WO2014111440A2

WO2014111440A2 - Aqueous polyaldehyde and polyphenol adhesive composition

Info

Publication number: WO2014111440A2
Application number: PCT/EP2014/050751
Authority: WO
Inventors: David DOISNEAU; Hélène DECORPS
Original assignee: Compagnie Generale Des Etablissements Michelin; Michelin Recherche Et Technique S.A.
Priority date: 2013-01-16
Filing date: 2014-01-16
Publication date: 2014-07-24
Also published as: FR3000963B1; WO2014111440A3; FR3000963A1

Abstract

The invention relates to an aqueous adhesive composition which comprises an unsaturated elastomer latex and a phenol-aldehyde resin consisting of at least: an aromatic polyaldehyde having at least two aldehyde functions, including at least one aromatic ring; a polyphenol comprising at least one aromatic ring: in the event of a single aromatic ring, the latter has two or three hydroxyl functions in meta position relative to one another or relative to each other. The rest of the ring is non-substituted. In the event of a plurality of aromatic rings, at least two of same each have two or three hydroxyl functions in meta position relative to one another or relative to each other. The two ortho positions of at least one of said hydroxyl functions are non-substituted. The weight ratio of polyphenol to polyaldehyde is no lower than 3.0.

Description

AQUEOUS ADHESIVE COMPOSITION BASED ON POLYALDEHYDE AND POLYPHENOL

The field of the present invention is that of textile materials and adhesive compositions or "glues" for adhering such textile materials to unsaturated rubber matrices such as those commonly used in semi-finished rubber articles or products.

The present invention is more particularly related to textile materials glued by adhesive layers based on a phenol-aldehyde resin, in particular to glued textile materials capable of reinforcing tire structures.

It has long been known to adhere textile materials to diene elastomer compositions through the use of adhesives known under the name "RFL" (for resorcinol-formaldehyde-latex), for example for bonding compositions. rubber on polyester or polyamide textile cords such as those commonly used in tires (see for example US 2,561,215, US 3,817,778). These RFL adhesives comprise, in a well known manner, a thermosetting phenolic resin obtained by the condensation of resorcinol with formaldehyde and one or more diene rubber latex in aqueous solution.

Experience shows that the above RFL adhesives confer excellent adhesion of the textile materials to the crosslinkable rubber compositions. However, these RFL glues are not without drawbacks; they include in particular as a basic substance formaldehyde (or formaldehyde) that it is desirable to reduce or even eventually eliminate adhesive compositions, because of the recent evolution of European regulations on this type of compound. Thus, designers of rubber articles, including tire manufacturers, are now aiming to find new adhesive systems or new textile materials that overcome the aforementioned drawback.

In the course of their research, the Applicants have discovered an aqueous adhesive composition that does not use formaldehyde, which makes it possible to meet the above objective.

Thus, a first object of the invention relates to an aqueous adhesive composition comprising at least firstly A) a phenol-aldehyde resin and secondly B) an unsaturated elastomer latex, in which the phenol-aldehyde resin is based on at least: an aromatic polyaldehyde bearing at least two aldehyde functional groups, comprising at least one aromatic nucleus;

a polyphenol having one or more aromatic ring (s), it being understood that:

in the case of a single aromatic ring, the latter carries two or three hydroxyl functions in the meta position with respect to each other or to each other, the remainder of the aromatic ring being unsubstituted; in the case of several aromatic nuclei, at least two of them are each carrying two or three hydroxyl functions in the meta position relative to one another or to each other, it being understood that the two positions ortho of at least one of these hydroxyl functions are unsubstituted. and wherein the weight ratio of polyphenol to polyaldehyde is greater than or equal to 3.0.

Another object of the invention relates to the use of the aqueous adhesive composition according to the invention to adhere by baking a textile material to a crosslinkable rubber composition, and a textile material of which at least a portion is coated with an adhesive layer, said layer comprising an aqueous adhesive composition according to the invention.

The invention also relates to a method of manufacturing a textile material comprising at least one deposition step on a textile material, an adhesive composition according to the invention.

The invention also relates to the use of the textile material of the invention as reinforcing element for semi-finished articles or products of rubber, particularly pneumatic tires, in particular those intended for equipping tourism-type motor vehicles, SUVs. "Sport Utility Vehicles"), two wheels (including bicycles, motorcycles), aircraft, such as industrial vehicles chosen from light trucks, "heavy vehicles" - that is to say, subway, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering -, other transport or handling vehicles.

The invention also relates to any composite (article or semi-finished product) of rubber, in particular any tire, before or after firing (for crosslinking or final vulcanization), comprising a textile material according to the invention. The invention as well as its advantages will be readily understood in the light of the description and the following exemplary embodiments.

I - FORMULATION OF THE AQUEOUS ADHESIVE COMPOSITION

In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight.

By "diene" elastomer (or indistinctly rubber) is meant an elastomer derived at least in part (that is to say a homopolymer or a copolymer) from monomer (s) diene (s) (ie, carrier (s) two carbon-carbon double bonds, conjugated or not). By "isoprene elastomer" is meant a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), the various copolymers of isoprene, isoprene and mixtures of these elastomers.

On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b).

By the term "composition based on", it is of course understood a composition comprising the mixture and / or the reaction product of the various basic constituents used for this composition, some of them may be intended to react or susceptible to react with each other or with their surrounding chemical environment, at least in part, during the various phases of manufacture of the composition, the textile material, composites or finished articles comprising such composites, in particular during a cooking step .

The aqueous adhesive composition according to the invention therefore comprises at least firstly A) a (at least one) phenol-aldehyde resin and secondly B) an (at least one) unsaturated elastomer latex; this phenol-aldehyde resin is based on at least one (that is to say one or more) aromatic polyaldehyde and at least one (that is to say one or more) polyphenol, constituents which will be described in detail below. Preferably, the weight ratio of polyphenol to polyaldehyde is strictly greater than 3.0.

In one embodiment, preferably applied to a textile material whose textile material is selected from the group consisting of non-thermoplastic polymers and assemblies of thermoplastic polymers and non-thermoplastic polymers, by aramid or an aramid / nylon assembly, the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 30, preferably from 3 to 25 and more preferably from 3 to 20. In another embodiment, embodiment, preferably applied to a textile material whose textile material is selected from the group consisting of thermoplastic polymers, cellulose and assemblages of these materials, for example polyester, nylon or rayon, the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 20, preferably from 3 to 15 and more preferably from 3 to 10.

1.1 - Aromatic polyaldehyde

The first essential component of the phenol-aldehyde resin is an aromatic polyaldehyde bearing at least two aldehyde functional groups, comprising at least one aromatic ring.

According to a preferred embodiment, it is said aromatic nucleus which carries the aldehyde functions, the latter being able to be in the ortho, meta or para position on the aromatic nucleus. Preferably, the aromatic nucleus of polyaldehyde is a benzene nucleus. More preferably, this polyaldehyde is selected from the group consisting of 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5 tricarbaldehyde, and mixtures of these compounds. Even more preferably, the aromatic polyaldehyde used is 1,4-benzenedicarboxaldehyde, also called terephthaldehyde, as a reminder of the chemical formula developed:

(I)

1.2 - Polyphenol

The second essential component of the phenol-aldehyde resin is a polyphenol having one or more aromatic ring (s).

In the case of a polyphenol having a single aromatic ring, the latter carries two or three hydroxyl functions in the meta position with respect to each other (in the case of two functions) or with respect to each other (in the case of three functions), the remainder of the aromatic ring being by definition unsubstituted; by this is meant that the other carbon atoms of the rest of the aromatic ring (those other than the carbon atoms carrying the hydroxyl functions) carry a single hydrogen atom.

As a preferred example of a polyphenol comprising a single aromatic ring, mention may in particular be made of resorcinol, as a reminder of the structural formula:

(Π)

By way of still more preferred example comprising a single aromatic nucleus, mention may be made of phloroglucinol, as a reminder of the structural formula:

(III)

In the case of a polyphenol comprising several (two or more) aromatic rings, at least two of them are each carrying two or three hydroxyl functions in the meta position with respect to each other (in the case of two functions), or with respect to each other (in the case of three functions), it being understood that the two ortho positions of at least one of these hydroxyl functions are unsubstituted; by this is meant that the two carbon atoms located on both sides (in the ortho position) of the hydroxyl carbon atom (i.e., carrying the hydroxyl function) carry a single hydrogen atom.

As preferred examples, in the case where the polyphenol molecule comprises several aromatic nuclei, at least two of these aromatic nuclei, identical or different, are chosen from those of general formulas:

(IV-a) (IV-b) (IV-c) (IV-d) in which the symbols Z _ls Z _2, identical or different if several are present on the same aromatic ring, represent an atom (e.g., carbon, sulfur or oxygen) or a linking group, by definition is at least divalent, linking at least these two aromatic nuclei to the rest of the polyphenol molecule.

According to a particular and preferred embodiment of the invention, the polyphenol is for example a flavonoid, characterized for recall by a basic structure with 15 carbon atoms, formed by two benzene rings connected by three carbon atoms. More particularly, the flavonoid used is 2 ', 4', 3, 5, 7-pentahydroxyflavone, also called "Morin", of formula (V) below:

(V)

It is noted that this compound is a polyphenol having two aromatic rings (of respective formulas IV-c and IV-d above), each of which is indeed carrying two hydroxyl functional groups in the meta position with respect to each other, the two ortho positions of at least one of these two hydroxyl functions being unsubstituted.

According to another particular and preferred embodiment of the invention, the polyphenol is for example phloroglucide, also called 2,4,6,3 ', 5' -biphenylpentol, of the following structural formula:

(VI)

It is noted that this compound is a polyphenol comprising two aromatic rings (of the respective formulas IV-a and IV-b above), each of which is indeed carrying at least two (in this case, a carrier of two, the other carrier of three) hydroxyl functions in position meta with respect to each other, the two ortho positions of at least one of these two hydroxyl functions being unsubstituted.

According to yet another particular and preferred embodiment of the invention, the polyphenol is for example 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide of the following structural formula:

(VII)

In a preferred embodiment, the polyphenol is selected from the group consisting of phloroglucinol (III), 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide (VII) and mixtures of these compounds.

1.3 - Unsaturated elastomer latex

It is recalled that a latex is a stable dispersion of elastomer microparticles (s) suspended in an aqueous solution.

The unsaturated elastomer latexes (that is to say bearing carbon-carbon double bonds), in particular diene elastomer, are well known to those skilled in the art. They constitute in particular the elastomeric base of the RFL glues described in the introduction to this memo.

According to the invention, the unsaturated elastomer of the latex is preferably a diene elastomer, more preferably a diene elastomer chosen from the group consisting of polybutadienes, butadiene copolymers, polyisoprenes, isoprene copolymers and mixtures of these. elastomers. It is even more preferably selected from the group consisting of butadiene copolymers, vinylpyridine-styrene-butadiene terpolymers, natural rubber, and mixtures of these elastomers.

1.4 - Additives - Manufacture of the aqueous adhesive composition

The aqueous adhesive composition according to the invention and / or its phenol-aldehyde resin and / or its starting unsaturated elastomer latex may, of course, comprise all or part of the usual additives for aqueous adhesive compositions such as those used in the conventional RFL glues; examples are bases such as ammonia, sodium hydroxide, potassium hydroxide or ammonium hydroxide, dyes, fillers such as carbon black or silica, antioxidants or other stabilizers. Typically, during a first manufacturing step, the resin itself is prepared by gradually mixing the polyphenol and the aromatic polyaldehyde in a basic solvent such as an aqueous solution of sodium hydroxide, preferably having a pH of between 9 and 13. more preferably between 10 and 12. All the constituents are mixed with stirring for a variable time depending on the temperature used and the specific composition targeted, for example for a period which may vary between 1 min and 6 h, at a temperature between 20 ° C and 90 ° C, preferably between 20 and 60 ° C.

The phenol-aldehyde resin thus pre-condensed is generally diluted in water, before being added to the latex or to the latices (if there are more) of unsaturated elastomer (s) to form the aqueous adhesive composition of the according to a general procedure which is well known to those skilled in the field of RFL adhesives.

For example, the constituents of the adhesive composition are added in the following order: water, any additives soaked in water (eg ammonia), latex (s) (in any order), phenol-aldehyde resin (diluted). The mixture is mixed with stirring for 1 to 30 minutes, for example at 20 ° C.

In a final manufacturing step, the aqueous adhesive composition is generally stored at room temperature (23 ° C) for a maturation time that can typically vary from 1 to several hours or even days, before its final use.

In the final adhesive composition thus prepared, the content of solids content of phenol-aldehyde resin preferably represents between 5 and 60%, more preferably between 10 and 30% by weight of the dry extract of adhesive composition.

The level of unsaturated elastomer (that is to say the solids content of the latex) is in turn preferably between 40 and 95%, more preferably between 70 and 90%, by weight of the extract. dry of the adhesive composition. The weight ratio of the resin solids content to the dry latex extract is preferably between 0.1 and 2.0, more preferably between 0.15 and 1.0.

The water content of the aqueous adhesive composition of the invention is preferably between 60 and 90%, more preferably between 60 and 85%. II - TEXTILE MATERIAL AND COMPOSITE OF THE INVENTION

As indicated above, the present invention also relates to the use of the previously described aqueous adhesive composition for bonding any textile material to an unsaturated rubber composition, for forming a rubber composite reinforced with such material, as well as as such, the textile material of which at least a part is coated with an adhesive composition according to the invention.

IL 1 - Definitions; examples of textile materials

By definition, in the present application, the term "textile" or "textile material", in a manner well known to those skilled in the art, any material other than metal material, whether natural or synthetic, capable of be transformed into yarn, fiber or film by any suitable processing method. For example, without the following examples being limiting, there may be mentioned a polymer spinning process such as, for example, melt spinning, solution spinning or gel spinning.

This textile material may consist of a yarn or fiber, a ribbon or film, or also of a fabric made from yarns or fibers, for example a woven fabric with warp yarns and weft threads, or a crossover fabric with crossed threads.

Preferably, this textile material of the invention is chosen from the group consisting of films, monofilaments (or unitary threads), multifilament fibers, assemblies of such threads or fibers, and mixtures of such materials. It is more particularly a monofilament, a multifilament fiber or a plied yarn.

By "wire" or "fiber" is generally meant any elongated element of great length relative to its cross section, whatever the shape of the latter, for example circular, oblong, rectangular or square, or even flat, this wire that can be rectilinear as non-rectilinear, for example twisted, or corrugated. The largest dimension of its cross section is preferably less than 5 mm, more preferably less than 3 mm.

This wire or this fiber can take any known shape, it can act for example of a single elementary filament of large diameter (for example and preferably equal to or greater than 50 μιη), a multifilament fiber (consisting of a plurality of elementary filaments of small diameter, typically less than 30 μιη), of a twisted or cabled textile formed of several fibers or monofilament textiles twisted or cabled together, or an assembly, a group, a row of threads or fibers such as for example a band or strip comprising several of these monoflaments, fibers, twisted or cabled grouped together, for example aligned in a main direction, rectilinear or not.

By "film" or "tape" is generally meant an elongate member, of great length relative to its cross section, the cross section has a shape ratio (width over thickness) greater than 5, preferably greater than 10 and whose width is preferably at least 3 mm, more preferably at least 5 mm. The aqueous adhesive composition of the invention may be applied to any textile material as described above and capable of reinforcing rubber articles such as tires, including textile materials of organic or polymeric material, such as inorganic material. As examples of inorganic materials, mention will be made of glass and carbon.

The invention is preferably implemented with polymeric materials, thermoplastic type, non-thermoplastic and assemblies of these materials. By way of examples of non-thermoplastic polymeric materials, mention may be made of aromatic polyamides, for example aramid, and cellulose, both natural and artificial, such as cotton, rayon, flax and hemp.

As examples of polymeric materials of the thermoplastic type, mention will preferably be made of aliphatic polyamides and polyesters. Among the aliphatic polyamides, there may be mentioned polyamides 4-6, 6, 6-6 (nylon), 11 or 12. Among the polyesters, there may be mentioned for example PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate).

In a preferred embodiment, the material of the textile material is selected from the group consisting of non-thermoplastic polymers such as aramid and assemblies of thermoplastic polymers and non-thermoplastic polymers, such as an aramid / nylon assembly, and the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 30, preferably from 3 to 25 and more preferably from 3 to 20.

In another preferred embodiment, the material of the textile material is selected from the group consisting of thermoplastic polymers, such as polyester, for example PET or nylon, celluloses, such as rayon, and assemblies thereof. materials, and The weight ratio of polyphenol to polyaldehyde is in a range from 3 to 20, preferably from 3 to 15 and more preferably from 3 to 10.

U.2 - Manufacture of textile material and composite

The textile material of the invention may be prepared according to a sizing process comprising at least one deposition step, on a textile material (initial), of an adhesive composition according to the invention. The step of depositing the adhesive composition on the initial textile material (starting textile material) may be carried out according to any suitable method, in particular by any known coating technique such as, for example, spraying, soaking impregnation, scrolling in a bath or other equivalent technique of thin or ultra-thin glue film deposition, or a combination of one or more of these techniques.

The weight of dry extract of the aqueous adhesive composition deposited on a kilogram of textile material is preferably between 5 and 100 g, more preferably between 30 and 70 g, more preferably between 40 and 60 g. The invention also applies to cases where the starting textile material has been preadherised by an adhesion primer such as those commonly used by those skilled in the art for the pre-sizing of certain textile fibers (polyester fibers, for example). example PET, aramid, aramid / nylon). The thus preadherised fibers then undergo a subsequent and definitive sizing with the aqueous adhesive composition according to the invention.

After the previously described step of depositing the adhesive composition, the bonded material undergoes a first heat treatment to remove any solvent or water, at a temperature preferably between 1 10 ° C and 260 ° C, more preferably between 130 ° C and 250 ° C, for example by crossing a tunnel furnace, typically several meters long, such as those commonly used for the heat treatment after gluing of textile materials by an RFL glue.

The invention also relates to the textile material obtained after drying, that is to say after a thermal treatment to remove water, of the textile material according to the invention, at least a portion of which is coated with an adhesive layer comprising an adhesive composition according to the invention.

Then, the anhydrous material thus obtained undergoes a second heat treatment to complete the crosslinking of the adhesive composition, preferably led to air in a tunnel oven as described above. The treatment temperature is preferably between 150 ° C. and 350 ° C. The treatment times are from a few seconds to a few minutes depending on the case (for example between 10 s and 10 min).

Those skilled in the art will be able to adjust, if necessary, the temperature and duration of the above heat treatment, depending on the particular conditions of implementation of the invention, in particular the exact nature of the textile material manufactured, in particular depending on whether monofilaments, multifilament fibers, twists consisting of several fibers twisted together, or films are treated. In particular, those skilled in the art will benefit from performing scans in temperature and treatment time, so as to seek, by successive approaches, the operating conditions leading to the best adhesion results, for each particular embodiment of the invention. invention.

Thus glued, the textile material of the invention is preferably intended to adhere to an unsaturated rubber composition such as a diene rubber, to form a reinforced rubber composite which constitutes another object of the invention.

This rubber composite may be prepared according to a process comprising at least the following steps: in a first step, combining at least a portion of the textile material according to the invention with an unsaturated rubber composition (crosslinkable), to form a rubber composite reinforced with the textile material;

- Then, in a second step, crosslink by baking, preferably under pressure, the composite thus formed.

The invention therefore applies to any type of rubber composite capable of being obtained by the method described above, comprising at least one matrix of crosslinkable rubber composition, in particular diene rubber, bonded to the textile material via an adhesive interphase to base of the adhesive composition according to the invention.

The diene elastomer of the composite is preferably chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene-styrene copolymers (SBR) and isoprene copolymers. butadiene (BIR), isoprene-styrene copolymers (SIR), butadiene-styrene-isoprene copolymers (SBIR) and mixtures of these elastomers. A preferred embodiment consists in using an "isoprene" elastomer, that is to say a homopolymer or a copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR). , the synthetic polyisoprenes (IR), the various isoprene copolymers and the mixtures of these elastomers. The isoprene elastomer is preferably natural rubber or a synthetic polyisoprene of the cis-1,4 type. II.3 - Application in tires

The textile material of the invention is advantageously usable for the reinforcement of tires of all types of vehicles, in particular passenger vehicles or industrial vehicles such as heavy vehicles.

By way of example, the single appended figure shows very schematically (without respecting a specific scale), a radial section of a tire according to the invention for tourism type vehicle.

This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5. The crown 2 is surmounted by a tread not shown in this schematic figure. A carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9. The carcass reinforcement 7 is in known manner constituted by at least one sheet reinforced by so-called "radial" cables, for example textiles, that is to say that these cables are arranged substantially parallel to each other and extend from a bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located midway between the two beads 4 and passes through the middle of the crown frame 6). This tire 1 of the invention for example has the essential feature that at least one crown reinforcement 6 and / or its carcass reinforcement 7 comprises a textile material according to the invention. According to another example of a possible embodiment of the invention, it is for example the rods 5 which could consist, in whole or in part, of a textile material according to the invention.

Of course, the invention relates to the objects previously described, namely the textile material and the rubber composite such as pneumatic comprising it, both in the raw state (before cooking or vulcanization) and in the cooked state (after cooking ). III - EXAMPLES OF CARRYING OUT THE INVENTION AND COMPARATIVE TESTS

These tests demonstrate that adhesion to a diene elastomer composition, textile cords glued with an aqueous adhesive composition according to the invention, is equivalent or even even improved in some cases, compared with cords glued with a conventional adhesive composition of the invention. RFL type. For this, several aqueous adhesive compositions have been prepared as indicated above, several in accordance with the invention (hereinafter denoted C-1.2 to C-1.5) and one not according to the invention (control composition noted below Cl. l). Their formulations (expressed in percentage by weight) are presented in the attached Table 1. The amounts listed in this table are those of dry constituents, reduced to a total of 100 parts by weight of aqueous adhesive composition (i.e. constituents plus water). The adhesive composition Cl. 1 is a control composition, of the RFL type, commonly used for the adhesion of polyamide cords to a rubber composition. This adhesive composition is based on resorcinol and formalin.

Each aqueous adhesive composition C-1.2 and C-1.3 according to the invention is based on phloroglucinol and 1,4-benzenedicarboxaldehyde.

Each aqueous adhesive composition C-1.4 and C-1.5 according to the invention is based on 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide and 1,4-benzenedicarboxaldehyde. Each adhesive composition C-1.2 to C-1.5 has a weight ratio of polyphenol to polyaldehyde is greater than or equal to 3.0.

These adhesive compositions C-1. 1 to C-1.5 are also based on natural rubber latex (NR), styrene-butadiene copolymer latex (SBR) and vynilpyridine-styrene-butadiene latex (VPSBR).

The quality of the bond between the rubber composition and the textile material is determined by a test in which the force required to extract sections of textile cords from the vulcanized rubber composition is measured. This rubber composition is a conventional composition that can be used for calendering tire carcass reinforcement textile webs, based on natural rubber, carbon black and conventional additives.

More specifically, the vulcanizate is a rubber block consisting of two plates of dimensions 200 mm by 4.5 mm and thickness 3.5 mm, applied one on the other before firing (the thickness of the resulting block is then 7 mm). It is during the manufacture of this block that the textile cords (15 sections in total) are trapped between the two rubber plates in the raw state, at equal distance and leaving to go over on both sides of these plates a cable end of sufficient length for subsequent traction. The block comprising the cords is then placed in a suitable mold and then cooked under pressure. The temperature and the cooking time are adapted to the targeted test conditions and left to the initiative of those skilled in the art; by way of example, in the present case, the block is fired at 160 ° C. for 15 minutes. At the end of the cooking, the test piece thus constituted of the vulcanized block and the sections of cords is placed in the jaws of a traction machine adapted to allow each section to be tested in isolation, at a speed and a temperature. data (for example, in the present case at 100 mm / min and 20 ° C). The adhesion levels are characterized by measuring the so-called pulling force (denoted F _max ) to tear off the reinforcements of the test piece. A value greater than that of the control sample, arbitrarily set at 100, indicates an improved result, i.e., a tearing force greater than that of the control sample. The results of the tests carried out on the specimens are summarized in Table 1.

III.1 - Test 1: Adhesion of Aramide textile cords

In the case of aramid cords (aromatic polyamide), it is known to proceed with their pre-adhesion in a first bath generally based on epoxy in aqueous solution, for example based on polyglycerol polyglycidyl ether. The ingredients are introduced into the water with stirring, for example in the following order: 0.5 weight percent of polyglycerol polyglycidyl ether (for example "Denacol EX-512" from Nagase Chemicals), 0.03 weight percent of surfactant (sodium dioctyl sulfosuccinate sold under the name "AOT 75") and 0.03 percent by weight of sodium hydroxide, 99.44 percent by weight of water.

The aramid cords of these examples consist of three-strand folds 167x3 construction (title of each strand equal to 167 tex) and 360/360 (torsion in t / m); thus pre-adhered, they are then glued with aqueous adhesive compositions according to the invention and a control composition, and then dried in a drying oven at 180 ° C for 30 s. The adhesive composition was then cured by passing the textile cords through a treatment oven at 240 ° C for 30 seconds. Then the assembly was fired to a natural rubber composition, by vulcanization heat treatment, to form composite specimens as described above. It can be seen that the textile cords glued together with the adhesive compositions C-1.2, C-1.4 and C-1.5 according to the invention have a particularly high and unexpected pull-out force F _max for the person skilled in the art, since it is very substantially increased ( between 12% and 15%) compared to the reference tear force measured on the control textile cord glued with the conventional "RFL" glue. As for textile cords glued together with composition C-1.3, they have a pulling force F _max equivalent to that measured on the control textile cord glued with this RFL glue.

III.2 - Test 2: Hybrid Aramid / Nylon Cable Adhesion

In the case of aramid / nylon cords, it is known to pre-adhere them in a manner similar to that used for aramid cords.

The Aramid / Nylon hybrid cords of these examples consist of 330/330/188 three-stranded construction yarns (title of each Aramid strand equal to 330 tex and nylon equal to 188 tex) and 230/230 (T twist). / m); pre-adhered, they are then glued in a manner similar to that used for aramid cords. Then they were joined by firing to a natural rubber composition, as previously for Aramide cords, through a vulcanization heat treatment, to form composite specimens.

It can be seen that the textile cords glued together with the adhesive compositions C-1.2, C-1.4 and C-1.5 according to the invention have a particularly high and unexpected pull-out force F _max for the person skilled in the art, since it is very substantially increased ( between 8% and 17%) compared to the reference tear force measured on the control textile cord glued with conventional "RFL" glue. As for the textile cords glued with the composition C-1.3, they have a tearing force F _max certainly less but significant and sufficient for the skilled person, compared to that measured on the control textile cord glued with this RFL glue. III.3 - Test 3: Adhesion of Rayonne cords

Rayon cords consist of two-stranded twists of 244x2 construction (title of each strand equal to 244 tex) and 385/385 (torsion in t / m); they were glued with each of the aqueous adhesive compositions C-1.1, C-1.2 and C-1.4, and then dried in a drying oven at 180 ° C for 60s. The adhesive composition was then cross-linked by passing the textile cords through a treatment oven at 230 ° C. for 60 seconds. Then the assembly was fired to a natural rubber composition, by vulcanization heat treatment, to form composite specimens as described above. It can be seen that the textile cords glued together with the adhesive compositions C-1.2 and C-1.4 have a pulling force F _{max which is} certainly lower but significant and sufficient for those skilled in the art, compared with that measured on the control textile cord glued with this RFL glue. III.4 - Test 4: Adhesion of nylon cords

Nylon cords (aliphatic polyamide 6,6) consist of two-stranded yarns of construction 140x2 (titer of each strand equal to 140 tex) and 250/250 (twist in t / m); they were glued with each of the aqueous adhesive compositions C-1. 1, C-1.2 and C-1.4, then dried in a drying oven at 180 ° C for 30s. The adhesive composition was then cured by passing the textile cords through a 230 ° C treatment oven for 30 seconds. Then the assembly was fired to a natural rubber composition, by vulcanization heat treatment, to form composite specimens as described above.

It is found that the textile cords glued with the adhesive composition C-1.4 according to the invention have a pulling force F _max high and unexpected to the skilled person, since slightly increased (4%) compared to the strength of reference tear measured on the control textile cord glued with the conventional "RFL" glue. As for the textile cords glued with the composition C-1.2, they have a tearing force F _max certainly less but significant and sufficient for the skilled person, compared to that measured on the control textile cord glued with this RFL glue. In conclusion, the results of these various tests clearly demonstrate that the adhesive compositions according to the invention constitute a very interesting alternative to the use of conventional RFL glues.

Table 1

(1) Formol (from Caldic, diluted at 36%);

(2) 1,4-benzenedicarboxaldehyde (from ABCR, 98% pure);

(3) Resorcinol (Sumitomo company, purity 99.5%);

(4) Phloroglucinol (from Alfa Aesar, 99% pure);

(5) 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide (from Alfa Aesar, 98% purity);

(6) Sodium hydroxide (from Aldrich, diluted to 30%);

(7) Latex NR ("Trang Latex" from the company Bee tex, diluted to 61% by weight);

(8) Latex SBR ("Encord-201" from Jubilant, diluted to 41% by weight);

(9) Vinylpyridine-styrene-butadiene latex ("VP 106S" from Eliokem, diluted to 41%);

(10) Ammonia (from Aldrich, diluted 21%).

Claims

claims

1. An aqueous adhesive composition, comprising at least firstly A) a phenol-aldehyde resin and secondly B) an unsaturated elastomer latex, characterized in that the phenol-aldehyde resin is based on at least :

Al) an aromatic polyaldehyde bearing at least two aldehyde functions, comprising at least one aromatic ring; A2) a polyphenol having one or more aromatic ring (s), it being understood that: o in the case of a single aromatic ring, the latter is carrying two or three hydroxyl functions in the meta position relative to one another to each other or to each other, the remainder of the aromatic ring being unsubstituted; in the case of several aromatic rings, at least two of them are each carrying two or three hydroxyl functions in the meta position relative to one another or to each other, it being understood that both Ortho positions of at least one of these hydroxyl functions are unsubstituted. and wherein the weight ratio of polyphenol to polyaldehyde is greater than or equal to 3.0.

2. Composition according to the preceding claim, wherein the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 30, preferably from 3 to 25 and more preferably from 3 to 20.

3. Composition according to any one of the preceding claims, wherein the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 20, preferably from 3 to 15 and more preferably from 3 to 10.

A composition according to any one of the preceding claims, wherein the aromatic polyaldehyde is selected from the group consisting of 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde , 2-hydroxybenzene-1,3,5-tricarbaldehyde and mixtures of these compounds.

The composition of claim 4 wherein the polyaldehyde is 1,4-benzenedicarboxaldehyde.

A composition according to any one of the preceding claims wherein the polyphenol is selected from the group consisting of phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide and mixtures thereof.

7. Composition according to any one of the preceding claims, in which the unsaturated elastomer of the latex is a diene elastomer, preferably chosen from the group consisting of polybutadienes, butadiene copolymers, polyisoprenes and isoprene copolymers. vinylpyridine-styrene-butadiene terpolymers and mixtures of these elastomers.

8. Textile material at least a portion of which is coated with an adhesive layer comprising an adhesive composition according to any one of the preceding claims.

The textile material of claim 8, wherein the material of the textile material is selected from the group consisting of thermoplastic polymers, non-thermoplastic polymers, and assemblies thereof.

The textile material of claim 8 or 9, wherein:

the material of the textile material is chosen from the group consisting of non-thermoplastic polymers and assemblies of thermoplastic polymers and non-thermoplastic polymers, and

the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 30, preferably from 3 to 25 and more preferably from 3 to 20.

11. Textile material according to claim 8 or 9, wherein:

the material of the textile material is chosen from the group consisting of thermoplastic polymers, celluloses and the assemblies of these materials, and

the weight ratio of polyphenol to polyaldehyde is in a range of values ranging from 3 to 20, preferably from 3 to 15 and more preferably from 3 to 10.

12. A method of manufacturing a textile material, characterized in that it comprises at least one step of depositing on a textile material, an adhesive composition according to any one of claims 1 to 7.

13. Use, for bonding a textile material to an unsaturated rubber, of an adhesive composition according to any one of claims 1 to 7.

14. A textile-reinforced rubber composite according to any one of claims 8 to 11.

Rubber composite according to claim 14, consisting of a tire.