Improvement of a method for adhering one or more strands of a glass resin composite GRP

Abstract

The present invention relates to the sizing of one or more strands of glass-reinforced plastic (GRP), comprising: a) pre-bonding this or these strands by immersing one or more strands of GRP plastic in a first water bath containing a composition based on an epoxy compound and a blocked diisocyanate compound; b) depositing on the GRP plastic strands by immersing the GRP plastic strands in a second bath containing an aqueous adhesive composition based on at least one unsaturated elastomer latex comprising at least one compound A1 containing at least one aldehyde functional group, at least one phenol A21, and at least one elastomer selected from the group consisting of butadiene copolymers, styrene-butadiene copolymers, vinylpyridine-styrene-butadiene terpolymers, natural rubber excluding chlorinated natural rubber, and mixtures of these elastomers, wherein the content of the blocked diisocyanate compound in the aqueous adhesive composition of the second bath is strictly less than 0.50% by mass content, regarding the sizing.

Description

Technical Field

[0001] The field of the present invention is glass-reinforced plastic, abbreviated as GRP, and an adhesive composition intended to adhere such elements to an elastomeric matrix, such as a semi-finished elastomeric article or product, or otherwise to those commonly used in the field of tires or belts, i.e., the field of "adhesives". More particularly, the present invention relates to an improvement in a method for sizing one or more strands of glass-reinforced plastic GRP, an elastomeric composite comprising the sized GRP, and a tire reinforced by such an elastomeric composite.

Background Art

[0002] Conventional methods for sizing glass-reinforced plastics described in application WO2016116457 are known from the prior art, in which the pre-bonding is conventionally carried out in a first bath generally based on epoxy and isocyanate in an aqueous solution, and then the glass-reinforced plastic is sized in a second bath containing a conventional aqueous adhesive composition, such as an adhesive composition known by the name "RFL" (resorcinol-formaldehyde latex) (e.g., described in EP2006341), mixed with an aqueous solution based on blocked diisocyanate, and then mixed in an elastomeric matrix containing a 100% vinyl pyridine latex phase, which is a known practice. The blocked diisocyanate is added to the adhesive composition at a mass content of 9% to improve adhesion. Similarly, a method for adhering the polyester described in Application WO2021117519 is known from the prior art, but the mechanism of adhesion between the adhesive composition and the polyester is different from the mechanism of adhesion between the adhesive composition and the glass-reinforced plastic. In the mechanism of adhesion between the polyester and the adhesive composition, covalent bonds and, similarly, secondary chemical bonds are formed between the polyester and the adhesive system. The polyester is not very polar, and therefore a pre-bonding step is required to enable adhesion. In the mechanism of adhesion between the glass-reinforced plastic and the adhesive composition described in Application WO2008061544, the glass-reinforced plastic is pre-crosslinked, and the surface chemical functional groups are different from those used between the polyester and the adhesive composition, and a pre-bonding treatment is not necessarily required.

[0003] Therefore, currently, designers of elastomeric articles, especially tire manufacturers, are aiming to find a new and simple method of satisfactorily adhering glass-reinforced plastic (GRP) to an elastomeric matrix, such that such an elastomeric matrix does not require the use of an adhesive composition in combination with a product that has an adverse effect on the environment. Furthermore, it is desirable that this adhesive strength is relatively high initially, i.e., after cooling after curing, and that this adhesive strength decreases slightly under wet conditions. In the course of that research, the Applicant has discovered a method that enables the achievement of the above object.

Summary of the Invention

[0004] Accordingly, the present invention is a method for sizing one or more strands of a glass-reinforced plastic, abbreviated as GRP, the method comprising the following steps: a) the following: - an epoxy compound, and - a blocked diisocyanate compound pre-bonding this or these strands by immersing one or more strands of the GRP plastic in a first water bath containing a composition based thereon; b) The following: - At least one compound A1 containing at least one aldehyde functional group, - At least one phenol A21, - At least one unsaturated elastomer latex containing at least one elastomer selected from the group consisting of butadiene copolymers, styrene-butadiene copolymers, vinylpyridine-styrene-butadiene terpolymers, natural rubber excluding chlorinated natural rubber, and mixtures of these elastomers, Depositing on the GRP plastic strand by dipping the GRP plastic strand into a second bath containing an aqueous adhesive composition based on, Characterized by comprising, The content of the blocked diisocyanate compound in the aqueous adhesive composition of the second bath is a mass content of strictly less than 0.50%, Regarding the said method.

[0005] Therefore, the applicant hypothesizes that, on the one hand, the pre-bonding step is an essential step in order to maintain a good level of adhesion first and, on the other hand, to guarantee the resistance of the adhesive interface to wet conditions and / or temperature, but it is not necessary to use blocked diisocyanate in the aqueous adhesive composition and it is desirable to reduce its usage amount. The present invention also relates to an elastomer composite reinforced by one or more sized glass-reinforced plastic (GRP) strands embedded in an elastomer matrix, wherein the sized glass-reinforced plastic (GRP) strands are obtained by the above method.

[0006] The composite according to the present invention thus produced can advantageously be used, inter alia, to reinforce all types of pneumatic or non-pneumatic tires of motor vehicles, in particular passenger vehicles or industrial vehicles such as large vehicles or civil engineering vehicles, aircraft and other transport vehicles or carrier vehicles. The present invention also relates to a tire comprising the above elastomeric composite. The present invention also relates to a belt comprising the above elastomeric composite. The method according to the invention makes it possible, inter alia, to considerably increase the service life of the composite according to the invention, i.e. a tire or a belt comprising it, under wet conditions, and demonstrates the resistance of the produced adhesive interface.

[0007] Any interval of values indicated by the expression "between a and b" represents a range extending from a value greater than a to a value less than b (i.e., excluding the end points a and b), while any interval of values indicated by the expression "a - b" means a range of values from a to b (i.e., strictly including the end points a and b). Within the scope of the present invention, the carbon products specified in this description can be of fossil or biomass origin. In the latter case, the carbon products can be partially or entirely derivable from biomass or obtained from renewable raw materials derived from biomass. In this description, unless otherwise explicitly specified, all the percentages (%) shown are by mass. The term "elastomeric composition" means a composition comprising at least one elastomer (or equivalently, rubber) and at least one other constituent material. A "diene" elastomer (or equivalently, rubber) is understood as an elastomer (i.e., a homopolymer or copolymer) that is at least partially derived from a diene monomer (i.e., a monomer having two conjugated or non-conjugated carbon-carbon double bonds). An "isoprene elastomer" is understood as a diene elastomer selected from the group consisting of isoprene homopolymers or copolymers, that is to say, natural rubber (NR), synthetic isoprene (IR), various isoprene copolymers, and mixtures of these elastomers.

[0008] The term "elastomeric matrix" means a matrix exhibiting elastomeric behavior. The term "meta to each other" means that the hydroxyl functional groups are carried by the carbon atoms of the aromatic ring that are separated from each other by a single other carbon of the aromatic ring. The term "at the ortho position to the functional group" means the position occupied by a carbon atom of the aromatic ring that is directly adjacent to the carbon atom of the aromatic ring having the functional group. The term "member" of a ring means the constituent atoms of the main chain of the ring. That is, for example, a benzene ring consists of 6 members, each member being a carbon atom. In another example, a furan ring consists of 5 members, 4 of which are each a carbon atom and the remaining member is an oxygen atom.

[0009] "CHO" represents an aldehyde functional group. "CH 2 OH" represents a hydroxymethyl functional group. The term "aromatic polyphenol" means an aromatic compound containing at least one benzene ring having more than one hydroxyl functional group. The term "resin based on" is to be understood to mean that the resin contains a mixture of the various basic constituent substances used in this resin as defined above and / or the products of their reactions, and that this resin is based solely on the constituent substances of the resin. Thus, the basic constituent substances are the reactants that are intended to react together during the final condensation of the resin, and not the reagents that are intended to react together to form these basic constituent substances. Thus, according to the present invention, the basic constituent substances of the aqueous adhesive composition include at least one compound A1 and at least one phenol A21. In one embodiment, the basic constituent substances can include other additional constituent substances different from compound A1 and phenol A21. In another embodiment, the basic constituent substances consist of at least one compound A1 and at least one phenol A21.

[0010] Preferably, in embodiments where the basic constituent substance contains other additional constituent substances, these other additional constituent substances do not contain formaldehyde and / or do not contain a methylene donor selected from the group consisting of hexamethylenetetramine (HMT), hexamethoxymethylmelamine (H3M), hexaethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, a polymer of trioxane of hexamethoxymethylmelamine, hexakis(methoxymethyl)melamine, N,N’,N”-trimethyl-N,N’,N”-trimethylolmelamine, hexamethylolmelamine, N-methylolmelamine, N,N’-dimethylolmelamine, N,N’,N”-tris(methoxymethyl)melamine, and N,N’,N”-tributyl-N,N’,N”-trimethylolmelamine. More advantageously, these other additional constituent substances do not contain formaldehyde and do not contain a methylene donor described in this paragraph. More preferably, in embodiments where the basic constituent substance contains other additional constituent substances, these other additional constituent substances do not contain formaldehyde and / or do not contain a methylene donor selected from the group consisting of hexamethylenetetramine, hexaethoxymethylmelamine, hexamethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, hexamethoxymethylmelamine of trioxane, and the general formula: [Chemical formula] (wherein Q represents an alkyl group containing 1 to 8 carbon atoms, and F 1 , F 2 , F3, F 4 and F 5 are independently selected from each other from the group consisting of a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms, a -CH 2 OQ group, and a condensation product thereof) and do not contain a methylene donor selected from the group consisting of N-substituted oxymethylmelamines corresponding to. More advantageously, these other additional constituent substances do not contain formaldehyde and do not contain a methylene donor described in this paragraph.

[0011] Even more preferably, in embodiments where the basic constituent material contains other additional constituent materials, these other additional constituent materials do not contain formaldehyde and / or do not contain a methylene donor. More advantageously, these other additional constituent materials do not contain formaldehyde and do not contain a methylene donor. The term "not containing formaldehyde or not containing a methylene donor" means that the total mass content ratio of formaldehyde or the methylene donor belonging to the above group to the total mass of compound A1 in the basic constituent material is 10% or less, preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less.

[0012] The term "not containing formaldehyde or not containing a methylene donor" means that the total mass content ratio of formaldehyde and the methylene donor belonging to the above group to the total mass of compound A1 in the basic constituent material is 10% or less, preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. The term "strand of glass-reinforced plastic GRP" means a monofilament-based composite reinforcing material of the GRP type containing continuous unidirectional multifilament glass fibers embedded in a thermosetting resin, which can be used in particular as a reinforcing element for tires. The method according to the invention A) Pre-bonding step The pre-bonding of the GRP strand is carried out in a first bath based on epoxy and blocked diisocyanate in an aqueous solution. Advantageously, the epoxy compound is selected from the group consisting of diethylene glycol diglycidyl ether, polyethylene diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 - hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether or isosorbide diglycidyl ether, and preferably is polyglycerol polyglycidyl ether.

[0013] Advantageously, the blocked diisocyanate compound is selected from the group consisting of diphenylmethane diisocyanate or polyphenylene polymethylene polyisocyanate, and preferably N,N'-(methylenedi - p - phenylene)bis[hexahydro - 2 - oxo - 1H - azepine - 1 - carboxamide 4,4'-diisocyanate. Advantageously, after this pre - bonding step, a step of drying the GRP plastic at a temperature of 120°C or higher for at least 5 seconds is followed by a heat treatment at a temperature of 180°C or higher for at least 5 seconds. B) Step of depositing the aqueous adhesive composition Next, the aqueous adhesive composition is deposited on the pre - bonded GRP strands.

[0014] Thus, according to the present invention, the basic constituent substances of the resin include at least one compound A1 and at least one phenol A2. In one embodiment, the basic constituent substances can include other additional constituent substances different from compound A1 and phenol A2. In another embodiment, the basic constituent substances consist of at least one compound A1 and at least one phenol A2.

[0015] According to the present invention, an aqueous adhesive composition is prepared, and as a result, the blocked diisocyanate has a mass content of exactly 0.50% or less in the aqueous adhesive composition. Preferably, the blocked diisocyanate compound in the aqueous adhesive composition of the second bath is strictly less than 0.40%, preferably 0.30% or less, more preferably 0.20% or less, even more preferably 0.10% or less, and still even more preferably 0.05% or less by mass content. More preferably, the aqueous adhesive composition of the second bath does not contain a blocked diisocyanate.

[0016] Compound A1 Another essential constituent of the adhesive composition is Compound A1, which contains at least one aldehyde functional group. According to the present invention, the resin is based on at least one (i.e., one or more) Compound A1. In the first embodiment, Compound A1 is formaldehyde. In the second embodiment, Compound A1 contains at least one aromatic ring having at least one aldehyde functional group. More preferably, Compound A1 has at least two aldehyde functional groups.

[0017] Still more preferably, the aromatic ring of Compound A1 has two aldehyde functional groups. In one embodiment, the aromatic ring of Compound A1 is selected from the group consisting of a benzene ring and a furan ring, and preferably, the aromatic ring of the aromatic aldehyde is a benzene ring. Preferably, Compound A1 is selected from the group consisting of 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarboxaldehyde, and mixtures of these compounds. In a variant of the second embodiment, Compound A1 has the general formula (A):

Chemical formula

[0018] Preferably, compound A1 has the general formula (A’): [Chemical formula] (wherein X represents O) and is as follows.

[0019] More preferably, R represents -CHO. According to a preferred embodiment, X represents O. In a variant of compound A1 of general formula (A), X represents O and R represents -H. Next, the compound A1 used has the formula (Ba): [Chemical formula] and is as follows.

[0020] In a variant of the aldehyde of general formula (A’), X represents O and R represents -H. Next, the compound A1 used is furfuraldehyde and has the formula (B’a): [Chemical formula] and is as follows.

[0021] In another variant of compound A1 of general formula (A), X represents O and R represents -CHO. Next, the compound A1 used has the formula (Bb): [Chemical formula] and is as follows. In another variant of compound A1 of general formula (A’), X represents O and R represents -CHO. Next, the compound A1 used is 2,5-furandicarboxaldehyde and has the formula (B’b): [Chemical formula] and is as follows.

[0022] In another embodiment, X contains N. Preferably, compound A1 is selected from the group consisting of furfural, 2,5-furandicarboxaldehyde, and mixtures of these compounds. In one variant form of compound A1 of general formula (A), X represents NH. The compound A12 used is of formula (Ca):

Chemical formula

Chemical formula

[0023] In another variant form of compound A1 of general formula (A), X represents NT 1 and T 1 represents an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group, or a cycloalkyl group. The compound A12 used is of formula (Cb):

Chemical formula

Chemical formula

[0024] In one variant form of compound A1 of general formula (A’), X represents S. The compound A12 used is of formula (D’a):

Chemical formula

[0025] Preferably, in the variant form of compound A1 of formula (IV’a), R represents -CHO, and next, it is 2,5-thiophenedicarboxaldehyde. In another variant form of compound A1 of general formula (A), X is ST 2 represents, and T 2 represents an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group or a cycloalkyl group. The compound A12 used is of formula (Db):

Chemical formula

[0026] In yet another variant form of compound A1 of general formula (A), X is T 3 -S-T 2 represents, and T 2 and T 3 each independently represent an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group or a cycloalkyl group. The compound A1 used is of formula (Dc):

Chemical formula

[0027] In yet another variant form of compound A1 of general formula (A), X represents S=O. The compound A12 used is of formula (Dd):

Chemical formula

Chemical formula

[0028] Among the various embodiments described above, embodiments and variants in which X represents NH, S or O are preferred. In these embodiments and variants, R can represent -H or -CHO, and preferably, R can represent -CHO. In these embodiments and variants, R is preferentially present at the 5-position and the -CHO group is preferentially present at the 2-position of the aromatic ring (general formula (A’)). Phenol A21 According to the present invention, the resin is based on at least one (i.e., one or more) kind of phenol A21. Advantageously, phenol A21 is as follows: - An aromatic polyphenol A2 containing at least one aromatic ring having at least two hydroxyl functional groups in the meta position to each other, wherein two ortho positions to at least one of the hydroxyl functional groups are unsubstituted, said aromatic polyphenol A2, - An aromatic monophenol A2’ containing at least one 6-membered aromatic ring having a single hydroxyl functional group, · Two ortho positions to the hydroxyl functional group are unsubstituted, or · At least one of the ortho and para positions to the hydroxyl functional group is unsubstituted, said aromatic monophenol A2’, - A mixture of A2 and A2’ selected from.

[0029] In one embodiment, the phenol is an aromatic polyphenol A2 containing one or more aromatic rings. The aromatic polyphenol contains at least one aromatic ring having at least two hydroxyl functional groups in the meta position to each other, and two ortho positions to at least one of the hydroxyl functional groups are unsubstituted. In another embodiment, the phenol is an aromatic monophenol A2' containing at least one 6-membered aromatic ring having a single hydroxyl functional group. Regarding this aromatic monophenol, two ortho positions with respect to the hydroxyl functional group are unsubstituted, or if not, at least one of the ortho position with respect to the hydroxyl functional group and the para position with respect to the hydroxyl functional group is unsubstituted. In yet another embodiment, the phenol is a mixture of the above aromatic polyphenol A2 and aromatic monophenol A2'.

[0030] According to the present invention, in one embodiment, the aromatic polyphenol A2 can be a single aromatic polyphenol molecule containing one or more aromatic rings, and at least one of these aromatic rings, actually even each aromatic ring, has at least two hydroxyl functional groups at the meta position to each other, and two ortho positions with respect to at least one of the hydroxyl functional groups are unsubstituted. Similarly, the aromatic monophenol A2' can be, in one embodiment, a single aromatic monophenol molecule containing one or more 6-membered aromatic rings, and at least one of these 6-membered aromatic rings, or even each 6-membered aromatic ring, has a single hydroxyl functional group, and two ortho positions with respect to the hydroxyl functional group are unsubstituted, or if not, at least one of the ortho position with respect to the hydroxyl functional group and the para position with respect to the hydroxyl functional group is unsubstituted. Such a single molecule does not contain repeating units.

[0031] According to the present invention, in another embodiment, the aromatic polyphenol A2 is as follows: - At least one aromatic polyphenol containing at least one aromatic ring having at least two hydroxyl functional groups at the meta position to each other, wherein two ortho positions with respect to at least one of the hydroxyl functional groups are unsubstituted, at least one aromatic polyphenol, and - At least one compound containing at least one aldehyde functional group and / or at least one compound containing at least two hydroxymethyl functional groups, which are possessed by the aromatic ring can be a precondensed resin based thereon.

[0032] Such a precondensed resin based on aromatic polyphenols is according to the present invention and, unlike the above single molecule, contains repeating units. Where appropriate, the repeating units contain at least one aromatic ring having at least two hydroxyl functional groups in the meta position to each other. Similarly, and according to the present invention, the aromatic monophenol A2’ is, in another embodiment, as follows: - At least one aromatic monophenol containing at least one 6-membered aromatic ring having a single hydroxyl functional group, - Two ortho positions to the hydroxyl functional group are unsubstituted, or - At least one of the ortho position to the hydroxyl functional group and the para position to the hydroxyl functional group is unsubstituted, said at least one aromatic monophenol, - It may be a precondensed resin based on at least one compound containing at least one aldehyde functional group and / or at least one compound containing at least two hydroxymethyl functional groups, which are possessed by the aromatic ring.

[0033] Such a precondensed resin based on aromatic monophenols is according to the present invention and, unlike the above single molecule, contains repeating units. Where appropriate, the repeating units contain at least one 6-membered aromatic ring having a single hydroxyl functional group. In another embodiment, phenol A21 is a mixture of an aromatic polyphenol forming a single molecule and a precondensed resin based on aromatic polyphenols. In yet another embodiment, phenol A21 is a mixture of an aromatic monophenol forming a single molecule and a precondensed resin based on aromatic monophenols. In the following specific embodiments, the aromatic rings of aromatic polyphenols and / or aromatic monophenols are described. For clarity, "aromatic polyphenols" and / or "aromatic monophenols" are described herein in their single molecular form. This aromatic polyphenol and / or this aromatic monophenol can subsequently be condensed, and some define repeating units. The characteristics of the pre-condensed resin are described in more detail later.

[0034] Aromatic polyphenol A2 In a preferred embodiment, the aromatic ring of the aromatic polyphenol has three hydroxyl functional groups in the meta position to each other. Preferably, two ortho positions to each hydroxyl functional group are unsubstituted. It is understood that this means that two carbon atoms located on both sides (ortho positions to the hydroxylated carbon atom) of the hydroxylated carbon atom (i.e., the carbon atom having a hydroxyl functional group) have a single hydrogen atom.

[0035] More preferably still, the remainder of the aromatic ring of the aromatic polyphenol is unsubstituted. It is understood that this means that the other carbon atoms of the remainder of the aromatic ring (other than the carbon atom having a hydroxyl functional group) have a single hydrogen atom. In one embodiment, the aromatic polyphenol contains several aromatic rings, at least two of which each have at least two hydroxyl functional groups in the meta position to each other, and two ortho positions to at least one of the hydroxyl functional groups of at least one aromatic ring are unsubstituted. In a preferred embodiment, at least one of the aromatic rings of the aromatic polyphenol has three hydroxyl functional groups in the meta position to each other. Preferably, two ortho positions to each hydroxyl functional group of at least one aromatic ring are unsubstituted.

[0036] More preferably still, two ortho positions to each hydroxyl functional group of each aromatic ring are unsubstituted. Advantageously, the aromatic ring of the aromatic polyphenol or each of them is a benzene ring. As examples of aromatic polyphenols containing exactly one aromatic ring, resorcinol and phloroglucinol can be specifically mentioned, each reminding of structural formulas (IV) and (V):

Chem.

[0037] As an example, when the aromatic polyphenol contains several aromatic rings, at least two of these aromatic rings are identical or different and have the general formula:

Chem.

Chem.

Chem.

[0038] In the case of an aromatic polyphenol containing at least one aromatic ring according to formula VI-b, it is noted that two ortho positions with respect to each hydroxyl functional group of at least one aromatic ring are unsubstituted. In the case of an aromatic polyphenol containing several aromatic rings according to formula VI-b, two ortho positions with respect to each hydroxyl functional group of each aromatic ring are unsubstituted.

[0039] According to one embodiment of the present invention, the aromatic polyphenol is selected from the group consisting of resorcinol, phloroglucinol, 2,2',4,4'-tetrahydroxydiphenyl sulfide, 2,2',4,4'-tetrahydroxybenzophenone and mixtures of these compounds. In a particularly advantageous embodiment, the aromatic polyphenol is phloroglucinol. In one embodiment, the aromatic polyphenol A2 comprises a precondensed resin based on the aromatic polyphenol described in any one of these embodiments. This precondensed resin preferably comprises the following: · At least one aromatic polyphenol, preferably selected from the group consisting of resorcinol, phloroglucinol, 2,2',4,4'-tetrahydroxydiphenyl sulfide, 2,2',4,4'-tetrahydroxybenzophenone and mixtures thereof, as defined above, and · At least one compound capable of reacting with an aromatic polyphenol containing at least one aldehyde functional group and / or at least one compound capable of reacting with an aromatic polyphenol containing at least two hydroxymethyl functional groups, and preferably, an aromatic aldehyde containing at least one aromatic ring having at least one aldehyde functional group, based on.

[0040] The compounds capable of reacting with the aromatic polyphenol containing compound A1 may be the aromatic compounds defined above, or any other aldehyde. Advantageously, the compound is an aromatic compound containing an aromatic ring having at least two functional groups (one of these functional groups is a hydroxymethyl functional group, and the other is an aldehyde functional group or a hydroxymethyl functional group), formaldehyde, furfuraldehyde, 2,5-furandicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,2-benzenedicarboxaldehyde, and mixtures of these compounds, selected from the group consisting of. Very advantageously, when the compound capable of reacting with the aromatic polyphenol is an aromatic compound containing an aromatic ring having at least two functional groups, one of these functional groups is a hydroxymethyl functional group, and the other is an aldehyde functional group or a hydroxymethyl functional group, this compound is selected from the group consisting of 5-(hydroxymethyl)furfural, 2,5-di(hydroxymethyl)furan, and mixtures of these compounds.

[0041] Therefore, in the precondensed resin based on aromatic polyphenol, the repeating unit corresponds to the characteristics of the aromatic polyphenol defined above, except that at least one of the unsubstituted carbon atoms of the aromatic ring is bonded to another unit. Regardless of the compound other than the aromatic polyphenol which is the base of the precondensed resin, this precondensed resin has no free formaldehyde. This is because even when the precondensed resin is based on the above aromatic polyphenol and formaldehyde, the formaldehyde has already reacted with the aromatic polyphenol, so the precondensed resin has no free formaldehyde which tends to react with compound A1 according to the present invention in subsequent steps. The aromatic polyphenol A2 can also contain a mixture of free aromatic polyphenol molecules and the precondensed resin based on the above aromatic polyphenol. In particular, the aromatic polyphenol A2 can also contain a mixture of phloroglucinol and the precondensed resin based on phloroglucinol.

[0042] Aromatic monophenol A2’ Aromatic monophenol A2’ can conform to two deformed forms. In one deformed form, the two ortho positions with respect to the hydroxyl functional group are unsubstituted. In another deformed form, at least one of the ortho position with respect to the hydroxyl functional group and the para position with respect to the hydroxyl functional group is unsubstituted. Advantageously, in the deformed form in which at least one of the ortho position with respect to the hydroxyl functional group and the para position with respect to the hydroxyl functional group is unsubstituted, one of the ortho positions is unsubstituted and the para position with respect to the hydroxyl functional group is unsubstituted. Preferably, regardless of the deformed form, the two ortho positions with respect to the hydroxyl functional group are unsubstituted. It is understood that this means that the two carbon atoms located on both sides (ortho positions with respect to the hydroxylated carbon atom) of the hydroxylated carbon atom (i.e., the carbon atom having the hydroxyl functional group) have a single hydrogen atom.

[0043] More preferably still, the remainder of the aromatic ring is unsubstituted. It is understood that this means that the other carbon atoms of the remainder of the aromatic ring (other than the carbon atom having the hydroxyl functional group) have a single hydrogen atom. In one embodiment, the aromatic monophenol contains several six-membered aromatic rings, at least two of which each have a single hydroxyl functional group, and with respect to at least one of the hydroxyl functional groups, the two ortho positions with respect to the hydroxyl functional group are unsubstituted, or at least one of the ortho position with respect to the hydroxyl functional group and the para position with respect to the hydroxyl functional group is unsubstituted. Preferably, the two ortho positions with respect to each hydroxyl functional group of at least one six-membered aromatic ring are unsubstituted.

[0044] More preferably still, the two ortho positions with respect to each hydroxyl functional group of each six-membered aromatic ring are unsubstituted. More preferably, still, each remainder of the aromatic ring is unsubstituted. It is understood that this means that the other carbon atoms of each remainder of the aromatic ring (other than those having a hydroxyl functional group or those having a group linking the aromatic rings together) have a single hydrogen atom. Advantageously, the aromatic ring of the aromatic monophenol or each thereof is a benzene ring. Preferably, the aromatic monophenol is selected from the group consisting of phenol, ortho-cresol, meta-cresol, para-cresol, ortho-chlorophenol, meta-chlorophenol, para-chlorophenol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-vinylphenol, 4-ethylphenol, 4-isopropylphenol, 4-isobutylphenol, para-coumaric acid, and mixtures of these compounds.

[0045] In one embodiment, the aromatic monophenol A2' comprises a precondensed resin based on the aromatic monophenol described in any one of these embodiments. This precondensed resin preferably is as follows: · At least one aromatic monophenol, preferentially selected from the group consisting of phenol, ortho-cresol, meta-cresol, para-cresol, ortho-chlorophenol, meta-chlorophenol, para-chlorophenol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-vinylphenol, 4-ethylphenol, 4-isopropylphenol, 4-isobutylphenol, para-coumaric acid, and mixtures of these compounds, as defined above, and · At least one compound capable of reacting with an aromatic monophenol containing at least one aldehyde functional group and / or at least one compound capable of reacting with an aromatic monophenol containing at least two hydroxymethyl functional groups, and preferably, an aromatic aldehyde containing at least one aromatic ring having at least one aldehyde functional group is based on.

[0046] The compound capable of reacting with an aromatic monophenol may be the previously defined compound A1 or any other aldehyde. Advantageously, the compound capable of reacting with an aromatic polyphenol is an aromatic compound containing an aromatic ring having at least two functional groups, one of these functional groups being a hydroxymethyl functional group and the other being an aldehyde functional group or a hydroxymethyl functional group, formaldehyde, furfuraldehyde, 2,5-furandicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,2-benzenedicarboxaldehyde, and mixtures of these compounds. Very advantageously, when the compound is an aromatic compound containing an aromatic ring having at least two functional groups, one of these functional groups being a hydroxymethyl functional group and the other being an aldehyde functional group or a hydroxymethyl functional group, this compound is selected from the group consisting of 5-(hydroxymethyl)furfural, 2,5-di(hydroxymethyl)furan, and mixtures of these compounds.

[0047] Thus, in the precondensed resin based on an aromatic monophenol, the repeating unit corresponds to the characteristics of the aromatic monophenol defined above, except that at least one of the carbon atoms of the unsubstituted 6-membered aromatic ring is bonded to another unit. Regardless of what the compound other than the aromatic monophenol, which is the base of the precondensed resin, is, this precondensed resin is free of free formaldehyde. This is because, even when the precondensed resin is based on the previously described aromatic monophenol and formaldehyde, the formaldehyde has already reacted with the aromatic monophenol, so the precondensed resin has no free formaldehyde that tends to react with compound A1 according to the present invention in subsequent steps.

[0048] Aromatic monophenol A2’ can also include a mixture of free aromatic monophenol molecules and precondensed resins based on the aforementioned aromatic monophenols. In particular, aromatic monophenol A2’ can also include a mixture of phenol and precondensed resins based on phenol. Mixture of aromatic polyphenol A2 and aromatic monophenol A2’ Phenol A21 can also include a mixture of aromatic polyphenol A2 and the aforementioned aromatic monophenol A2’. Preferably, phenol A21 includes a mixture of an aromatic polyphenol and a precondensed resin based on the aromatic polyphenol. Elastomer latex The adhesive composition also includes an elastomer latex, preferably an unsaturated elastomer latex. When the adhesive composition is used for a coating element intended to be embedded in an elastomer matrix, such an elastomer latex can provide a physical interface of the elastomer. When the elastomer latex is unsaturated, the elastomer latex also provides a chemical interface by an unsaturated portion capable of forming a crosslink with the crosslinking system of the elastomer matrix.

[0049] It is recalled that latex is a suspension, generally a stable dispersion consisting of microparticles of an elastomer in an aqueous solution. That is, an elastomer latex is a liquid composition containing a liquid solvent, generally water, and at least one elastomer or rubber dispersed in the liquid solvent, thus forming a suspension. Therefore, latex is not a rubber composition containing an elastomer or rubber matrix in which at least one other component is dispersed. The rubber composition is in a plastic state in an uncured (non-crosslinked) state and an elastic state in a cured (crosslinked) state, but unlike latex, it is never in a liquid state.

[0050] Unsaturated (i.e., having carbon-carbon double bonds) elastomer latices, and in particular, diene elastomer latices, are well known to those skilled in the art. They are particularly used to form the elastomeric substrates of the RFL adhesives described in the introduction section of this specification. The unsaturated elastomers of the latex are preferably diene elastomers, more preferably diene elastomers selected from the group consisting of butadiene copolymers, styrene-butadiene copolymers, vinylpyridine-styrene-butadiene terpolymers, natural rubber excluding chlorinated natural rubber, and mixtures of these elastomers. Advantageously, after this step of depositing the aqueous adhesive composition, the GRP plastic is dried at a temperature of 120 °C or higher for at least 5 seconds, and then heat treatment at a temperature of 180 °C or higher continues for at least 5 seconds.

[0051] The composite according to the invention The present invention also relates to an elastomeric composite reinforced by one or more sized glass-reinforced plastic (GRP) strands as already defined. The elastomeric matrix is based on an elastomeric composition containing at least one elastomer and another constituent material. Preferably, the elastomeric composition contains a diene elastomer. A "diene" type elastomer or rubber (the two terms are synonymous) generally means an elastomer that is at least partially derived from a diene monomer (a monomer having two conjugated or non-conjugated carbon-carbon double bonds), i.e., a homopolymer or copolymer. The elastomeric composition can contain exactly one diene elastomer, or a mixture of several diene elastomers, and the diene elastomers can be used in combination with any type of synthetic elastomer other than diene elastomers, and in fact, even polymers other than elastomers, such as thermoplastic polymers. In a first embodiment that is preferentially intended for use in a tire, the elastomer composition comprises a diene elastomer selected from the group consisting of polybutadiene (BR), natural rubber (NR), synthetic polyisoprene (IR), various butadiene copolymers, various isoprene copolymers, and mixtures of these elastomers.

[0052] Such copolymers are more preferentially selected from the group consisting of butadiene / styrene copolymers (SBR) (regardless of whether it is prepared by emulsion polymerization (ESBR) or solution polymerization (SSBR)), isoprene / butadiene copolymers (BIR), isoprene / styrene copolymers (SIR), and isoprene / butadiene / styrene copolymers (SBIR). In a second embodiment that is preferentially intended for use in a belt, the elastomer composition comprises an elastomer selected from the group consisting of α-olefin ethylene-type elastomers, polychloroprene elastomers, and mixtures of these elastomers, one or more other elastomers. The elastomer composition may also include one or more other constituents. Advantageously, the ethylene / α-olefin-type elastomer is selected from the group consisting of ethylene / propylene copolymers (EPM), ethylene / propylene / diene copolymers (EPDM), and mixtures of these copolymers. Preferably, the elastomer composition comprises a reinforcing filler. When a reinforcing filler is used, any type of reinforcing filler known for its ability to reinforce the elastomer composition that can be used in the manufacture of a tire, for example, organic fillers such as carbon black, reinforcing inorganic fillers such as silica, or otherwise a blend of these two types of fillers, in particular, a blend of carbon black and silica may be used.

[0053] Conventionally, all carbon blacks used in tires ("tire-grade" blacks) are suitable as carbon blacks. More specifically, for example, reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades) can be mentioned. When using carbon black with isoprene elastomers, the carbon black may already be incorporated into the isoprene elastomer, for example, in the form of a masterbatch (see, for example, applications WO97 / 36724 and WO99 / 16600). As an example of organic fillers other than carbon black, mention can be made of the functionalized polyvinyl aromatic organic fillers described in applications WO-A-2006 / 069792 and WO-A-2006 / 069793. In the present application, the term "reinforcing inorganic filler" is, by definition, in contrast to carbon black, also known as "white filler", "transparent filler" or actually "non-black filler", and without using intermediate coupling agents, means other than those of the elastomer composition, it is possible to reinforce by itself alone, in other words, in its reinforcing role, it should be understood to mean any inorganic or mineral filler (regardless of its color and its origin (natural or synthetic)) that can replace conventional tire-grade carbon black. Such fillers are generally characterized by the presence of hydroxyl (-OH) groups on their surface by known methods.

[0054] The physical state in which the reinforcing inorganic filler is provided is not important whether it is in the form of powder, microparticles, granules, beads, or any other suitable densified form. Of course, "reinforcing inorganic filler" is also understood to mean mixtures of different reinforcing inorganic fillers, such as those described hereinafter, in particular, highly dispersible silica and / or aluminum fillers. Silica type, especially silica (SiO 2 ) or aluminum type, especially alumina (Al 2 O 3) The mineral filler is particularly suitable as a reinforcing inorganic filler. The silica used can be any reinforcing silica known to those skilled in the art, in particular, both having a BET specific surface area and a CTAB specific surface area of less than 450 m 2 / g, preferably 30 - 400 m 2 / g, and can be any precipitated silica or fumed silica. As highly dispersible precipitated silica (HDS), for example, Ultrasil 7000 and Ultrasil 7005 silica from Evonik, Zeosil 1165MP, 1135MP and 1115MP silica from Rhodia, Hi-Sil EZ150G silica from PPG, Zeopol 8715, 8745 and 8755 silica from Huber, or silica with a high specific surface area described in application WO03 / 16837 can be mentioned.

[0055] Finally, those skilled in the art will understand that as a filler equivalent to the reinforcing inorganic filler described in this section, a reinforcing filler of another nature, particularly of organic nature, may be used, provided that this reinforcing filler is coated with an inorganic layer such as silica, or, if not, contains functional sites on its surface, in particular hydroxyl sites that require the use of a coupling agent to establish a bond between the filler and the elastomer. Preferably, the content of the total reinforcing filler (carbon black and / or reinforcing inorganic filler such as silica) is in the range of 5 - 120 phr, more preferably 5 - 100 phr, and even more preferably 5 - 90 phr.

[0056] Carbon black can advantageously constitute the only reinforcing filler or the main reinforcing filler. Of course, it is possible to use just one type of carbon black or a blend of several carbon blacks of different ASTM grades. Carbon black can also be used as a blend with other reinforcing fillers, particularly the above-mentioned reinforcing inorganic fillers, especially silica. When using an inorganic filler (e.g., silica) in a rubber composition, the content of the inorganic filler, either alone or as a blend with carbon black, is in the range of 0 to 70 phr, preferably 0 to 50 phr, particularly still 5 to 70 phr, and even more preferably, this ratio varies from 5 to 50 phr, particularly 5 to 40 phr. Preferably, the elastomer composition contains various additives. The rubber composition can also contain, for example, a plasticizer or extender oil (regardless of whether these properties are aromatic or non-aromatic), a pigment, a protective agent (such as an anti-ozone degradation wax, a chemical anti-ozone degradation agent or an antioxidant), an anti-fatigue agent or otherwise a tackifier, or all or part of the usual additives commonly used in elastomer compositions for tire manufacturing.

[0057] Preferably, the elastomer composition contains a crosslinking system, more preferably a vulcanization system. In a first embodiment preferably intended for use in a tire, the elastomer composition contains a vulcanization system. The vulcanization system contains a sulfur donor, such as sulfur. Preferably, the vulcanization system contains vulcanization activators such as zinc oxide and stearic acid. Preferably, the vulcanization system contains a vulcanization accelerator and / or a vulcanization retarder. Advantageously, the composite is based on an elastomer composition in which the elastomer matrix contains a crosslinking system containing molecular sulfur at a content in the range of 1 to 5 phr. Molecular sulfur means sulfur derived from S n compounds (n>2). Specifically, the inventors propose a hypothesis that there is competition between the adhesion by the adhesive composition and the adhesion by copper and zinc sulfide dendrites. This competition tends to reduce the general level of adhesion. The lower the content of sulfur present in the elastomer matrix, the lower this competition and the more the adhesion level by the adhesive composition alone is promoted.

[0058] Very advantageously, the molecular sulfur content of the crosslinking system of the elastomer composition is 4 phr or less, preferably 3 phr or less, more preferably 2.5 phr or less. In addition to further reducing the competition between adhesion by the adhesive composition and adhesion by copper and zinc sulfide dendrites, the shelf life of the elastomer composition at room temperature is improved, avoiding the risk of premature vulcanization that seems to increase when using a higher sulfur content. Very advantageously, the molecular sulfur content of the crosslinking system of the elastomer composition is 1.5 phr or more, preferably 2 phr or more. The vulcanization content is measured by elemental analysis using a Thermo Scientific Flash2000 trace analyzer. This analysis includes a combustion step of the sample and then a step of separating the formed compounds. A sample of approximately 1 mg is introduced into the trace analyzer, where the sample is subjected to flash combustion at 1000 °C under oxygen. Next, the formed gas is oxidized by excess oxygen and an anhydrous tungsten catalyst. Subsequently, the excess oxygen is trapped by a reduction step of passing over copper, and nitrogen oxides are reduced to N 2 to, and similarly sulfite is reduced to sulfur dioxide SO 2 . Water is trapped, and the formed compounds N 2 , CO 2 and SO 2 are then separated on a chromatography column and then detected by a katharometer. The total amount of sulfur is quantified by measuring the area of the SO 2 peak after calibration using a standard.

[0059] The combined vulcanization accelerator, vulcanization retarder and activator are used at a preferred content rate within the range of 0.5 - 15 phr. The vulcanization activator is used at a preferred content rate within the range of 0.5 - 12 phr. A suitable crosslinking system is preferably based on sulfur and primary vulcanization accelerators, especially sulfenamide - type accelerators. In addition to this vulcanization system, various secondary vulcanization accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine) are known. Any compound capable of acting as an accelerator for vulcanizing a diene elastomer in the presence of sulfur, in particular an accelerator of the thiazole type and similarly its derivatives, and accelerators of the thiuram type and zinc dithiocarbamate type, may be used as (primary or secondary) accelerators. These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviation "MBTS"), N-cyclohexyl-2-benzothiazole sulfenamide (abbreviation "CBS"), N,N-dicyclohexyl-2-benzothiazole sulfenamide (abbreviation "DCBS"), N-(tert-butyl)-2-benzothiazole sulfenamide (abbreviation "TBBS"), N-(tert-butyl)-2-benzothiazole sulfenimide (abbreviation "TBSI"), zinc dibenzyldithiocarbamate (abbreviation "ZBEC") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used. In a second embodiment preferably intended for use in a belt, the crosslinking system substantially does not contain sulfur and advantageously contains a peroxide, preferably an organic peroxide. Advantageously, the peroxide content ranges from 0.5 to 8 phr. Advantageously, the crosslinking system contains a co-crosslinking agent, preferably sulfur or triallyl cyanurate. Advantageously, the co-crosslinking agent content ranges from 0.5 to 5 phr. The tire according to the present invention The present invention also relates to a tire. The elastomer composite of the present invention can advantageously be used to reinforce tires for all types of motor vehicles, in particular passenger vehicles or industrial vehicles such as large vehicles.

[0060] The belt according to the present invention The present invention also relates to a belt. For example, such a belt can be a power transmission belt. The present invention will be better understood by a first reading with reference to the following description and drawings which are presented merely by way of non-limiting examples.

Brief Description of the Drawings

[0061]

Figure 1

Figure 2

DETAILED DESCRIPTION OF THE INVENTION

[0062] The attached FIG. 1 is a very schematic (specific scale This tire 1 comprises 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 by a bead wire 5. The crown 2 carries a tread, which is not shown in this schematic. The carcass reinforcement 7 is wound around the two bead wires 5 at each bead 4, and the upward fold 8 of this reinforcement 7 is positioned towards the outside of the tire 1, for example, attached to its rim 9 and shown here. The carcass reinforcement 7 is formed of at least one ply reinforced in a manner known per se by a "radial" cord, for example a fiber cord, i.e., these cords are positioned substantially parallel to each other, extending from one bead to the other bead, and thus forming an angle between 80° and 90° with the central circumferential plane (a plane perpendicular to the axis of rotation of the tire, located in the middle between the two beads 4 and passing through the central part of the crown reinforcement 6).

[0063] This tire 1 of the invention has, for example, the essential feature that at least one crown reinforcement 6 and / or carcass reinforcement 7 comprises an elastomer composite according to the invention. This tire has the preferential feature that at least its belt and / or its carcass reinforcement consists of at least one multi-composite reinforcement according to the invention which is a multi-layer laminate according to the invention and is located between and in contact with two layers of a diene rubber composition, constituting the above multi-layer laminate. According to a particular embodiment of the invention, this composite of the invention can be used in the form of parallel pieces arranged under the tread, as described in patent EP1167080. According to another possible exemplary embodiment of the invention, what can be reinforced by such a composite is the bead zone. For example, all or part of the bead wire can be formed from the composite according to the invention. The belt according to the invention has, for example, the essential feature that it comprises an elastomer composite according to the invention.

[0064] Needless to say, the present invention relates to the elastomer composite, and the tire or belt containing the same, which have the above-described objects, namely, both in the uncured state (before crosslinking) and in the cured state (after crosslinking). FIG. 2 illustrates an embodiment of a facility for sizing one or more GRP strands according to the invention, represented by general reference 30. The production facility 30 is capable of producing one or more sized GRP strands. The equipment 30 includes, from upstream to downstream, in the running direction of the GRP strands passing through the equipment 30, means 34 for storing the GRP strands upstream, a first pre-bonding water bath 36 containing a composition based on an epoxy compound and a blocked diisocyanate compound in which the GRP strands are immersed, a device 40 for drying the pre-bonded strands by heat treatment, a second bath 42 consisting of an aqueous adhesive composition for depositing this adhesive composition on the GRP strands, a device 44 for heat-treating the sized GRP strands, and means 46 for storing the heat-treated sized GRP downstream.

[0065] The upstream storage means 34 and the downstream storage means 46 each comprise a reel for storing the GRP strands, whereby the unwinding and winding of the GRP strands are respectively possible. An example of a process for sizing one or more glass-reinforced plastic (GRP) strands will now be described. During this process, the pre-bonding step is carried out in a first bath based on an epoxy resin and a blocked diisocyanate in an aqueous solution, for example, polyglycerol polyglycidyl ether and N,N'-(methylenedi-p-phenylene)bis[hexahydro-2-oxo-1H-azepine-1-carboxamide 4,4'-diisocyanate. The components are introduced into water with stirring, for example, in the following order: 1.5% by mass of polyglycerol polyglycidyl ether (e.g., Denacol EX-512 manufactured by Nagase Chemicals Ltd.), 0.02% of zinc acetate, 0.08% of an antifoaming agent, 15.15% of a 20% solution of N,N'-(methylenedi-p-phenylene)bis[hexahydro-2-oxo-1H-azepine-1-carboxamide 4,4'-diisocyanate, and 83.6% by mass of water. To do this, some glass-reinforced plastic (GRP) strands are brought into contact with the first bath. Next, the glass-reinforced plastic (GRP) strands are dried, for example, by passing them through a high-frequency heating tunnel or oven (e.g., at 170°C for 20 seconds), and these strands are subjected to a heat treatment (e.g., at 220°C for 30 seconds).

[0066] Next, a step of depositing an aqueous adhesive composition containing water, a mixture of an unsaturated elastomeric matrix, and a resin based on phloroglucinol and 1,4-benzenedicarboxaldehyde is performed. The proportions of these various constituent materials are described below. To do this, some glass-reinforced plastic (GRP) strands are brought into contact with the adhesive composition. To do this, the glass-reinforced plastic (GRP) strands are continuously unwound from the storage reel of the storage means 34, the glass-reinforced plastic (GRP) strands pass through a first bath, and then these strands pass through a heat treatment apparatus and then through a second bath containing the aqueous adhesive composition. These strands pass through the heat treatment apparatus, for example, by passing through a heating tunnel or oven (e.g., at 170°C for 20 seconds), and the strands are subjected to a heat treatment (e.g., at 220°C for 30 seconds).

[0067] Comparative test Adhesion test Various controls, sized glass-reinforced plastic (GRP) strands T, T1, T1', T2, and T2', and sized glass-reinforced plastic (GRP) strands C1 and C2 according to the present invention were tested by a test aimed at measuring the pull-out force of these sized glass-reinforced plastic (GRP) strands embedded in an elastomeric matrix. Glass-reinforced plastic (GRP) strands were coated with each of the protocols described below in Table 1 below and then dried in a drying oven at 170 °C for 20 seconds. Next, the glass-reinforced plastic (GRP) strands were passed through a treatment oven at 220 °C for 30 seconds to crosslink the adhesive composition. Next, in order to form the composite test specimens described below, this assembly was integrated by curing with a natural rubber composition by means of a vulcanization heat treatment.

[0068] Subsequently, the quality of the bond between the rubber composition and the glass-reinforced plastic (GRP) strands was determined by a test measuring the force required to pull a fragment of the glass-reinforced plastic (GRP) strands from the vulcanized rubber composition. This rubber composition is a conventional composition that can be used for the calendering of tire carcass reinforcing plies, and these plies contain glass-reinforced plastic (GRP) strands embedded in an elastomeric matrix based on natural rubber, carbon black and standard additives. More specifically, the vulcanizate is, prior to curing, a block of an elastomeric composition consisting of two sheets measuring 200 mm × 4.5 mm and having a thickness of 3.5 mm, which are applied to each other (the resulting block then has a thickness of 7 mm). During the production of this block, glass-reinforced plastic (GRP) strands (15 fragments in total) are evenly sandwiched between two rubber sheets of the uncured elastomeric composition, with the cord ends protruding on both sides of these sheets to a length sufficient for the subsequent tensile test. Next, the block containing the glass-reinforced plastic (GRP) strands is placed in a suitable mold and then cured under pressure. The curing temperature and curing time are left to the discretion of the person skilled in the art, adapted to the intended test conditions. By way of example, in this case, the block is cured at 160 °C for 15 minutes.

[0069] Once curing is complete, the vulcanized block and the thus formed test specimens from 15 glass-reinforced plastic (GRP) strands are placed between the jaws of a suitable tensile testing machine so that each fragment can be individually tested at a given speed and a given temperature (e.g., in this case, 100 mm / min and 20 °C). The adhesion level is characterized by measuring the "pull-out" force (denoted by Fmax0) required to pull the glass-reinforced plastic (GRP) strand out of the test specimen. Regarding the pull-out force (Fmax0), the control T is set to an adhesion value of 100, which is a conventional method for sizing glass-reinforced plastics as described in application WO2016116457. The results of the adhesion tests performed on the sized glass-reinforced plastic (GRP) strands are summarized in Table 1 below.

[0070] Moisture sensitivity test Each glass-reinforced plastic (GRP) strand was coated with the adhesive composition tested in accordance with the process described in Table 1 below, with or without using the first bath. Each sized glass-reinforced plastic (GRP) strand was dried in a drying oven at 170 °C for 20 seconds. Next, the sized glass-reinforced plastic (GRP) strand was passed through a treatment oven at 220 °C for 30 seconds to crosslink the adhesive composition.

[0071] The resistance of the interface to wet conditions is characterized by measuring the breaking strength of sized glass-reinforced plastic (GRP) strands (denoted as Fmax0), and the breaking strength of sized glass-reinforced plastic (GRP) strands after heat treatment in an oven for 70 hours at a humidity level of 90°C and 90% (denoted as Fmax70). The breaking strength Fmax0 was arbitrarily set to 100. The value of the breaking strength Fmax70 of each sized glass-reinforced plastic (GRP) strand is always less than 100, and the more sensitive the sized glass-reinforced plastic (GRP) strand is to wet conditions, the greater this value becomes. The decrease D, expressed as a percentage, corresponding to the decrease in breaking strength between Fmax0 and Fmax70 was calculated. D is given by D = (1 - Fmax70 / Fmax0) × 100. The lower the decrease value D, the lower the sensitivity of the sized glass-reinforced plastic (GRP) strand to wet conditions. The results of the sensitivity test to wet conditions performed on the sized glass-reinforced plastic (GRP) strands are summarized in Table 1 below. The values of the various compounds are the mass percentages of solids relative to a formulation based on 100 for the first and second baths.

Table 1

[0072] The decrease is limited when the blocked diisocyanate is present in the first bath, and this applies regardless of the second bath used (T, T2”, C1 and C2), and it is also observed that the resistance to wet conditions is affected when comparing T1 with C1 and T2 with C2 in the presence of the diisocyanate. Therefore, the presence of the blocked diisocyanate affects the resistance to moisture. Therefore, the pre-bonding step is an essential step, on the one hand, to initially maintain a good adhesion level and, on the other hand, to guarantee the resistance of the adhesion interface to wet conditions without using products that have a negative impact on the environment.

[0073] Therefore, by the method according to the invention, it is possible to adhere the composite C2 according to the invention to these elastomeric matrices to a satisfactory extent without the need to use an adhesive composition in combination with products that have a negative impact on the environment. Furthermore, the adhesion of this composite is relatively high and is hardly reduced by wet conditions. The present invention is not limited to the above embodiments.

Claims

1. A method for sizing one or more strands of glass-reinforced plastic, abbreviated as GRP, a) A step of pre-joining one or more strands of GRP plastic by immersing them in a first water bath, b) The method is characterized by comprising the step of depositing the GRP plastic strands on the GRP plastic strands by immersing them in a second bath, The first water bath, - Epoxy compounds, and - Blocked diisocyanate compounds It contains a composition based on, The second bath, - At least one compound A1 containing at least one aldehyde functional group, - At least one type of phenol A21, and - At least one unsaturated elastomer latex comprising at least one elastomer selected from the group consisting of butadiene copolymer, styrene-butadiene copolymer, vinylpyridine-styrene-butadiene copolymer, natural rubber (excluding chlorous natural rubber), and mixtures thereof. It contains an aqueous adhesive composition based on, The method wherein the content of the blocked diisocyanate compound in the aqueous adhesive composition of the second bath is strictly less than 0.50% by mass.

2. The method according to claim 1, wherein the block diisocyanate compound in the aqueous adhesive composition of the second bath has a mass content of 0.05% or less.

3. The method according to claim 1, wherein the epoxy compound is selected from the group consisting of diethylene glycol diglycidyl ether, polyethylene diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, or isosorbide diglycidyl ether.

4. The method according to claim 1, wherein the blocked diisocyanate compound is selected from the group consisting of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate.

5. The method according to claim 1, wherein compound A1 is formaldehyde.

6. The method according to claim 1, wherein compound A1 comprises at least one aromatic ring having at least one aldehyde functional group.

7. The method according to claim 1, wherein aromatic polyphenol A2 is selected from the group consisting of resorcinol, phloroglucinol, 2,2',4,4'-tetrahydroxydiphenyl sulfide, 2,2',4,4'-tetrahydroxybenzophenone, and mixtures thereof.

8. An elastomer composite reinforced with one or more sized glass-reinforced plastic (GRP) strands embedded in an elastomer matrix, wherein the sized glass-reinforced plastic (GRP) strands are obtained by the method described in claim 1.

9. A tire (1) characterized by comprising the elastomer composite described in claim 8.

10. A belt (P) characterized by comprising the elastomer composite described in claim 8.

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