert mineral support to obtain a solid powder. The adsorption of the mono, di or tri phosphate ester can be carried out by any conventional method of adsorption of compounds on mineral supports inorganic. Mention may in particular be made of the methods described in documents FR 74 27893 or FR 74 36083.

A preferred embodiment for preparing the solid powder of mono, di or tri phosphate esters is a process comprising a step of dry impregnation of a mineral oxide with a sufficient quantity of mono, di or tri phosphate esters.

The mineral oxide can be chosen from silica, alumina, silica-alumina, sodium silico-alurninate, calcium silicate, magnesium silicate, zirconia, magnesium oxide, oxide of calcium, cerium oxide or titanium oxide. The mineral oxide can be completely or partially hydroxylated or carbonate.

The mineral oxide must be of high porosity. This means that its total pore volume must be at least 1 ml / g and preferably at least 2 ml / g. The total pore volume of the mineral oxide is measured by a mercury porosimetry method using a MICROMERITICS Autopore III 9420 porosimeter. The preparation of each sample is carried out as follows: the sample is previously dried for 2 hours in an oven at 200 ° C. The measurements are then carried out according to the procedure described in the manual supplied by the manufacturer. The pore diameters are calculated by the relation of WASHBURN with a teta contact angle equal to 140 ° and a gamma surface tension equal to

485 Dynes / cm.

Preferably the mineral oxide has a useful pore volume greater than or equal to 0.5 ml / g. By useful volume is meant the volume of the pores whose diameter is less than 1 micron. This volume is measured by the same method as the total pore volume. Preferably, a silica is used as the mineral oxide. Even more preferably, an amorphous silica is used. This can be a natural silica or a synthetic silica such as silica gels, combustion silicas or, very preferably, precipitated silicas.

When the mineral oxide is precipitated silica, it may for example be a Tixosil 38A, Tixosil 38D or Tixosil 365 silica from the company Rhodia.

In particular, the precipitated silica may be in the form of substantially spherical beads, in particular of average size of at least 80 microns, for example at least 150 microns, obtained by means of a nozzle atomizer, as described for example in document EP 0018866. It can for example be silica called Microperle. This form makes it possible to optimize the impregnation capacity and the flowability of the powder as described for example in documents EP 0966207 or EP 0984772. It can be, for example, a silica Tixosil 38X or Tixosil 68 from the Rhodia company.

This allows in particular to obtain a mono, di or tri phosphate phosphate powder which flows well and does not dust.

The precipitated silica can be a highly dispersible silica, such as the silicas described in documents EP 0520862, WO 95/09127 or WO 95/09128, which, in particular, facilitates its dispersion in the film-forming polymer composition insoluble in water or in the composition of mineral binder. It may for example be a Z1165 MP or Z1115 MP silica from the company Rhodia.

Amorphous silica can be silica with low water uptake. The "water uptake" corresponds to the amount of water integrated into the sample relative to the mass of the sample in the dry state, after 24 hours at 20 ° C and 70% relative humidity. By low water uptake is meant a water uptake of less than 6% and preferably less than 3%. It can be precipitated silicas described in patent application FR 01 16881 (in the name of the company Rhodia), silicas pyrogenated or partially dehydroxylated silicas by calcination or by surface treatment.

This composition can be in the form of an aqueous dispersion of film-forming polymer insoluble in water (latex) or in the form of a redispersible latex powder. By redispersible latex powder means latex powder redispersible in water.

The process for the preparation of this composition consists in mixing a mono, di or tri phosphate ester or their mixture with a film-forming polymer insoluble in water (latex).

This mixture of the mono, di or tri phosphate ester and the latex can be produced in the form of a mixture of solid powder of mono, di or tri phosphate esters with a redispersible latex powder composition.

It is also possible to introduce the mono, di or tri phosphate ester into the latex during the polymerization or in post-polymerization. The additivated latex can thus be obtained in the form of an aqueous dispersion. It is also possible to carry out drying of the aqueous dispersion thus obtained in order to obtain a redispersible latex powder additivated as a mono, di or tri phosphate ester.

It is also possible to add the mono, di or tri phosphate ester in powder form in the latex atomization tower, that is to say at the time of drying of the latex. Among all these possible forms of mixture, the case is preferred where the mono, di or tri phosphate ester is introduced to an aqueous dispersion of film-forming polymer (latex) in post-polymerization. The latex can then be dried.

The amount of mono, di or tri phosphate ester added to the water-insoluble film-forming polymer must be sufficient to provide the water-insoluble film-forming polymer composition with good adhesion properties to the polystyrene, even at low temperatures. 'wet condition.

The amount of mono, di or tri phosphate ester added to the film-forming polymer insoluble in water is thus generally between 0.02 and 25% by weight of mono, di or tri phosphate ester relative to the weight of dry latex.

Preferably, this amount is between 0.5 and 8% by weight of mono, di or tri phosphate ester relative to the weight of the dry latex.

Even more preferably, this amount is between 1 and 5% by weight of mono, di or tri phosphate ester relative to the weight of dry latex.

Particularly suitable water-insoluble polymers are homo- or copolymers which are in the form of an aqueous dispersion or which can be converted into an aqueous dispersion, and then can be formed into a powder form by spray drying. The average particle size of the powder is preferably from 10 to 1000 μm, more preferably from 20 to 700 μm, and particularly from 50 to 500 μm. The preferred water-insoluble polymers are obtained by polymerization of monomers chosen from: - vinyl esters and more particularly vinyl acetate; - alkyl acrylates and methacrylates in which the alkyl group contains from 1 to 10 carbon atoms, for example methyl, ethyl, n-butyl, 2-ethylhexyl acrylates and methacrylates; - vinyl aromatic monomers, in particular styrene. These monomers can be copolymerized with each other or with other ethylenically unsaturated monomers, to form homopolymers, copolymers or terpolymers. As nonlimiting examples of monomers copolymerizable with vinyl acetate and / or acrylic esters and / or styrene, mention may be made of ethylene and olefins such as isobutene or alpha-olefins having from 6 to 20 carbon atoms and preferably from 8 to 14 carbon atoms; vinyl esters of saturated monocarboxylic acids, branched or not, having from 1 to 16 carbon atoms, such as vinyl propionate, vinyl "Versatate" (registered trademark for esters of branched acids in Cg-Cι ι) and in particular for vinyl neodecanoate called Veova 10, vinyl pivalate, vinyl butyrate, vinyl 2-ethylhexylhexanoate, or vinyl laurate; esters of mono- or dicarboxylic unsaturated acids having 3 to 6 carbon atoms with alkanols having 1 to 10 carbon atoms, such as maleates, methyl, ethyl, butyl, ethylhexyl fumarates; vinyl aromatic monomers such as methylstyrenes, vinyltoluenes; vinyl halides such as vinyl chloride, vinylidene chloride, diolefins especially butadiene; (meth) allyl esters of acid

(meth) acrylic, the (meth) allyl esters of mono and diesters of maleic, fumaric, crotonic and itaconic acids, as well as the alkenic derivatives of amides of acrylic and methacrylic acids, such as N-methallylmaleimide.

One can in particular choose at least 2 copolymerizable monomers of different natures to obtain a terpolymer.

By way of example, there may be mentioned a terpolymer of vinyl acetate / vinyl versatate / dibutyl maleate type.

It is also possible to add to the monomers copolymerizable with vinyl acetate and / or acrylic esters and / or styrene at least one other monomer chosen from the following list: - acrylamide, ethylenically unsaturated carboxylic acids or dibasic acids, preferably acrylic acid, methacrylic acid, or crotonic acid, ethylenically unsaturated sulfonic acids and salts thereof, preferably vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or sodium methallylsulfonate; crosslinking monomers carrying at least two ethylenic unsaturations such as diallylphthalate, diallylmaleate, allylmethacrylate, triallylcyanurate, divinyladipate or ethylene glycol dimethacrylate; monomers with silane functions such as vinyltrimethoxy silane or vinyltriethoxy silane.

These monomers are added in an amount generally between 0.05 and 10.0% by weight, relative to the total weight of the monomers. These monomers are added during the polymerization.

Generally, the polymerization of the monomers is carried out in an emulsion polymerization process in the presence of an emulsifier and / or a protective colloid, and of a polymerization initiator.

The monomers used can be introduced as a mixture or separately and simultaneously into the reaction medium, either before the start of the polymerization in one go, or during the polymerization by successive fractions or continuously.

The emulsifiers which can be used are anionic, cationic or nonionic emulsifiers.

They are generally used in an amount of 0.01 to 5% by weight relative to the total weight of the monomers.

As an emulsifying agent, the conventional anionic agents generally used are represented, in particular by alkylsulfates, alkylsulfonates, alkylarylsulfates, alkylarylsulfonates, arylsulfates, arylsulfonates, sulfosuccinates, alkali metal alkylphosphates, salts of l hydrogenated abietic acid or not. The emulsion polymerization initiator is more particularly represented by hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydro peroxide, paramenthane hydroperoxide, tert-butyl hydroperoxide, and by persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in an amount generally between 0.05 and 3% by weight relative to the total of the monomers. These initiators are optionally combined with a reducing agent, such as bisulfite, hydrogen sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, polyethyleneamines, sugars (dextrose, sucrose), ascorbic or isoascorbic acid, or metal salts . The amount of reducing agent used usually varies from 0 to 3% by weight relative to the total weight of the monomers.

The reaction temperature, depending on the initiator used, is generally between 0 and 100 ° C, preferably between 30 and 90 ° C.

A transfer agent can be used in proportions ranging from 0 to 3% by weight relative to the monomer (s), generally chosen from mercaptans such as N-dodecylmercaptan, tertiododecylmercaptan, 2-mercaptoethanol, allylic derivatives such as allylic alcohol, cyclohexene, halogenated hydrocarbons such as chloroform, bromoform, carbon tetrachloride. It adjusts the length of the molecular chains. It is added to the reaction medium either before the polymerization, or during polymerization.

Protective colloids can also be used at the start, during or after the polymerization.

The particularly suitable protective colloids are polyvinyl alcohols and derivatives thereof, for example vinyl alcohol-vinyl acetate copolymers, modified polyvinyl alcohols comprising reactive functions such as silanols, mercaptans, amines, formamides, and comprising hydrophobic co-monomers such as ethylene, vinyl versatate, vinyl 2-ethylhexylhexanoate, polyvinylpyrrolidones (PVP), polysaccharides, for example starches (amylose and amylopectin), cellulose, cellulose ethers such as hydroxyethylcellulose, guar, tragacantic acid, dextran, alginates and their carboxymethyl, methyl, hydroxyethyl or hydroxypropyl derivatives , proteins, for example casein, soy proteins, gelatins, synthetic polymers, for example poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, and copolymers soluble in l water thereof, melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, styrene / maleic acid copolymers, and vinyl ether-maleic acid copolymers. Polyvinyl alcohol is particularly preferred as a protective colloid for polymerization. A particular protective colloid used is a polyvinyl alcohol having a degree of polymerization of

- 200 to 3500 and having a degree of hydrolysis of 80 to 99 mol% and preferably from 86 to 92%. The protective colloids are added in proportions of between 0.5 and 15% by weight relative to the total weight of the monomers and preferably between 2 and 10% by weight relative to the total weight of the monomers.

In a particularly preferred embodiment, the latex composition with mono, di or tri phosphate esters in the form of redispersible powder comprises 0 to 35% by weight, preferably 3 to 15% by weight, of protective colloid, relative to the total weight of the polymer insoluble in water. The particularly suitable protective colloids are the same as those mentioned above.

Preferred anti-caking agents are aluminum silicates, calcium or magnesium carbonates, or mixtures thereof, silicas, hydrated alumina, bentonite, talc, or dolomite mixtures and talc, or calcite and talc, kaolin, barium sulfate, titanium oxide, or calcium sulfoaluminate (satin white). The particle size of the anti-caking agents is preferably between 0.001 and 0.5 mm. The water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or their mixture can also comprise a water-repellent agent chosen from fatty acids, or their salts such as calcium, magnesium or sodium stearate, or sodium laurate, fatty acid esters such as those described in document WO 01/90023 (MBT). Mention may be made, as particular water-repellent agents, of the methyl esters of C10-C16 fatty acids (having 10 to 16 carbon atoms) such as those sold under the brand Estorob 1214 by the company Novance, the methyl ester of erucic acid, the methyl ester _. e of linoleic acid, the ethylhexyl ester of lauric acid, the butyl ester of oleic acid, the ethylhexyl ester of oleic acid, or the methyl ester of oleic acid.

Preferably, the water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or their mixture comprises, as a particularly advantageous water-repellent agent, a C10-C16 fatty acid methyl ester.

This water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or their mixture has in particular the advantage of being able to be used as it is or in combination with other additives as an adhesion primer on a support to base of thermal insulation and in particular on a support based on polystyrene.

Thus, the subject of the invention is also the use of the film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester or their mixture as an adhesion primer on a support based on thermal insulator and in especially a support based on polystyrene.

This water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or a mixture thereof also has the advantage of reducing the glass transition temperature (Tg) and the minimum temperature. film formation (TMFF) of the non-additive water-insoluble film-forming polymer (latex).

The mineral binders can be aerial binders or hydraulic binders.

By aerial binder is meant plaster-based binders.

The hydraulic mineral binders can be chosen from cements which can be of portian, aluminous or blast furnace type. Other compounds often added as additives to cement also have hydraulic properties such as fly ash, calcined shales. Mention may also be made of pozzolans which react with lime and form calcium silicates. Mineral binders are generally made from natural materials which are treated at very high temperature to remove water and transform the materials into mineral compounds capable of reacting with water to produce a binder which after drying forms a compact mass having good mechanical properties. The mineral binders can be in the form of grout, mortar or concrete; thus, generally when mixing with water, fine or coarser aggregates, such as sand or pebbles, are added.

The mono, di or tri phosphate ester can be added directly to the construction composition, in an amount which may be between 0.01 and 50% by dry weight of the mono, di or tri phosphate ester relative to the total weight of building composition.

Preferably, this amount is between 0.05 and 20% by dry weight of mono, di or tri phosphate ester relative to the total weight of the construction composition. Even more preferably, this amount is between 0.02 and 2% by dry weight of mono, di or tri phosphate ester relative to the total weight of the construction composition.

The mono, di or tri phosphate ester can also be premixed in a sufficient amount with a film-forming polymer composition insoluble in water in the form of an aqueous dispersion (latex) or in the form of a redispersible latex powder before d be added to the mineral binder composition.

The binder composition thus further comprises said mono, di or tri phosphate ester at least one film-forming polymer insoluble in water.

The amounts of mono, di or tri-ester of phosphate or of their mixture generally introduced into the compositions of film-forming polymer insoluble in water are the same as those indicated above.

The redispersible latex powder additivated as a mono, di or tri phosphate ester used can be very varied in nature.

Particularly preferred is a latex composition in the form of a redispersible powder comprising: at least one polymer insoluble in water, from 0 to 35% by weight, in particular from 3 to 15% by weight, relative to the total weight of the polymer , at least one protective colloid, from 0 to 30% by weight, in particular from 1 to 12% by weight, relative to the total weight of the polymer, of anti-caking agent, and from 0.02 to 25% by weight, in particular from 0.5 to 8% by weight, relative to the total weight of the polymer of the mono, di or tri phosphate ester.

The redispersible latex powder with mono, di or tri phosphate esters is preferably prepared by spray drying the aqueous polymer dispersion. This drying can be carried out in conventional spray drying systems, using atomization by means of single, double or multiple liquid nozzles or a rotating disc. The product outlet temperature chosen is generally in the range of 50 to 100 ° C, preferably 60 to 90 ° C, depending on the system, the glass transition temperature of the latex, and the degree of drying desired.

In order to increase the storage stability and the flowability of the redispersible latex powder, it is preferable to introduce an anti-caking agent in the atomization tower together with the aqueous polymer dispersion, which results in a preferable deposit of the anti-caking agent on the particles of the dispersion.

The mineral binder composition thus obtained has, after consolidation, good adhesion properties on thermal insulators and in particular on polystyrene, in particular in the wet state or under the effect of a significant variation in temperature. It also has good water repellency properties and a reduction in the uptake of water by capillarity.

Apart from the mineral constituents, the mineral binder compositions can also comprise organic additives, for example hydrocolloids such as cellulose ethers or guars, plasticizers, water-repellent agents such as those mentioned previously in the insoluble film-forming polymer compositions in water, mineral or organic fibers such as fibers of the polypropylene, polyethylene, polyamide, cellulose, crosslinked polyvinyl alcohol type or a mixture thereof.

The mineral binder composition can also include mineral or organic dyes. This is particularly the case when this mineral binder composition is used as a top coat. The mineral binder composition can also comprise any additive usually used in mineral binder compositions. The composition according to the invention, in particular the mineral binder composition according to the invention, can also comprise a silicone, preferably chosen from polyorganosiloxanes, in particular polyorganosiloxanes which are liquid at room temperature. This silicone can be introduced in post-polymerization, or in the form of a powder.

The subject of the invention is also a process for increasing the adhesion properties on a thermal insulator and in particular on polystyrene, in particular in the wet state or under the effect of a significant variation in temperature, after consolidation, of a composition of mineral binders, characterized in that a sufficient amount of at least one mono, di or tri phosphate ester or their mixture is added to said composition.

The present invention also relates to the use of this mineral binder composition to increase the adhesion of a thermal insulator and in particular of polystyrene on a support material.

The support materials can be composed of concrete, bricks, aerated concrete, agglomerated concrete (concrete block), fiber cement, masonry or wall plaster.

Other advantages of the compositions or methods of the invention are indicated in the examples above which are given by way of illustration and without limitation.

The proportions and percentages indicated in the examples are by weight unless otherwise indicated. The particle sizes (d50) are measured using a Coulter LS 230 laser diffraction particle size analyzer. Examples

Description of the tests

1- Adhesion test on polystyrene

The mortar is spread over the insulation with a thickness of 3 mm a quarter of an hour after mixing. After drying the mortar for 28 days (at (23 ± 2) ° C and (50 ±

5)% RH (relative humidity)), eight circles 50 mm in diameter are cut using a core drilling machine in the mortar up to the insulation. Round metal pellets of appropriate size are fixed on these areas using an araldite glue.

The pull-out test is carried out under the following conditions without additional conditioning (in the dry state), - after immersion of the mortar in water for 2 days and drying for 2 hours (at (23 ± 2) ° C and (50 ± 5)% RH).

The average peel value is based on the results of eight trials. The individual and average values are recorded and the results expressed in

MPa.

2- Capillary water recovery test on stone

Three sandstone tiles are prepared for each formulation. The coating (thickness 3 mm) is applied using a trowel on one side of the sandstone tile. The sandstone tile thus prepared is conditioned for 28 days (at (23 ± 2) ° C and (50 ± 5)% RH). The lateral faces of the sandstone tile are sealed against water so as to ensure that only the face coated with the coating layer is subjected to the uptake of water for the duration of the test. The surface covered by the coating of the sandstone tile is brought into contact with a sponge (a paper filter is previously deposited between the sandstone tile and the sponge) placed in a tank containing water. The sandstone tiles are weighed before immersion (reference weight) and then after 30 minutes, 1 hour, 2 hours, 4 hours, 6 hours, 24 hours. Before the second and subsequent weighings, the surface of the sandstone tiles is wiped with absorbent paper. The calculation aims to determine the average water uptake per square meter over time.

Example 1 - Production of a latex emulsion with additive from a vinyl acetate / vinyl neodecanoate copolymer (sold under the brand Veova 10 by the company Resolution) and tris (2-butoxyethyl) phosphate

Use is made, as control binder, of a latex composed of a vinyl acetate-vinyl versatate copolymer with a composition of 50% vinyl acetate and 50% vinyl versatate (Veova 10) by weight. This latex is synthesized by an emulsion polymerization process using polyvinyl alcohol with a hydrolysis rate of about 88% as a protective colloid and potassium persulfate as a radical initiator. The characteristics of this latex: Dry extract: 50.73% pH: 4.7 TMFF: 7.6 ° C Tg: 16 ° C Brookfield viscosity at 50 rpm: 2420 mPa.s Granulometry: d50: 2 μm

Additive: Amgard TBEP (Rhodia) = tris (2-butoxyethyl) phosphate (CAS = 78-

51-3) Physical form: liquid Preparation of the latex which is the subject of the invention

801.7 grams of control latex are introduced into a 1 liter reactor fitted with anchor type stirring. This latex is heated to a temperature between 60 and 70 ° C. and 16.3 grams of Amgard TBEP are poured in over a period of approximately 20 minutes. After the addition of the Amgard TBEP is completed, the temperature is further maintained for 20 to 30 minutes, then the mixture is cooled to room temperature.

This latex can then be formulated as or be atomized in the presence of an anti-caking agent (for example kaolin or silica) in order to obtain a powder redispersible in water.

Characteristics of the latex which is the subject of the invention

Amgard rate TBEP / dry latex: 4% Dry extract: 51, 91% pH: 4.7 TMFF: 0 ° C Tg: 7 ° C Brookfield viscosity at 50 rpm: 2068 mPa.s Granulometry: d50: 2 microns

Composition of the coating formulation used for bonding and the basic polystyrene coating • CPA CEMI 42.5 gray cement: 600g • Sand HN38 (0.4-4 mm) 1296g • Cellulosic ether Culminai 9101: 1g • Cellulosic ether Culminai 9104: 3g • Lime: 40g • Latex emulsion with additive Amgard TBEP: 115.6g

Water / powder ratio = 0.22 • CPA CEMI 42.5 gray cement: 600g • HN38 sand (0.4-4 mm) 1296g • Culminai 9101 ig cellulosic ether • Culminai 9104 3g cellulosic ether • Lime: 40g • Control latex emulsion: 118.3g

Water / powder ratio = 0.22

Physico-chemical properties of control and additive emulsions

Table 1

The addition of the phosphate ester results in a plasticizing effect on the polymer, with the consequence of a significant drop in its Tg (glass transition temperature) and in its TMFF (minimum film formation temperature). Adhesion test on polystyrene of the additive control latex The results of the adhesion test on polystyrene of the additive control latex in Amgard TBEP are presented in Table 2. Table 2

The mortar containing the control latex additive with Amgard TBEP has an adhesion to polystyrene (0.065 N / mm2) after immersion in water for 2 days and drying for 2 hours (at 23 ° C ± 2 ° C) superior to the mortar containing the non-additive control latex (0.045 N / mm ² ).

Test of water recovery by capillary action on stone of the additive control latex The results of the water recovery test by capillary action on stone of the additive control latex in Amgard TBEP are presented in Table 3.

Table 3

The quantity of water absorbed by capillarity measured after 24 hours is lower in the case where the mortar contains the control latex additive with Amgard TBEP (7.1 kg / m ² ) compared to the mortar containing the control latex (18, 3 kg / m ² ). Example 2

Amgard TOF = tris (2-ethylhexyl) phosphate (CAS 1806-54-8) sold by the company Rhodia.

Amgard TBEP = tris (2-butoxyethyl) phosphate (CAS 78-51-3) sold by the company Rhodia. Physical form: liquid

Preparation of the Latex Powders Subject of the Invention As a control binder, a latex composed of a copolymer of vinyl acetate-vinyl versatate with a composition of 50% vinyl acetate and 50% of versatate is used. vinyl (Veova 10) by weight. This latex is synthesized by an emulsion polymerization process using polyvinyl alcohol with a hydrolysis rate of approximately 88% as a protective colloid and potassium persulfate as a radical initiator. The characteristics of this latex are: Dry extract: 50.0% pH: 4.8 TMFF: 7.5 ° C Tg: 15.5 ° C Brookfield viscosity at 50 rpm: 3000 mPa.s Granulometry: d50: 1.9 microns

11 kg of control latex are introduced into a 25 liter reactor fitted with an anchor type agitation. This latex is heated to a temperature between 60 and 70 ° C. and 220 grams of Amgard TBEP or Amgard TOF are poured over a period of approximately 20 minutes. After the addition of the Amgard is complete, the temperature is further maintained for 20 to 30 minutes and then the mixture is cooled to room temperature. The drying of the suspension was developed by a Niro type atomization process. The temperature of the attack air is between 110 and 160 ° C, preferably here between 120 and 150 ° C, the outlet temperature is between 50 and 90 ° C, preferably here between 60 and 80 ° C. The polymer suspension is sprayed in the presence of mineral or organic fillers which improve the flowability of the product and prevent caking. These fillers can be, for example, carbonates, silicates, silica, double salts (talc, kaolin) or mixtures of these different fillers. The contents of these mineral fillers vary from 2 to 20% and preferably here between 5 and 15%.

Characteristics of the latex powders which are the subject of the invention Control powder:% residual moisture: 1% Average rate of mineral agent: 9.6% Average particle size d50: 74 μm

Example latex powder additive Amgard TBEP Amgard rate / dry latex: 4% - Characteristics of the latex: Dry extract: 50.8% pH: 4.8 TMFF: 0 ° C Brookfield viscosity at 50 rpm: 3024 mPa. s Grain size: d50: 1.9 μm - Characteristics of the powder:% residual moisture: 1.2% Average mineral agent level: 12% Average grain size d50: 79 μm

Example latex powder additive Amgard TOF Amgard rate / dry latex: 4% - Characteristics of the latex: Dry extract: 51, 1% pH: 4.8 TMFF 0 ° C Brookfield viscosity at 50 rpm: 2968 mPa.s Granulometry: d50: 1, 9 μm - Characteristics of the powder:% residual humidity: 0.83% Average rate of mineral agent: 13% Average granulometry d50: 62 μm

Composition of the coating formulation used for the bonding mortar and the base coating on polystyrene

Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7 g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex powder: 60g Water / powder ratio = 0.22 Results

Adhesion to polystyrene Table 4

The adhesion measured after 28 days and after curing in water is greater in the case of mortars containing control powders additive with Amgard TBEP and Amgard TOF compared to the mortar containing control powder not additive.

Water recovery by capillary action on stone

Table 5

The amounts of water absorbed are lower in the case of mortars containing the control powders additive with Amgard TBEP and Amgard TOF compared to the mortar containing the non-additive control powder.

Example 3 (Terpo emulsion + additives) Estorob 1214: C10-C16 acid methyl ester (CAS = 66762-40-7) sold by the company Novance Montasolve CLP: propoxylated cresol with approximately 6 propylene oxide units ( CAS = 9064-13-5) marketed by the company Seppic Preparation of the latex which is the subject of the invention

As a control binder, a latex composed of a copolymer of vinyl acetate-vinyl versatate and dibutyl maleate having a composition of 50% vinyl acetate, 50% vinyl versatate (Veova 10) and 25% dibutyl is used maleate by weight. This latex is synthesized by an emulsion polymerization process using polyvinyl alcohol having a hydrolysis rate of about 88% as a protective colloid and potassium persulfate as a radical initiator. The characteristics of this latex are: Dry extract: 50.73% pH: 4.7 TMFF: 5 ° C Tg: 16 ° C Brookfield viscosity at 50 rpm: 2420 mPa.s Granulometry: d50: 2 μm

Characteristics of the latex which is the subject of the invention

Example terpo control latex

Dry extract: 50.73% pH: 4.7 TMFF: 5 ° C Brookfield viscosity at 50 rpm: 2420 mPa.s Grain size: d50: 2 μm

Example additive control latex with Amgard TBEP

Amgard / dry latex rate: 4% Dry extract: 52.0% pH: 4.8 TMFF: 0 ° C Brookfield viscosity at 50 rpm: 1320 mPa.s Granulometry: d50: 2 μm

Comparative example: additive control latex with propoxyl cresol (Montasolve CLP)

Propoxylated Cresol / dry latex rate: 4% Dry extract: 51.9% pH: 4.8 TMFF: 0 ° C Brookfield viscosity at 50 rpm: 1390 mPa.s Granulometry: d50: 2 μm

Example additive control latex with Amgard TBEP and Estorob 1214

Estorob 1214: CAS = 66762-40-7 marketed by the company Novance

Amgard / dry latex rate: 2% Estorob 1214 rate: 2% Dry extract: 51.9% pH: 4.8 TMFF: 0 ° C Brookfield viscosity at 50 rpm: 1216 mPa.s Granulometry: d50: 2 microns

Composition of the coating formulation used for the bonding mortar and the base coating on polystyrene Example latex control Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Emulsion of latex control: 118.3g Water / ratio powder = 0.22

Example control latex added with Amgard TBEP Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex emulsion additive Amgard : 116.3g Water / powder ratio = 0.22

Comparative example: control latex additive with propoxyl cresol (Montasolve CLP) Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex emulsion with propoxylated cresol additive: 116.3 g Water / powder ratio = 0.22

Example control latex additive Amgard TBEP and Estorob 1214 Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex emulsion with additive Amgard TBEP and Estorob 1214: 116g Water / powder ratio = 0.22

Results

Adhesion on polystyrene

Table 6

The adhesion on polystyrene measured after 28 days and cure in water in the case of mortars containing the control emulsion and the control emulsion additivated with cresol propoxyl is lower than that measured in the case of mortars containing the control emulsion additive with Amgard TBEP and the mixture Amgard TBEP and Estorob 1214. Water recovery by capillary action on stone

Table 7

The quantities of water absorbed are lower in the case of the mortar containing the control emulsion added with the mixture Amgard TBEP and Estorob 1214.

Example 4 (control powder / DEHPA mixture)

DEHPA: di- (2-ethylhexyl) phosphoric acid (CAS = 298-07-7) sold by the company Rhodia

Preparation of the mixture

DEHPA (0.5% by weight / latex powder) is pre-mixed with the latex powder before introduction into the mixture containing the different fillers. Composition of the coating formulation used for the bonding mortar and the base coating on polystyrene

Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.4g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex powder: 60g DEHPA: 0.3g Water / powder ratio = 0.22

Results

Adhesion on polystyrene

Table 8

The adhesion on polystyrene measured after 28 days and after curing in water is greater in the case of the mortar containing the control powder mixed with DEHPA compared to the control powder not additivated. Water recovery by capillary action on stone

Table 9

The amount of water absorbed is lower in the case of the mortar containing the control powder mixed with DEHPA compared to the mortar containing the non-additive control powder.

Claims

1. Adhesion promoting agent on a thermal insulating surface, in particular on a polystyrene surface, in particular in the wet state or under the effect of a significant variation in temperature, based on a mono, di or tri phosphate ester or mixture thereof.

2. Agent according to claim 1, characterized in that said mono, di or tri phosphate ester is a compound of formula (I) below: O = P (OR1) (OR2) (OR3) (I)

in which,

R1, R2 and R3, identical or different, represent: - a hydrogen atom, or a saturated or unsaturated, linear or branched or cyclic alkyl radical, having from 1 to 22 carbon atoms, preferably from 2 to 12 atoms carbon, and even more preferably from 2 to 8 carbon atoms, optionally substituted by halogen atoms, such as fluorine or chlorine, hydroxyl groups, ether groups having between 1 and 12 carbon atoms and preferably between 1 and 6 carbon atoms, thioether groups, ester groups, amide groups, carboxy groups, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups, or - an aryl radical, having 6 with 22 carbon atoms, preferably from 6 to 8 carbon atoms, optionally substituted by halogen atoms, such as fluorine or chlorine, hydroxyl groups, ether groups having between 1 and 12 carbon atoms and preferably that between 1 and 6 carbon atoms, thioether groups, ester groups, amide groups, carboxy groups, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups, it being understood that at least one of the substituents R1, R2 or R3 is different from a hydrogen atom.

3. Agent according to one of claims 1 and 2, characterized in that the mono, di or tri phosphate esters of formula (I) is chosen from: tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl ) phosphate, di (2-ethylhexyl) phosphate, mono (2-ethylhexyl) phosphate, - tris (2-isooctyl) phosphate, tricresylphosphate, cresyldiphenylphosphate, trixylilphosphate, triphenylphosphate, - tributyl phosphate, triethyl phosphate, tri (2chloroethyl) phosphate, or a mixture thereof.

4. Agent according to one of claims 1 to 3, characterized in that the mono, di or tri phosphate ester is adsorbed on an inert mineral support.

5. Agent according to claim 4, characterized in that the inert mineral support is chosen from silica, alumina, silica-alumina, sodium silico-aluminate, calcium silicate, magnesium silicate, zirconia , magnesium oxide, calcium oxide, cerium oxide or titanium oxide.

6. Agent according to one of claims 4 and 5, characterized in that the inert mineral support is silica.

7. Composition of film-forming polymer insoluble in water comprising a mono, di or tri phosphate ester according to one of claims 1 to 6.

8. Composition according to claim 7, characterized in that the composition is in the form of an aqueous dispersion of film-forming polymer insoluble in water (latex).

9. Composition according to claim 7, characterized in that the composition is in the form of a redispersible latex powder.

10. Composition according to one of claims 7 to 9, characterized in that the amount of mono, di or tri phosphate ester is between 0.02 and 25% by weight of mono, di or tri phosphate ester relative to by weight of dry latex.

11. Composition according to claim 10, characterized in that the amount of mono, di or tri phosphate ester is between 0.5 and 8% by weight of mono, di or tri phosphate ester relative to the weight of dry latex .

12. Composition according to one of claims 10 and 11, characterized in that the amount of mono, di or tri phosphate ester is between 1 and 5% by weight of mono, di or tri phosphate ester relative to the weight dry latex.

13. Composition according to one of claims 7 to 12, characterized in that the film-forming polymer insoluble in water is obtained by polymerization of monomers chosen from:

- vinyl esters and more particularly vinyl acetate; - alkyl acrylates and methacrylates in which the alkyl group contains from 1 to 10 carbon atoms, for example methyl, ethyl, n-butyl, 2-ethylhexyl acrylates and methacrylates;

- vinyl aromatic monomers, in particular styrene, these monomers can be copolymerized with one another or with other ethylenically unsaturated monomers, to form homopolymers, copolymers or terpolymers.

14. Composition according to claim 13, characterized in that said monomers are copolymerized with other ethylenically unsaturated monomers chosen from ethylene and olefins such as isobutene or alpha-olefins having from 6 to 20 carbon atoms and preferably from 8 to 14 carbon atoms; vinyl esters of saturated, branched or unbranched monocarboxylic acids having from 1 to 16 carbon atoms, such as vinyl propionate, vinyl "Versatate" and in particular for vinyl neodecanoate called Veova 10, vinyl pivalate , vinyl butyrate, vinyl 2-ethylhexylhexanoate, or vinyl laurate; esters of mono- or dicarboxylic unsaturated acids having 3 to 6 carbon atoms with alkanols having 1 to 10 carbon atoms, such as maleates, methyl, ethyl, butyl, ethylhexyl fumarates; vinyl aromatic monomers such as methylstyrenes, vinyltoluenes; vinyl halides such as vinyl chloride, vinylidene chloride, diolefins especially butadiene; (meth) allyl esters of (meth) acrylic acid, esters

(meth) allylics of mono and diesters of maleic, fumaric, crotonic and itaconic acids, as well as alkenic derivatives of amides of acrylic and methacrylic acids, such as N-methallylmaleimide.

15. Composition according to Claim 14, characterized in that at least one other monomer chosen from the following list: acrylamide, is added to the monomers copolymerizable with vinyl acetate and / or acrylic esters and / or styrene. ethylenically unsaturated carboxylic acids or diacids, preferably acrylic acid, methacrylic acid or crotonic acid, ethylenically unsaturated sulfonic acids and salts thereof, preferably vinylsulfonic acid or acid 2-acrylamido-2-methylpropanesulfonic (AMPS), or sodium methallylsulfonate; crosslinking monomers carrying at least two ethylenic unsaturations such as diallylphthalate, diallylmaleate, allylmethacrylate, triallyl cyanurate, divinyladipate or ethylene glycol dimethacrylate; monomers with silane functions such as vinyltrimethoxy silane or vinyltriethoxy silane.

16. Composition according to one of claims 7 to 15, characterized in. that it also comprises a water-repellent agent chosen from fatty acids, salts of fatty acids such as calcium, magnesium or sodium stearate, sodium laurate, esters of fatty acids such as methyl esters of fatty acids in

C10-C16, methyl ester of erucic acid, methyl ester of linoleic acid, ethylhexyl ester of lauric acid, butyl ester of oleic acid, ethylhexyl ester of acid oleic, or the methyl ester of oleic acid.

17. Composition according to claim 16, characterized in that the water-repellent agent is a mixture of methyl esters of C10-C16 fatty acids.

18. Use of the composition according to one of claims 7 to 17 as an adhesion primer on a support based on a thermal insulator and in particular a support based on polystyrene.

19. Composition of mineral binder comprising a mono, di or tri phosphate ester as defined in one of claims 1 to 6.

20. Composition according to claim 19, characterized in that the mineral binder is an air binder chosen from plasters.

21. Composition according to claim 19, characterized in that the mineral binder is a hydraulic binder chosen from cements, in particular of portiand, aluminous or blast furnace type, fly ash, calcined shales or pozzolans.

22. Composition according to one of claims 19 to 21, characterized in that the amount of mono, di or tri phosphate ester is between 0.01 and 50% by dry weight of the mono, di or tri phosphate ester by relative to the total weight of the composition.

23. Composition according to claim 22, characterized in that the amount of mono; di or tri phosphate ester is between 0.05 and 20% by dry weight of _. mono, di or tri phosphate ester relative to the total weight of the composition.

24. Composition according to one of claims 22 and 23, characterized in that the amount of mono, di or tri phosphate ester is between 0.02 and 2% by dry weight of the mono, di or tri phosphate ester by relative to the total weight of the composition.

25. Composition according to one of claims 19 to 24, characterized in that it further comprises a film-forming polymer insoluble in water.

26. Composition according to one of claims 19 to 25, characterized in that it. further comprises a water repellant selected from fatty acids, salts of fatty acids such as calcium, magnesium or sodium stearate, sodium laurate, esters of fatty acids such as methyl esters of fatty acids C10-C16, methyl ester of erucic acid, methyl ester of linoleic acid, ethylhexyl ester of lauric acid, butyl ester of oleic acid, ethylhexyl ester of acid oleic, or the methyl ester of oleic acid.

27. Composition according to claim 26, characterized in that the water-repellent agent is a mixture of methyl esters of fatty acids C10-C16.

28. Process for the preparation of a mineral binder composition according to one of claims 19 to 27, characterized in that the mono, di or tri phosphate ester is premixed with a film-forming polymer composition insoluble in water in the form of an aqueous dispersion (latex) or in the form of a redispersible latex powder.

29. Method for increasing, after consolidation, the properties of adhesion to a surface of a thermal insulator and in particular of polystyrene, in particular in the state wet, of a composition of mineral binders, characterized in that at least one mono, di or tri phosphate ester is added to said composition.

30. Use of the mineral binder composition according to one of claims 19 to 27 to increase the adhesion of a thermal insulator and in particular of polystyrene on a support material.

31. Use according to claim 30, characterized in that the support material is composed of concrete, bricks, aerated concrete, agglomerated concrete (concrete block), fiber cement, masonry or wall plaster.